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O C 0The Chemistry of Nucleic AcidsSeventh International Conference onCoordination ChemistryCrystallizationGas Chromatography I962Edited by M. van Swaay.I962 I72 illustrations 41 I pages 1005.Naturally Occurring Oxygen Ring CompoundsI963 404 illustrations 661 pages 1205.Practical Mathematics for ChemistsI963 9 illustrations 156 pages 205.Progress in Medicinal Chemistry - 3By D. 0.Jordon.I960 100 illustrations 358 pages 605.International Union of Pure and Applied ChemistryI963 44 illustrations 123 pages 305.By]. w. Mullin, BSc., Ph.D., F.R.I.C., M.I.Chem.E.1961 I22 illustrations 268 pages 605.By F. M. Dean, B.Sc., Ph.D.By F. H. C. Kelley, D.Sc.(Tas.), M.Sc.(Melb.), A.Melb.T.C.,F.R.A.C.I., A.Aust.1.M.M.Edited by G. P. Ellis, B.Sc., Ph.D., F.R.I.C.,G.B. West, B.Pharm., D.Sc., Ph.D.I963 30 illustrations 420 pages 805.Edited b y j . W. Cook, D.Sc., F.R.S., and W. 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ISSN:0365-6217    

DOI:10.1039/AR96259FP001

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

ANNUAL REPORTSON THEPROGRESS OF CHEMISTRYGENERAL AND PHYSICAL CHEMISTRY1. INTRODUCTIONTHE reports this year cover a small number of selected topics, and refer todevelopments over a'period of more than one year. The extensive anddetailed studies of the thermodynamic properties of liquid mixtures havenot been reported for some time, so this work is summarised in considerabledetail. We also include reports on the kinetics of oxidation reactions andon the uses of ultra-high vacuum techniques. The availability of such lowpressures now has a very important bearing on the study of gas-solid surfacephenomena.I n recent years impressive progress has been made in the study of energylevels of simple molecules. The accurate and extraordinarily detailedinformation available from the spectra of these molecules is a challenge tothe theoretical chemist, and we report the present state of this field of work.The study of electron-spin resonance spectra has grown in a most remark-able way in recent years; it therefore seemed desirable to include a furtherreport on this subject.A report on nuclear magnetic resonance spectroscopyof organic compounds appeared last year, and this is now supplemented byan account of work which has been done on solutions of electrolytes.R. E. R.2. ULTRA-HIGH VACUAAs this subject has not been reported on previously, the intention is to givea rather general account of results of interest to chemists. Sufficient refer-ences have been included to make it possible for those who wish to pursuethe subject further to do so.mm.Hg will be implied.A simple calculation based on the kinetic theory of gases demonstrates theadvantage to be gained by reducing the pressure from the conventionalhigh-vacuum region (ca. mm.) to the ultra-high vacuum region. Therate of collision of gas molecules with a surface, p, is given byp = P(SnmkT)-4 collisions cm.-2 sec.-lwhere rn = the mass of a molecule.,u is 5 x 1014 collisions cm.-2 sec.-l.atomsBy ultra-high vacuum, a pressure belowFor oxygen a t loF6 mm. and 23" cA typical metal surface has ca. 10l5so that, unless the colliding gas has a very small probability o8 GENERAL AND PHYSICAL CHEMISTRYsticking, a surface which was clean originally will become covered by a mono-layer of gas within a few seconds.However, a thousand-fold decrease inpressure increases the time for monolayer formation by the same factor andthe surface stays clean long enough to be studied. , It is also possible toinvestigate the interaction of the surface with an experimental gas a t pres-sures in the loe7 mm. region without significant interference from the resi-dual vapour. It is in the field of gas/metal-surface interactions that themost considerable progress has been made and with which this report willmainly deal.Experimental Methods.-There is evidence that pressures approachingthe ultra-high vacuum region were being obtained a t times when conven-tional ionization gauges were recording pressures in the ordinary high-vacuum region.This is now known to be due to the ‘( X-ray limit ’’ of anionization gauge, which arises as follows. The impact of the electrons, com-prising the grid current, causes the grid metal to emit soft X-rays. TheseX-rays eject electrons from the positive-ion collector and thus give rise toa current at the collector in the same sense as that which records the pres-sure. The usefulness of the conventional ionization gauge is limited by thisprocess to the recording of pressures down to theA pioneering paper in the ultra-high vacuum field is that of Alpert,lwho, recognizing the limitations of the ionization gauge, designed a newgauge with a much lower X-ray limit. He also demonstrated the conditionsunder which ultra-high vacuum could be obtained repeatedly and withoutsealing off the apparatus from the pumps.The ionization gauge designedby Bayard and Alpert 2 is widely used in ultra-high vacuum studies. Itreduces the X-ray limit to below 10-10 mm. by inverting the arrangement ofthe electrodes. The cathode is outside the cylindrical wire grid and thepositive-ion collector is a fine wire running axially down the grid. This wirecollects positive ions produced by electron bombardment in the volumedefined by the grid. The positive ion current thus produced is directly pro-portional to the gas density, and therefore to the pressure. This fine wirecollector presents a much smaller area for X-ray bombardment than theusual collector so that the X-ray limit is correspondingly lower.(i) The use of lanthanum boride-coated filaments. These give off thermionicelectrons a t much lower temperatures than tungsten, which is normally used.This is an improvement because one of the problems associated with the useof thermionic gauges is that of the interaction of the hot filament with thegases in the system; the lower the filament temperature, the less importantare these undesirable side reactions.(ii) The use of still finer wires to reduce the X-ray limit even further.An important condition for obtaining ultra-high vacua is to avoid com-pletely the use of greased taps.Alpert has designed an all-metal closurevalve which is turned off by forcing a metal cone very hard into a metalseating. Movement is allowed by use of a flexible metal diaphragm, attachedto the cone.Although such a valve does not switch off completely, con-mm. region.Current modifications to the original gauge include :D. Alpert, J. Appl. Phys., 1953, 24, 860.a R. T. Bayard and D. Alpert, Rev. Sci. Instr., 1950, 21, 571GASSER: ULTRA-HIGH VACUA 9ductances as low as 10-14 1. sec.-l can be obtained. It has the very impor-tant properties that it is robust, and can be heated to temperatures as highas 500" c without harm. It thus becomes possible to outgas an entirevacuum assembly by heating it as a whole in a bake-out oven. It is com-mon to use temperatures approaching the softening point of glass. Furtheroutgassing of the metal electrode assembly of the gauge is usually necessary,and electron bombardment or radio-frequency heating to red-heat willaccomplish this.Conventional diffusion pumps can be used for ultra-high vacuum work,provided that a very efficient trap is incorporated between the pump andthe apparatus, to collect back-streaming vapour.A common and reliabletrap is a vessel, cooled with liquid air, so designed that back-streamingmolecules have to make many collisions with the cold walls before theyreach the apparatus. Non-refrigerated traps have also been used withsuccess; trapping materials include rolled up copper foil and artificialzeolite.4 mm. can be obtainedas a matter of routine. On isolation of the system from the pumps, thepressure can be reduced still further by operating the gauge a t a high emis-sion (Le. cathode to grid) current, when it will act as an " ion pump " ofmaximum pumping speed about 2 1.sec.-l. When operating the gauge asa measuring device, this pumping is reduced as far as possible by using small(10-100 FA) emission currents.As an alternative to diffusion pumps, " getter-ion " pumps can be used.The details of the mode of operation of these pumps are still not clear, but inprinciple they are considered to transfer gas from the gaseous phase to thewalls of the pump by a combination of gettering and ionic pumping. Thebacking pressure required for them to start up can be obtained by coolingan adsorbent material in liquid air. It is thus possible to have a completelyoil-free system. I n spite of this, however, hydrocarbons are produced inthe system from impurities in the getter.The Theoretical Approach to Ultra-high Vacua.-The experimentalmethods described above represent a well-tried but largely empirical tech-nique, and it is useful to consider the factors which limit the attainment ofultra-high vacua.The strength of binding of molecules of the atmosphericgases to the walls of the apparatus plays an important part in determiningthe rate a t which the apparatus can be pumped out. I f the molecules,arestrongly held they cannot be removed, but neither do they evaporate, andthus they make no contribution to the vapour pressure. Weakly-held mole-cules evaporate rapidly and are removed by the pump. It is thus themolecules with intermediate binding energies which give rise to the con-tinuous evolution of gas experienced in unbaked apparatus.A quantitativetreatment has shown that, a t room temperature, gases with heats of adsorp-tion in the range 15-25 kcal. mole-1 are the most troublesome. However,on raising the temperature to 300" c these gases are rapidly evolved. ThisBy these means a pressure of ca. 3 xD. Alpert, Westinghouse Research Lab. Scientific Paper 1744 (East Pittsburgh,L. L. Levenson and N. Milleron, Trans. Vacuum Syrnp., 1961, 91.J. P. Hobson, Trans. Vacuum Syrnp., 1961, 26.U.S.A. 1953)10 GENERAL AND PHYSICAL CHEMISTRYresult implies that rather less extreme conditions of outgassing than thosepreviously described may be adequate to achieve ultra-high vacua, a con-clusion which can be confirmed by the Reporter who has obtained pressuresbelowBesides outgassing from the walls, another factor which may limit theattainment of ultra-high vacua is the diffusion of gas from the atmospherethrough the walls of the apparatus.l Glass is a very convenient construc-tional material and is widely used in vacuum apparatus, so that it is impor-tant to know in what circumstances the inflow of gas becomes significant.There is much information about the permeation of helium, and data arenow also available for other gases.6 The relative importance of the permea-tion of various gases can best be appreciated by considering their build-upin a sealed-off system.Consider a vitreous silica bulb of capacity 330 C.C.with walls 1 mm. thick and surface area 100 sq. em. a t 25" c. Then, startingwith a negligible pressure, at the end of one year the pressures would be:loW4 mm.of He, mm. of Ne, and mm. of H,. No other gaseswould be present. Even after 100 years only a few molecules of oxygenwould have penetrated. There is a marked difference in permeability be-tween various types of glass. In a bulb as specified the time taken for thepressure of helium to build up to mm. would be as follows: Silica,3 days; Pyrex, a month; soda-lime, about 100 years. All gases permeateglass a t a rate directly proportional to their partial pressure, the flow beingmolecular. Steel walls are impermeable to all gases a t room temperatureexcept hydrogen, which flows as atoms.The lowest pressure which could possibly be obtained would occur, ofcourse, when there were no gaseous molecules present a t all.This situationhas been approached through a combination of ultra-high vacuum and cryo-,genic techniques.7 mm.and isolated from the pumps. Then part of it was immersed in a liquidhelium bath, when physical adsorption of the residual gas occurred on thecold walls. Extrapolation from measurements a t high coverage indicatesthat, a t equilibrium, the pressure in the cold part should be in the regionof 10-35 mm., i.e. there is no gas molecule within its volume for most ofthe time.Results.-Any property of a surface which is modified by the adsorptionof gas can, in principle, be used to study the gas-surface interaction. Inthis section three widely used techniques utilizing ultra-high vacua will bedescribed.This is probably the most important andinformative method of studying gas-metal interactions.* The principle ofoperatioh of the field-emission microscope lies in the modification, by a verylarge potential gradient, of the potential-energy barrier preventing theescape of electrons from the surface of the metal. Under the influence ofa gradient of ca. lo7 v cm.-l, electrons can tunnel through the distortedmm. after bake-out in the 250-3OO"c range.The apparatus was first pumped down to ca.FieEd-emission microscopy.F. J. Norton, Trans. Vacuum Syrnp., 1961, 8.J. P. Hobson, Trans. Vacuum Symp., 1961, 146.R. Gomer, " Field Emission and Field Ionisation," Oxford University Press,1961GASSER: ULTRA-HIGH VACUA 11barrier at a rate which is approximately independent of temperature, in therange 0-300" K.Currents of the order of loA7 A can be drawn a t tem-peratures hundreds of degrees below that at which thermionic emission isappreciable. The actual current obtained depends on the work function, #,of the surface in a complex manner. However, the appearance of a term ofthe form exp(4312) shows that i will vary very markedly with changes in 4.The large voltage gradients required for a field-emission microscope areobtained by making the field-emission source in the form of a very finepoint (ca. 1000 A diameter), and mounting it at the centre of a bulb of about5 em. radius. The inner surface of the bulb is coated with conducting andfluorescent layers and the application of 1-20 kv.to this screen producesthe necessary voltage gradient at the tip. The fluorescent screen providesa visual demonstration of differences in work function of the surface, magni-fied some 105-106 times. The observed regions of light and dark, from aclean tip, are due to the differences in work function of the various crystalplanes present at the surface. Adsorption of a gas alters the work function,and therefore the field-emission pattern, of a tip. This has been used tostudy the physical adsorption of inert gases on tungsten.9 with the perhapssurprising results (i) that the adsorbed gas retains liquid-like propertiesbelow the bulk melting point of the adsorbate, and (ii) that adsorption givesrise to a substantial dipole moment (0.1-0.8 D) in the adsorbate.Theheats of adsorption, however, are in the expected range, 2-10 kcal. molew1.From the large number of papers dealing with chemisorption on field-emission tips, it has been possible to build up a fairly detailed picture of thesurface processes involving diatomic molecules and refractory metals, par-ticularly tungsten. Hydrogen, oxygen, nitrogen, and carbon monoxide areall adsorbed rapidly, and without activation, even at low temperatures((70" K). The homonuclear molecules are dissociated into atoms, butcarbon monoxide is adsorbed without decomposition.The migration of adsorbed species over the surface has been studied atlow temperatures (ca. 20-70' K). To do this, part of the tip is given amultimolecular-layer deposit of gas at liquid helium temperature, wherethe adsorbed layers are immobile.On warming the tip, migration of thephysically adsorbed layers occurs (at 27 O K for oxygen) on to the clean regionsof the surface, where they become chemisorbed and immobile. More physi-cally adsorbed gas can now migrate over the new deposit and extend theregion of chemisorption. This process produces changes in the field-emission pattern, and it continues until either all the tip is covered or allthe original deposit of gas is used up. If the latter happens, no furtherchange in the field-emission pattern occurs until the migration of chemisorbedatoms sets in at much higher temperatures (about 500" K for oxygen). Theactivation energies for the two types of migration are about 1 kcal.mole-1and 25 lwal. mole-l. At still higher temperatures the gas desorbs andeventually the pattern of the clean tip is regained. From these measure-ments the heats of desorption are obtained. For many systems, the activa-tion energy for migration is about one-fifth of the binding energy of theatom to the surface.OG. Ehrlich and F. G. Hudda, J . Chem. Phys., 1959, 30, 49312 GENERAL AND PHYSICAL CHEMISTRYThe field-emission microscope has recently been used to study the inter-action of simple hydrocarbons with an iridium tip10 It was suggested that,for ethylene, adsorption is dissociative and that heating progressively de-hydrogenates the adsorbed species, hydrogen being evolved, until a car-bonaceous deposit is left.Related to the field-emission microscope is the field ion microscope. Thisis essentially a field-emission microscope operated in reverse with the tipas anode, instead of the screen.For its operation it requires a reasonablepressure of gas (ca. mm.), and either hydrogen or helium is commonlyused. When a gas molecule comes into the region of high potential gradient,near the tip, it may be ionized by the tunnelling of one of its electrons on tothe tip. Thepattern produced on the screen by many such ions is characteristic of thesurface of the tip. The resolution of the field ion microscope is greater thanthat of the field-emission microscope and, indeed, is so great that it has beenpossible t o see the effect of a single nitrogen molecule upon the pattern froma tungsten tip.11 This very refined technique is unfortunately limited tothe observation of very strongly-bound species.This is because thepotential gradients required are some ten times greater than for the field-emission microscope, and subject the tips to such great mechanical stress,ca. 1011 dyne cm.-2, that any weakly bound species, including atoms of thetip itself, may be field desorbed.Flash-$lament experiments.and, since then, has been widely used as a method of studying the inter-action of simple gases with the very high-melting metals. The principle ofthe method is as follows. The metal is rapidly heated electrically to about2000” K, i.e. “flashed,” in an ultra-high vacuum to remove the adsorbedlayers of atmospheric gases.The experimental gas is then admitted to theapparatus and a pressure in the On coolingthe filament, gas is adsorbed. After a chosen time the filament is ‘‘ flashed ”thus desorbing all the gas and causing a rapid rise in the pressure. Providedthat the time constant of the pressure-measuring equipment is short com-pared with the flashing time (usually ca. 1 sec.), the evolution of gas can berecorded accurately on an oscilloscope or fast writing recorder. The kinetictheory of gases gives the number of molecules which have collided with afilament of known dimensions and the desorption curve gives the numberwhich have stuck.The results of these experiments are expressed in terms of the prob-ability that, on striking the surface, a molecule is adsorbed.For nitrogenon tungsten there is general agreement that there is a strong probabilityof a fruitful collision,12, 13, l4 which is independent of coverage over awide range. Similar results have been obtained for carbon monoxide,15~ l6The positive ion thus produced is accelerated to the screen.This technique was introduced in 1953mm. range is established.lo J. R. Arthur and R. S . Hansen, J. Chem. Phys., 1962, 36, 2063.l1 G. Ehrlich and F. G. Hudda, J. Chem. Phys., 1962, 36, 3233.l2 J. A. Becker and C. D. Hartman, J . Phys. Chem., 1953, 57, 153.l3 G. Ehrlich, J . Chem. Phys., 1961, 34, 29.l4 J. Eisinger, J . Chem. Phys., 1958, 28, 165.l5 G. Ehrlich, J. Chem. Phys., 1961, 34, 39.l6 J. Eisinger, J. Chem. Phys., 1957, 27, 1206GASSER: ULTRA-HIGH VACUA 13oxygen,17 and hydrogen.18 In all these cases the probability lay in therange 20-60y0.In marked contrast to these results was the behaviour ofoxygen on silicon,lS where the sticking probability started at only lyo, fora clean surface, and declined exponentially with coverage.A detailed study of the shapes of the desorption curves gives furtherinformation about surface processes. A striking feature observed for manysystems is the evolution of gas in discrete stages.13, 15, 20, 21 For example,after adsorption a t 115” K nitrogen is evolved from tungsten in three steps.The lowest arises from a physically-adsorbed molecular species while theother two are due to chemisorbed atomic states, of which the predominantone has atoms bound with an energy of about 155 kcal.molev1. In thedesorption of carbon monoxide from tungsten 21 one physically adsorbedand three chemically adsorbed species have been identified. Kinetic analysisof the desorption curves is also possible and gives the order, and thereforethe mechanism, of the desorption processes.Evaporated metalJilms. The use of evaporated metal films for the studyof gas-metal interactions was introduced in 1940 and has given much infor-mation. The particular property measured in early experiments was thecalorimetric heat of adsorption, and its variation with coverage.22 How-ever, more recent work in this field has cast some doubt on the interpreta-tion of the results.23 It was suggested that two effects may have occurredduring the evaporation of these films which led to the accumulation of gasof unknown composition in the system and therefore to an uncharacterizedfilm.These effects are: (i) replacement by the evaporated metal of gasmolecules adsorbed on the substrate surface, and (ii) heating of the innerwall of the vessel, which then desorbs gas. It is, however, possible to pre-pare an evaporated metal film under ultra-high vacuum conditions 24, 25, 26by evaporating the metal in short bursts. Measurements on such filmsinclude those of sticking probabilities and catalytic activity. I n the lattercase, a substantial difference in behaviour between films prepared in themm. and mm. regions has been found. The ultra-high vacuumfilms are more reactive, but are much reduced in catalytic activity by smallquantities of oxygen.BARROW AND MERER: SPECTROSCOPY O F DIATOMIC MOLECULES 125The 2 4 , state has notbeen observed, but there is evidence for two non-Rydberg aII stab, 211 and 211s a t64287 and 65931 cm. -l respectively.263agrees well with the Raman shifts of 2330 and 2340 crn.-l observed for NO+in solids and in solution, respectively.267Three Rydberg series have been analysed in the absorption spectrum ofnitric oxide a t the short-wavelength end of the Schumann 269Of these, one, the y-series, converges on AlII of NO+, and may be written[0z4n, A1II]npa, 2 I I : n = 4 , s . ..lo.The bands follow the formulaY = 147830 - R/(n - 1~78)~.Thus the first ionization potential of NO is given by147830 - To0(A1II) = 74746 cm.-l, or 9.267 & 0.005 ev, in good agree-ment with values 9.25 & 0.03 270 and 9-25 & 0.02 271 ev obtained by photo-ionization.Two other series, a and p, follow the formuke* Two very different values have been given for the vibrational interval in the/3 series, 1341 268 and 1980 269 cm.l-.265 M. Ogawa, Science of Light, 1954, 3, 39, 87; M. Brook and J. Kaplan, Phys.266 E. Miescher, Helv. Phys. Acta, 1956, 29, 135.267 W. R. Angus and A. H. Leckie, Proc. Roy. SOC., 1935, A, 149, 327; 1935, A26B Y . Tanaka, Sci. Papers Inst. Phys. Chem. Res., Tokyo, 1942, 39, 456.26s K. P. Huber, Helv. Phys. Acta, 1961, 34, 929.Rev., 1954, 96, 1540.150, 615; Trans. Paraday Xoc., 1935, 31, 958.H. Hurzeler, M. G. Inghram, and J.D. Morrison, J . Chem. Phys., 1958, 28, 76.K. Watanabe, J . Chem. Phys., 1957, 26, 542126 GENERAL AND PHYSICAL CHEMISTRYAs is to be expected, there are close parallels with the lower excited statesIn addition, there is a large number of states of NO whose identificationas Rydberg states, converging on the ground state of NO+, follows fromtheir values of cr), and of Be (Table 4). Comparison with the states of O,,N,, CO, and their ions, has assisted in the identification of some of these~ t a t e s , ~ ~ 9 but this is rendered diflicult by overlapping and by perturbations,so that series are not obvious features of the spectrum in this region, andmore work remains to be done. It is remarkable how closely the constantsfor A2X+, the first Rydberg state, agree with those for XIS+ in NO+.This suggests that it may be possible to predict, rather accurately, the con-stants of the isoelectronic monohalide ions such as CF+, whose spectra havenqt yet been observed, from observations on the lowest Rydberg states ofthe neutral molecules.The atomic dissociation products for several of thesestates have been 272n and potential energy curves d r a ~ n . ~ ~ , Transitions between excited states give rise to several systems observed inemission in the visible and infrared regions.263, z7ZcIn comparison with O,, rather little is known about the electronicstates of S,. The structure of the well-known system B3Zu--X3C,- isinteresting but is not yet fully understood.273, 274 The upper state is exten-sively perturbed, perhaps by a state 31-Iu, and the observation of branchesTR31, RP31, PR13, and NP,3 enables the spin-splitting constants in the groundstate to be determined.275 y is small, ca.-0.007 cm.-l, but h is quite large,and increases with v thus:8,.A, = 11.6, + 0*077,(V + *) + 0.0013,(~ + &)2.Several other systems have been observed in emission, both a t long wave-lengths 274 and in the ultraviolet regi0n.2~~ The lower state of some of thelatter systems is probably the lZg+ state from the lowest configuration. . . nU4og2ng2, but its position relative to X3Xg- is not yet known.272 (a) D. D. Konowalow and J. 0. Hirshfelder, Phys. Fluids, 1961, 4, 637; (b) R. A.Young and R. L. Sharpless, Disczlss. Faraday Soc., 1962, 33, 228; (c) W.H. Wurster,C. E. Tremor, and H. M. Thompson, J. Chem. Phys., 1962, 37, 2560.273 K. Ikenoue, Science of Light, 1960, 9, 79.2 7 4 J. E. Meakin and R. F. Barrow, Canad. J . Phys., 1962, 40, 377.276 R. F. Barrow and J. M. Ketteringham, Canad. J. Phys., 1963, 41, 419.276 Y. Tanaka and M. Ogawa, J. Chem. Phys., 1962, 36, 726BARROW AND MERER: SPECTROSCOPY OF DIATOMIC MOLECULES 127The value of the dissociation energy has not yet been established beyonddoubt: however it seems probable thatDo N 4.4 ev, or 0 2 9 8 ’ ’ = 102 & 3 k ~ a l . / m o l e . ~ ~ ~PF. The spectrum of the molecule PF, isoelectronic with SO, hasrecently been observed.2’8 Both singlet and triplet systems were observedand it appears that the ground state is 3Z-. However in place of the ex-pected 3C--3Z- system, there appeared a system 3H-3X-. The twosinglet states from the lowest configuration, 1A and l1: +, were both observed,but their positions relative to X3C- are not known. A 2Z-2rZ transitionin PF+ has also been a n a l y ~ e d . ~ ~ ~A new analysis 279 of bands of the 3110,+-1Cg+ system of C1,has led to improved constants for both states. A resonance fluorescencesystem has been observed 280 in the Schumann region, and gives informationabout the ground state constants at large values of v.A study of the resonance fluorescence system of I, has provided accurateinformation about the course of the ground-state vibrational levels to a pointvery close to the dissociation limit.16 The dissociation energy, Do, is124526 & 1.5 cm.-l. Between 4.6 and 6.4& the form of the potentialenergy curve for the ground state suggests that in this region dispersionforces are more important than valency forces.281Rotational structure has also been studied for the following mole-cules :G. Pannetier and L. Marsigny, Bull. SOC. chim. France, 1962, 1537

ISSN:0365-6217    

DOI:10.1039/AR9625900007

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

INORGANIC CHEMISTRY *1. INTRODUCTIONTHE number of papers dealing with organometallic compounds continues t oincrease, and the dividing line between organic and inorganic compoundsis becoming increasingly difficult to define. In this Report, we direct atten-tion to those papers where the emphasis is on the properties of elementsother than carbon, although organic groups may be used extensively in somecases to elucidate or illustrate these properties. As in the last few years,complex compounds, and compounds of boron, silicon, and phosphorus,continue to occupy a large proportion of the Report; it is perhaps not toofanciful to hope that sooner rather than later the intensive studies on theseparticular non-metals may produce groups of inorganic atoms which areas versatile and as tractable in their behaviour as the familiar organicgroups such as methyl, ethyl, and phenyl.The appearance of a new journal 1 devoted exclusively to inorganicchemistry is to be welcomed.The second volume of the revised Brauer’sHandbook has followed the first with commendable rapidity; two newtextbook^,^ and new editions of two established have also appeared.Tables of atomic weights on the new 12C = 12 standard have been pub-lished. General reviews cover inorganic heterocycles, 6 dissolution of metalsin fused halides, reactions in liquid ammonia,s properties of metal-aminesolutions, high-temperature inorganic chemistry, vinyl compounds of metals,and primary solid hydrides.1°A. K. H.D. N.Inorganic Chenzistry, American Chemical Society, 1962, 1.“ Handbuch der Praparativen anorganischen Chemie,” ed.G. Brauer, FerdinandEnke Verlag, Stuttgart, Part 11, 1962.P. J. Durrant and B. Durrant, “ Introduction to Advanced Inorganic Chemistry,”Longmans, London, 1962; F. A. Cotton and G. Wilkinson, “Advanced InorganicChemistry,” Interscience, New York, 1962.R. B. Heslop and P. L. Robinson, “ Inorganic Chemistry,” 2nd edn., Elsevier,Amsterdam, 1963; A. F. Wells, “ Structural Inorganic Chemistry,” 3rd edn., OxfordUniversity Press, London, 1962.Report of the Commission on Atomic Weights, Pure Appl. Chem., 1962, 5, 255.H. Garcia-Fernandez, Bull. Soc. chirn. France, 1961, 245.E. C. Evers, J . Chem. Educ., 1961, 38, 590.’ E. A. Ukshe and N. G. Bukun, Uspekhi Khim., 1961, 30, 243 (90).* G. W. A. Fowles and D. Nicholls, Quart. Rev., 1962, 16, 19.lo A. W. Searcy, Prog. Inorg. Chem., 1962, 3, 49; D. Seyferth, ibid., 129; T. R. P.Gibb, ibid., 315.* Throughout this section, numbers in parentheses a t the end of references to Russianperiodicals indicate the corresponding page number in the English or U.S. translation130 INORGANIC CHEMISTRY2. TYPICAL ELEMENTS(Iroup 0.-The first definite, stable compounds of an inert gas have beenreported ; tensiometric titration of xenon with platinum hexafluoride yieldsthe compound xenon hexafluoroplatinate(v), XeS(PtF6) --, a stable orange-yellow solid which sublimes when heated and is analogous to the previously-discovered dioxygenyl hexafluoroplatinate, 0,+(PtF6) -. Both compoundshave similar lattice energies, and the high electron-affinity of the PtF,group is the important factor in stabilising these compounds.1 Reaction ofxenon with fluorine under pressure a t 400" gives xenon tetrafluoride as acolourless solid, stable a t ordinary temperatures, and probably possessing atetrahedral or square-planar structure.Inductive heating of xenon withfluorine yields the unstable solid xenon difluoride which probably dispro-portionates to give xenon and the tetrafluoride.sGroup 1.-A re-examination of the structure of ethyl-lithium in hydro-carbon solvents suggests the presence of a single, probably hexamericspecies ;* t-butyl-lithium is, however, tetrameric, with lithium and a-carbonatoms occupying the vertices of interpenetrating tetrahedra.5 Lithiumperchlorate reacts with N-methylpropionamide in the absence of solvent togive complexes in which carbonyl oxygen atoms are linked to the lithiumion.6 Two new crystalline forms of sodium peroxide are reported,' onestable above 512".Group II.-Diethylberyllium forms complex salts MX,nBeEt,(n = I , 2, 4), e.g.KF,BeEt,, by direct addition.* The suggestion that thecolour of complexes of 2,2'-bipyridyl and beryllium allryls is due to electron-transfer from the beryllium to the bipyridyl is now supported by the pre-paration of the deep-green paramagnetic compound bipy,Be from bipyridyl-lithium and beryllium chloride. Reactionof sodium hydride with diethylberylliumyields sodium hydroberyllate, stable to 200'Na2 [ Et/ *...H...:Be\Et] (I) and containing no solvent ether, for whichthe structure (1) is suggested.10 ComplexesPure magnesium hydride is prepared by reaction of the elements atFurther investiga-Et\BS..H... / Etof beryllium chloride with dialkyl sulphides have been reported. l1400" under pressure in presence of a trace of iodine.12N. Bartlett, Proc. Chem. Soc., 1962, 218; N. Bartlett and D. H. Lohmann,a H. H. Claassen, H. Selig, and J. G. Malm, J . Amer. Chem. Soc., 1962, 84, 3593.R. Hoppe, W. DBhne, H. Mattauch, and K. M. Rodder, Angew. Chem., 1962,T. L. Brown, D. W. Dickerhorf, and D. A. Bafus, J. Amer. Chem. SOC., 1962,M. Weiner, G. Vogel, and R. West, Inorg. Chem., 1962, 1, 654.R. L. Tallmann and J. L. Margrave, J. Inorg. Nuclear Chem., 1961, 21, 40.G.E. Coates and S. I. E. Green, J., 1962, 3340; cf. Ann. Reports, 1961, 58, 80.lo G. E. Coates and G. F. Cox, Chem. and Ind., 1962, 269.I1N. S. Sitdykova, N. Ya. Turova, K. N. Semenenko, and A. V. Novoselova,la T. N. Dymova, Z. K. Sterlyadkina, and V. Safronov, Zhur. neorg. Khim., 1961,ibid., p. 115.74, 903.84, 1371.6 A. F. Diorio, E. Lippincott, and L. Mandelkern, Nature, 1962, 195, 1296.* W. Strohmeier and F. Gernert, Chem. Ber.,.1962, 95, 1420.Z h w . neorg. Kizim., 1961, 6, 2512 (1271).6, 763 ( 389); T. N. Dymova, Z. K. Sterlyadkina, and N. G. Eliseeva, ibid., p. 765 (392)HOLLIDAY : TYPICAL ELEMENTS 131tion of the reaction of diborane with dialkylmagnesium suggests that theinitial product is of the type RMg[HBR(BH,),]; when heated to 100" thisyields magnesium borohydride.l3Group III.-The stereochemistry of some Group 111 elements has beenreviewed.l4 The relative acceptor strengths of some Group I11 and GroupIV halides, with respect to ethyl acetate as reference Lewis base, have beendetermined by measurement of the infrared shift in the carbonyl stretchingfrequency. l5Boron. Boron has been prepared by the reduction of boron trifluoridewith sodium.16 An extensive study of the borides of magnesium andaluminium indicates the existence of MgB,, MgB,, MgB,, and AlB,; hydro-lysis of MgB, may yield the ion [BH2(OH),]-.17 Diborane prepared by thereaction of boron trifluoride and lithium aluminium hydride in ether con-tains ethyl fluoride as impurity, but can be purified by fractionation.18 Anew boron hydride of probable formula B&&, is formed when an alcoholicsolution of the salt (Et3NH)2(B,oHl,) is passed through an acidic ion-exchange column and the eluant hydr01ysed.l~ Reaction of the same saltwith a base yields the ion (BloH,0H)2- which is obtained as the thermallystable potassium salt; the ion (B20H18)2- is obtained in good yield by oxida-tion of the decahydrodecaborate ion (BloHlo)2- with an aqueous ferricsalt.2G However, oxidation of the same ion with an acidic ceric solutionyields another isomer of the ion, which is converted into the original isomerby hydrochloric acid.2I The formation and reactions of the ions (B10Hlo)2-and (B1,H1,)2- have been further investigated; they react readily withdonor molecules containing oxygen or sulphur, are stable to strong acidsand bases and to oxidising agents, are the anions of strong acids in aqueoussolution, and readily undergo partial or complete substitution with halogensto give stable ions such as (BloH61,)2- and (BlOCll,)2-.22 Possible sequen-tial substitution reactions of this kind have been predicted the ore tic all^.^^Sodium decaboronate, NaBloHl,, apparently exists in two forms, one pre-pared by the reaction of sodium hydride, and the other by reaction ofalkali, with de~aborane.~~ Substituted decaboranes can be prepared fromthis salt, and addition reactions with amines or phosphines (X) give saltsM+(BloH,,X)-; with X = NEt,H, hydrolysis by acid occurs thus:[ B I ~ H ~ ~ ( H N E ~ ~ ) I - + H30+ + 2H20 + 2% + B(OH), + B,HI3(HNEt2)l3 R.Bauer, 2. Naturforsch., 1962, 17b, 277.l4 D. C. Bradley, Progr. Stereochem., 1962, 3, 1.l5 M. F. Lappert, J., 1962, 542.l6 V. I. Khachishvili, T. G. Mozdokeli, R. Ya. Smolyar, and Ya. V. Asatiani,Zhur. neorg. Khim., 1961, 6, 1493 (767).l7 P. Duhart, Ann. Chim. (France), 1962, 7, 339.lS C. J. Danby, E. Gobbett, and J. W. Linnett, J., 1962, 2076.A. R. Pitochelli and M. F. Hawthorne, J . Amer. Chem. Soc., 1962, 84, 3218.2o A. Kacmarczyk, R. D. Dobrott, and W. N. Lipscomb, Proc. Nut. Acad. Sci.U.S.A., 1962, 48, 729.21 A. R. Pitochelli, W. N. Lipscomb, and M. F. Hawthorne, J. Amer. Chem. SOC.,1962, 84, 3026.*2 W. H. Knoth, H. C. Miller, D. C. EngIand, G. W. Parshall, and E. L. Muetterties,J.Amer. Chem. SOC., 1962, 84, 1056; A. R. Pitochelli, R. Ettinger, J. A. Dupont, andM. F. Hawthorne, {bid., p. 1058.23 R. Hoffman and W. N. Lipscomb, J. Chem. Phys., 1962, 37, 520.24 N. J. Blay, R. J. Pace, and R. L. Williams, J., 1962, 3416132 IN 0 R Gt A N I C C H E MI S TRYand from the enneaborane derivative so formed ions of type (BgHI2X)-are produced by proton abstraction, and ions (BgH12)- by the same processand ligand expulsion.25 The anion (BIoH15)- is precipitated as the quater-nary phosphonium salt by addition of a phosphonium halide to an acidsolution of the salt Na2BloH,,.26 Some reactions of the new hydrideB,oH16 are reported; heating in presence of iodine a t 150" yields decaborane,and reaction with hydrogen iodide breaks the central B-B bond with forma-tion of pentaborane-9 and B5H81.27 The decomposition of tetraborane-10and the pyrolysis of decaborane have been studied kinetically 28 and the ratesof reaction of decaborane with some nitriles and sulphides have been deter-mined.29 Treatment of pentaborane with deuterium chloride in presenceof aluminium chloride gives rapid exchange of hydrogen and deuterium inthe 1 -position.30 Synthesis of some long-chain quaternary borohydrideshas resulted in hydrocarbon-soluble salts with reducing pr0perties.~1 Thereis evidence for a complex between sodium borohydride and diborane, pos-sibly NaBH4,BH3, in ethereal solvents.32 Mechanisms of hydrolysis andmethanolysis of sodium borohydride have been investigated ; finely dividedmetals such as platinum are reported to be very effective catalysts forhydrolysis. 33The reaction of butadiene and diborane gives two compounds of empiri-cal formula B2C4H12, formulated as 1,2-tetrarnethylenediborane (2) and1 y2-( 1 '-methy1trimethylene)diborane (3).34 Reaction of pentaborane-9 withalkynes in presence of 2,6-dimethylpyridine gives compounds of typeB,H6C,RR', but reaction with acetylene in a silent discharge yields " car-borane-3," B,C2H5, which appears to be a member of a series B,C,H,+,formed by acetylene-borane reactions, and probably has a trigonal- bipyra-midal structure with the three boron atoms coplanar and the two carbonatoms a t the apices.35 A new synthesis of amine-borines, by reduction ofphenyl borate with aluminium and hydrogen in presence of the appropriatez 5 H.C. Beachell and D. E. Hoffman, J . Amer. Chem. SOC., 1962, 84, 180; B. M.Graybill, A. R. Pitochelli, and M. F. Hawthorne, Inorg. Chem., 1962, 1, 622.26 J. A. Dupont and M. F. Hawthorne, Chem. and Ind., 1962, 405.2 7 R. N. Grimes and W. N. Lipscomb, Proc. Nat. Acad. Sci. U.S.A., 1962, 48, 496.28 A. J. Owen, J., 1961, 5438; G. L. Brennan and R. Schaeffer, J . Inorg. Nuclear2 9 I. Dunstan and J. V. GrifEths, J., 1962, 1344.3O T. P. Onak and R. E. Williams, Inorg. Chem., 1962, 1, 106.31 E. A. Sullivan and A. A. Hinckley, J . Org. Chem., 1962, 27, 3731.32 E. B. Baker, R. B. Ellis, and W. S. Wilcox, J . Inorg. Nuclear Chem., 1961, 23, 41.33 R. E. Davis, E. Bromels, and C. K. Kibly, J .Amer. Chem. SOC., 1962, 84, 885;R. E. Davis, ibid., p. 892; R. E. Davis and J. A. Gottbrath, ibid., p. 895; H. C. Brownand C. A. Brown, ibid., p. 1494.34 H. G. Weiss, W. J. Lehmann, and I. Shapiro, J . Amer. Chem. SOC., 1962, 84,3840.35 T. P. Onak, R. E. Williams, and H. G. Weiss, J . Amer. Chem. SOC., 1962, 84,2830; I. Shapiro, C. D. Good, and Rt. E. Williams, ibid., p. 3837.Chem., 1961, 20, 205HOLLIDAY : TYPICAL ELEMENTS 133amine, is reported ;36 dimethylamino-derivatives of boron can be preparedby reaction of the compound Al(NMe,), with alkyl- or alkoxy-borine~.~~Some hitherto unknown bis( alkylamino) borines have been prepared bytreatment of dimethylamino-n-propylthioborine with a primary amine at70°, e.g.,Me,N.BH*SC,H, + ZRNH, + (RNH),BH + C3H,SH + Me,NH.On heating the product above 150°, an N-trialkylborazole is produced.38The stability of aminoborines in relation to the substituents on the nitrogenand boron atoms has been in~estigated.~~ Dichlorodimethylaminoborine,Me,N*BCl2, dimerises, whereas dimethyldimethylaminoborine, Me&*BMe,,does not ; when these are heated together the intermediate compoundMe,N*BClMe is formed, and this is stable to disproportionation but slowlyforms a solid dimer.40 The reaction of hydrogen chloride with trisdimethyl-aminoborine in ether yields the compound [Cl,B(HNMe,),]Cl, and thisis also obtained by reaction of hydrogen chloride with chlorobisdimethyl-amin~borine.~~ Trimethylamine-triborane, Me,N*B,H,, is cleaved by tri-phenylphosphine t o give the triphenylphosphinethe possible structure (a), i.e.a 2 : 1 adduct of theparent hydride of the diboron compounds.42 New ph3p+ + pph,3diboron compounds B,(NMe,),- ,$lZ have been pre-pared by reaction of tetrakisdimethylaminodiboron with hydrogen chloridein ether.43 The existence of trisdifluoroborinylamine, N(BF,),, stabilisedby B-N n-bonding, is predicted on theoretical grounds.44Boron-nitrogen ring compounds continue to receive attention ; mixturesof isomeric fluoroborazoles, B,N,H,F, and difluorobora-zoles, B,N,H,F,, have been synthesised by reaction ofdiborane with tetrafluorohydrazine a t 140-160°,45BBB-trisdialkylaminoborazoles, (R,NB*NH), (R = Me,Et, Prr’, Pri), by reaction of secondary amines with BBB-trichloroborazole, 46 NNN-t r i a 1 k y 1 b o r a z o 1 e s ,(BH-NR),, by heating the borine adduct RNH,*BH,with a thiol R’SH, whereupon the intermediate compoundRNH*BH*SR’ splits out R’SH to give the b o r a ~ o l e .~ ~ Thermal dehydro-chlorination of the addition compound of boron trichloride and 2,6-dimethyl-adduct of a new boron hydride, (Ph,P*BH,),, with H,- -/ HB--HI (4)H’Y-PN\ CI B/ CIRAN, /N,RBIHIand( s i36 E. C. Ashby and W. E. Foster, J . Arner. Chem. SOC., 1962, 84, 3408.37 J. K. Ruff, J . Org. Chem., 1962, 27, 1020.38 B. M. Mikhailov and V. A. Dorokhov, Izvest. Akad. Nauk S.S.S.R., Otdel. khim.39 G. M. Wyman, K. Niedenzu, and J. W. Dawson, J., 1962, 4068; D. W. Aubrey,40 F. C. Gunderloy and C. E. Erickson, Inorg. Chem., 1962, 1, 349.4 1 H.Noth and S. Lukas, Chena. Ber., 1962, 95, 1505.4 2 B. M. Graybill and J. K. Ruff, J . Amer. Chem. SOC., 1962, 84, 1062.43 H. Noth and W. Meister, 2. Naturforsch., 1962, 17b, 714.44A. D. Buckingham, Proc. Chem. SOC., 1962, 351.4 5 R. K. Pearson and J. W. Frazer, J . Inorg. Nuclear Chem., 1961, 21, 188.413 W. Gerrard, H. R. Hudson, and E. F. Mooney, J., 1962, 113.4 7 B. M. Mikhailov and V. A. Dorokhov, Izvest. Akad. Nauk S.S.X.R., Otdel. khim.Nauk, 1961, 1163 (1082).M. F. Lappert, and M. K. Majumdar, ibid., p. 4088.Nauk, 1961, 1346 (1251)134 INORGANIC CHEMISTRYMe MeI I I IMeB, ,BMe MeN, ,NMeI\: BMe MelN\BB B - - N’ ‘N _-aniline yields the dichloroborazole (5) (R = 2,6-Me2C,H,) in which thesingle B-H link is stable to nu~leophiles.~8 The preparation of N-lithio-borazoles, and reaction of these with B-chloroborazoles has given newpolymers consisting of borazole rings linked through B-N bonds, e.g., com-pound (6) (n < 23); similar units linked through B-O-B bonds are obtainedn ( 6 )L -1by controlled hydrolysis of B-chloroborazoles.4~ Reaction of boron tri-chloride or boron tribromide with ortho-substituted anilines gives fused-ringborazoles in which each B-N unit of a borazole ring is bridged as shown in(7) ;50 but reaction with fully a-substituted amines (e.g., ButNH,) yields tetra-meric borazynes, (RN-BX),, and not trimeric borazoles ; these are solidsX RRN<B-N\ BXand are generally much more stable than the borazoles. Structural studiessuggest a boat form of the ring structure (8; X = Cl); the relatively in-accessible boron atoms account for the low reactivity.51 Monomeric phos-phinoborines have been prepared by reaction of alkylchloroborines withlithium albylphosphines :Et,N.BCl, + BLiPEt, -+ Et,N*B(PEt,), + 2LiC1.These compounds are reactive liquids ; reaction with hydrogen chloride gives,e.g., Et,N*BCl*PEt,, and this on reduction with sodium-potassium alloyyields the diboron compound (9).52Et2N. PEt2,B- B(Et2P NEt2(9)I 1MeC=N, ,N=CMeMeC=N‘ N=CMeI N’, I48 R. K. Bartlett, H. S. Turner, R. J. Warne, M. A. Young, and (in part) W. 5.49 R. I. Wagner and J. L. Bradford, Inorg. Chem., 1962, 1, 93, 99.6 o J. J. Harris and B. Rudner, J . Org. Chem., 1962, 27, 3848.s1 H.S. Turner and R. J. Warne, Proc. Chem. SOC., 1962, 69.5*H. Noth and W. Schragle, Angew. Chem., 1962, 74, 587.McDonald, Proc. Chem. SOC., 1962, 153HOLLIDAY TYPICAL ELEMENTS 135Several examples of phosphinodecaboranes, BloH1,(PX,),, have beeninvestigated ; in bis( chlorodiphenylphosphino)decaborane, the phosphorus isattached at the 6- and 9-positions; reaction with a primary amine givesBloH12(Ph,P-NHR),, and with sodium azide BloHl,(Ph2PN,), is obtained;exchange of the attached phosphino-groups with acetonitrile has beennoted.53 Reaction of dimethylaminodifluorophosphine with the unstablecarbon monoxide adduct of tetraborane yields the stable compoundB,H,*F,P*NH,, where co-ordination is probably through the phosphorusatom. 54The reaction of boron with air or oxygen at temperatures above 1600"gives the solid oxide B60.55 A reactive form of boron monoxide, (BO),,which is soluble in alcohols and reacts with boron trichloride to form diborontetrachloride, is obtained by dehydration of hypoboric acid, which is re-formed on addition of water to the oxide; a boroxole ring structure is sug-gested for the latter.56 The cyclic structure of the trimeric boron oxy-fluoride, B303F3, has been confirmed by mass-spectroscopic observations ;the boron-oxygen bonds appear to be intermediate in character betweenB-0 and -B=O+, and conditions (high temperature and low pressure)for dissociation to the monomer have been defined.Addition of hydrogento the high-temperature reaction system, BF, + B,O,, yields gaseousproducts such as B,03F2H.57 Cyclic boronates have been prepared fromphenylboronic anhydride and appropriate diols, and the stability of theiramine complexes discussed with respect to ring size and s ~ l s t i t u e n t s .~ ~The introduction of boron into a metal-chelate ring system is reported;59bis(dimethylg1yoximato)nickel reacts with BX, (X = alkyl or halogen) com-pounds to effect ring closure through 0-B-0 bonding to give structure (10).A new class of non-stoicheiometric crystalline inclusion compounds, ofgeneral formula (MeO),B*(amine),,(solvent), (n < 1 and x < 3), is reported;the compounds can be sublimed without change of composition.60 Numer-ous cationic species of boron sulphides, up to BIOS,+, have been identifiedby mass spectrometry in the vapour of B,S,.61 Several studies of reactionsof thiols with boron compounds are reported; trialkylborons, R,B, andalkanethiols, R'SH, yield esters of diallcylthioboric acid, R,B-SR' , fromwhich the SR' group is displaced by ammonia to give R,BoNH,;~~ with53 H.Schroeder, J. E. Reiner, and T. L. Heying, Inorg. Chem., 1962, 1, 618; R. J.Pol& and T. L. Heying, J . Org. Chem., 1962,27, 1482;.L. I. Zakharkin and V. I. Stanko,Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Naulc, 1961, 2078 (1936).64 G. Ter Haar, M. A. Fleming, and R. W. Parry, J . Amer. Chem. Soc., 1962, 84,1767.6 6 H. F. Rizzo, W. C. Simmons, and H. 0. Bielstein, J . Electrochem. SOC., 1962,109, 1079.6 6 A. L. McCloskey, R. J. Brotherton, and 5.L. Boone, J . Amer. Chem. SOC., 1961,83, 4750; cf. Ann. Reports, 1961, 58, 85.57 M. Farber, J . Chem. Phys., 1962, 36, 661,.1101; R. F. Porter and W. P. Sholette,ibid., 37, 198; W. J. Lehmann, C. 0. Wilson, JW., and I. Shapiro, J . Inorg. NuclearChem., 1961, 21, 25; cf. Ann Reports, 1961, 58, 85.68A. Finch and J. C. Lockhart, J., 1962, 3723.69 F. Umland and D. Thierig, Angew. Chem., 1962, '74, 388; G. N. Schrauzer,Chem. Ber., 1962, 95, 1438.60D. M. Young and C . D. Anderson, Canad. J . Chem., 1962, 40, 1805.61 F. T. Greene and P. W. Gilles, J . Amer. Chem. SOC., 1962, 84, 3598.62 B. M. Mikhailov and Yu. N. Bubnov, Zhuv. obshchei Khim., 1961, 31, 160 (150)136 INORGANIC CHEMISTRYdiethylaminoborine the thiol affords an alkylthiodiethylaminoborine, e.g. ,E~,N*BHoSR';~~ and with the thiol and boric oxide in boiling benzene,cu-mercaptoalkylborates (HS*[CH,];O),B are formed.64 Metal thioborates,e.g., CUBS and AgBS, which are unreactive, are formed by direct union ofthe elements a t 800".65 The reaction of metal sulphates M1,S04 andM'ISO, with boric acid and sulphur trioxide gives bis-sulphatoborates, e.g.,MI[ B( SO,),], MI1[ B( SO4),],, and tris-sulphatodiborates, e.g. , MII[B,O( SO,),] ;these are sensitive to hydrolysis.66The chemistry of the boron sub-halides and related compounds withB-B bonds has been reviewed.67 Treatment of boric esters with sulphurtetrafluoride gives successive replacement of alkoxy-groups by fluorine,finally yielding boron trifluoride.68 Some addition compounds of borontrifluoride with primary aromatic diamines have been prepared and char-acterised.69 Diboron tetrafluoride reacts with oxygen to give boron tri-fluoride and a stable solid, (B,O,F),; with nitric oxide, the products aremainly nitrous oxide and nitrogen.70 Labelled boron trichloride is con-veniently prepared by heating together silver chloride and boron above600" in vacz~o; a 70% yield is 0btained.~1 An examination of the infraredspectra of phosphoryl chloride-boron trichloride and similar addition com-pounds suggests that these are oxygen-co-ordinated and not ionic. 72 Sterice&cts which control the replacement of chlorine atoms in boron trichlorideby dialkyl- and diaryl-amino-groups have been studied ; complete replace-ment does not occur if, e.g., the alkyl groups are branched in the ct-position,although mixed tris(dialliy1amino)-compounds, e.g., R,N*B(NPr',), (R = Me,Et), are thermally stabh73 The thermal decomposition of diboron tetra-chloride yields boron-chlorine compounds which are coloured solids ; oneof these is the red dodecaboron undecachloride, B,,Cl,,, which gives a singlebroad paramagnetic resonance band in cyclopentane solution.The solidis only slightly decomposed below its m.p. (115"), but is hydrolysed in basicsolution :2B12Cl11 + 140H- + 3H2 + 4B0,- + 2[B1,Cl,(OH)2]2- + 2H20 + 6C1-.With an excess of trimethylamine, the addition compound (B,,C1,,,2Me3N),is formed.74 The existence of the tetraiodoborate ion, B14-, has been con-firmed, and the tropenium salt prepared.75 The reaction of boron tri-chloride with sodium or potassium thiocyanate in liquid sulphur dioxide63 B.31. Mikhailov and V. A. Dorskhov, Zhur. obshchei Khirn., 1961, 31, 37506 4 R. C. Cass and H. B. Silver, Chem. and Ind., 1962, 265.6 5 J. Flahaut, L. Domange, and J. K. Korn, Compt. rend., 1962, 254, 299.6 6 G. Schott and H. U. Kibbel, 8. unorg. Chew,., 1962, 314, 104.6 7 A. K. Holliday and A. G. Massey, Chem. Rev., 1962, 62, 303.6 8 A. Dornow and M. Siebrecht, Chem. Ber., 1962, 95, 763.6 9 A. Kreutzberger and F. C. Ferris, J . Org. Chem., 1962, 27, 3496.7 0 A. K. Holliday and F. B. Taylor, J., 1962, 2767.71 K. H. Lieser, H. W. Kohlschutter, D. Maulbecker, and H. Elias, 2. anorg.7 2 M. E. Peach and T.C. Waddington, J., 1962, 3450.73 D. W. Aubrey, W. Gerrard, and E. F. Mooney, J., 1962, 1786.7 4 G. Urry, E. P. Schram, and S. I. Weissman, J . Amer. Chem. SOC., 1962, 84,7 5 K. H. Harman and F. E. Cummings, J . Amer. Chem. Xoc., 1962, 84, 1751.(3504).Chem., 1961, 313, 191.2654HOLLIDAY : TYPICAL ELEMENTS 137yields boron tri-isothiocyanate, B(NCS),, which has acceptor properties ;complex isothiocyanatoborates, e.g., Na[BH(NCS),] and Li[B(NCS),], areprepared (as etherates) by the reaction of the appropriate borohydride withethereal thiocyanogen. 76Aluminium. Bisdimethylaminoaluminium hydride adds on two moleculesof bis(dimethy1aminoborine) to give the adduct HA1(NMe2),,2(BH,*NMe2),but the structure of this is uncertain.77 Alkali-metal aluminium hydridescan be prepared directly and in good yield by reaction of the metal or itshydride with aluminium and hydrogen in ether solvents a t 140" underpressure.78 A variety of compounds containing A1-N bonds have beenproduced by using tetramethyltetrazen as a source of dimethylamino-radicals, e.g., MeAl(NMe,), and (Et,Al*NMe,),.7 9 Polymers containingA1-N bonds have been prepared by formation and then condensation ofaddition compounds of triphenylaluminium with aliphatic amines in toluene,and some of these have been characterised, e.g., (Me,N*AlPh,), and(MeN*A1Ph),.S0 The use of an aromatic amine with non-ortho ring substi-tuents (e.g., p-toluidine) in this reaction yields crystalline tetramers(C,H,Al-NAr),, analogous to the tetrameric borazynes ; a cubic structure,with aluminium and nitrogen atoms a t the corners, is suggested.81 Thereaction of trimethylammonium chloride and ethylaluminium chloride intoluene a t room temperature probably yields the salt (MeNH,)(EtA1Cl,).s2The white crystalline trimer (Et2P*A1C1,), is formed by the reaction ofaluminium chloride with 1 mol.of lithium diethylphosphide in ether; with4 mol. of the latter, the solid Li[Al(PEt,),] is obtained.83 A new low-temperature form of the aluminate, LiA1O2, prepared by heating lithiumcarbonate with alumina a t 600 O , is reported.84 Polymeric phthalocyanine-aluminium compounds have been prepared with organo- and organosiloxy-groups bonded to the aluminium, e.g., pcAl-O*SiPh, (pc = C3,Hl6Ns);others contain A1-O-A1 bonds and some are resistant to hydrolysi~.~~Solvated complex halogeno-acids, HAlX,,dioxan (X = C1, Rr), have beenobtained by reaction of aluminium metal and hydrogen halide in dioxan.86Trimethylaminegallane and the corre-sponding trideuterogallane have been prepared, and the vibrational fre-quencies assigned; there is evidence that the Ga-H bond is stronger thanthe A1-H bond in the corresponding aluminium adducts.87 Trialkylgallanes,Gallium, indium, and thallium.7 6 D. B. Sowerby, J . Amer. Chem. SOC., 1962, 84, 1831; F. Klanberg, 2. anorg.7 7 J. K. Ruff, Inorg. Chem., 1962, 1, 612.7 8 E . C. Ashby, Chem. and Ind., 1962, 108.7 9 N. Fetter and B. Bartocha, Cunad. J . Chem., 1962, 40, 342.Chem., 1962, 316, 197.A. W. Laubengayer, K.Wade, and G. Lengnick, Inorg. Chem., 1962, 1, 632.J. Idris Jones and W. S. McDonald, Proc. Chem. SOC., 1962, 366.82 J. D. Smith, J., 1962, 4734.83 G. Fritz and G. Trenczek, 2. unorg. Chem., 1961, 313, 236; Angew. Chem., 1962,8 4 H.-A. Lehmann and H. Hesselbarth, 2. anorg. Chem., 1961, 313, 117.8 5 J. E. Owen and M. E. Kenney, Inorg. Chem., 1962, 1, 331, 334.8 6 J. A. Miliotis and A. G. Galinos, Compt. rend., 1962, 254, 3368.8 7 D. F. Shriver, R. L. Amster, and R. C. Taylor, J . Amer. Chem. Soc., 1962, 84,1322; N. X. Greenwood, A. Storr, and M. G. H. Wallbridge, Proc. Chem. SOC., 1962,249.74, 942138 INORGANIC CHEMISTRYR,Ga, have been prepared by the reaction of gallium trihalides with alum-inium alkyls in the presence of potassium chloride, and dialkylgallanes,R,GaH, by the reaction of dialkylgallium halides with dialkylaluminiumhydrides under similar conditions; R,GaH is converted into R,GaR' byreaction with olefins or acetylenes.88 Gallium nitride has been prepared bythe reaction :Ga203 + 2NH3 -+ 2GaN + 3H20at 480"; it decomposes above 600O.89 Co-ordination compounds of types(GaL,)+X- and (GaL,)+(GaX,)- (L = monodentate ligand; X = C1, Br)have been prepared from GaX and Ga(GaX,), respectively, with a varietyof ligand~.~O Some complexes of gallium(r1r) halides with o-phenanthrolinehave been described.91 The compounds InSF and InSeF have been pre-pared by heating a mixture of indium(n1) fluoride and the sulphide orselenide at 400".92 Complexes of thallium(m) iodide and nitrate withammonia, 2,2'-bipyridyl, and 1,lO-phenanthroline are reported.93 Thal-lium(1) methoxide has been shown to be tetrameric, with the structure (1 1).94I / I / .'TI - OMeGroup IV.--Carbon. New methods for the preparation of cyanides,cyanates, and thiocyanates, using reactions in fused alkali or alkaline-earthchlorides, are described, e.g.g5Me2SiC1 + KCN + Me,SiCN + KCISiCl, + 4KSCN+ Si(SCN), + 4KC1.The products obtained by the fluorination of cyanogen depend upon themode of fluorination; reaction with silver difluoride a t 105-115" does notgive the same product (F,N*CF,*CF,*NF,) as direct fluorination but givesinstead the compound (12); this does not react with water but decomposesabove 150" to give nitrogen, tetrafluoroethylene, and other products.gsThe occurrence of multiple bonding with particular referenceto silicon has been reviewed,97 and the r6le of the 3d-orbitals in formingn-bonds from silicon and other elements to oxygen has been discussed.98Silicon.8 8 J. J.Eisch, J . Arner. Chem. SOC., 1962, 84, 3605, 3830.Q 0 F. M. Brewer. J. R. Chadwick. and G. Garton, J . Inorg. Nuclear Chem., 1961,M. R. Lorenz and B. B. Binkowski, J . Electrochem. SOC., 1962, 109, 24.23, 45.Q l B . N. Ivanov-Emin, L. A. Niselhon. Ya. I. Rabovik, and L. E. Larionova,Zhur. neorg. Khim., 1961, .6, 1142 (583)..Q 2 H. Hahn and W. Nickels, Z. anorg. Chem., 1962, 314, 303.Q3 F. Ya. Kul'ba, Yu. A. Makashev, and V. E. Mironov, Zhur. neorg. Khirn., 1961,Q 4 L. F. Dahl, G. L. Davis, D.L. Wsmpler, and R. West, J . Inorg. Nuclear Chem.,9 s W. Sundsrmeyer, Z. afaorg. Chem., 1962, 313, 290.Q6 H. J. Emelbus and G. L. Hurst, J., 1962, 3276.9 7 I. R. Beattie and T. Gibson, Nature, 1962, 193, 1041.Q8D. W. J. Cruickshank, J., 1961, 5486.8, 1481 (758).1962, 24, 357HOLLIDAY : TYPICAL ELEMENTS 139The preparation of high-purity silicon from silane by heating it above 777"is described.99 Conversion of silane into higher silanes can be achieved with68% conversion in an ozoniser, and mixed hydrides, e.g., SiH3,PH2 andGeH,,PH, can be prepared similarly. l o o In the preparation of silane deriva-tives from silicon, it is usually necessary to activate the latter, but reactionof unactivated silicon with cuprous chloride-activated hydrogen chloride a t300-400 O gives a 99% yield of trichlorosilane.101 Methylation of phenyl-silane has been effected with diazomethane.102 Bisaminomethyl(dimethy1)-silane, Me2Si(CH,*NH2),, has been prepared by the reaction of bischloro-methyl(dimethy1)silane with bisphthalimidomethyl(dimethyl)silane, and itspropertie$ are described.103 Considerable progress has been made in thechemistry of disilane and its derivatives. Disilane has been obtained ingood yield by reaction of iodosilane vapour with sodium amalgam at ordinarytemperatures, and 1,2-dimethyldisilane by analogous methods.Reactionof the previously reported iododisilane, H,Si*SiH,I, with mercuric sulphideyields the sulphide ( H3Si*SiH2),S, with ammonia the trisdisilanylamine(H,Si*SiH,),N (both spontaneously inflammable in air), and with silverbromide disilanyl bromide, H,Si*SiH,Br.Other disilane derivatives synthe-sised include the chloride and the cyanide, and the oxide (Me3Si*SiMe2),0.lo4From chloropentamethyldisilane, octamethyltrisilane , Me,Si,, has been pre-pared by reaction with chlorotrimethylsilane and sodium-potassium a.lloy ;use of the chloropentamethyldisilane alone gave decamethyltetrasilane,MeIoSil. lo5 Some interesting new compounds containing Si-B bonds havebeen prepared by the reaction:106R,SiLi + ClB(NMe,), + R,Si*B(NMe,), + LiCl j,,,,R,Si*BCl(NMe,) + Me,NH,HCl.New silazides have been prepared by several methods; thus, lithiumazide and chlorotriphenylsilane in tetrahydrofuran give triphenylsilazide,Ph,SiN,, and this on reaction with triphenylphosphine gives nitrogen andthe compound Ph,Si*N:PPh,; sodium azide in pyridine can be used to formthe same triphenylsilazide and also the diazide Ph,Si(N,),.107 Methylsilazides, e.g., Me,SiN,, have also been prepared, by reaction of chloro-trimethylsilane with sodium azide at 250" in an anhydrous melt of zinc andpotassium chlorides as solvent, or with sodium azide in tetrahydrofuran in99 C. H. Lewis, H. C. Kelly, M. B. Giasto, and S. Johnson, J . Electrochem. Soc.,1961, 108, 1114.100 J. E. Drake and W. L. Jolly, Chem. and Ind., 1962, 1470; E. J. Spanier andlol P. G. Dudani and H. G. Plust, Nature, 1962, 194, 85.l o 2 K. Kramer and A. Wright, Angew. Chem., 1962, 74, 468.lo3 J. Goubeau and H. D. Fromm, 2.anorg. Chem., 1962, 317, 41.lo4 L. G. L. Ward and A. G. MacDiarmid, J . Inorg. Nuclear Chem., 1961, 20, 345;1961, 21, 287; A. D. Craig and A. G. MacDiarmid, ibid., 1962, 24, 161; A. D. Craig,J. V. Urenovitch, and A. G. MacDiarmid, J., 1962, 548.lo5 U. G. zu Stolberg, Angew. Chem., 1962, 74, 696.lo6 H. Noth and G. Hollerer, Angew. Chem., 1962, 74, 718.lo' N. Wiberg, F. Raschig, and R. Sustmann, Angew. Chem., 1962, 74, 388, 716.A. G. MacDiarmid, Inorg. Chem., 1962, 1, 432140 INORGANIC CHEMISTRYpresence of aluminium azide as catalyst ; the compounds Me,Si(N,), andMeSi(N,), have been obtained similarly.108 The structure of tetramethyl-NN’-bis(trimethylsilyl)cyclodisilazane, reported last year, has been con-firmed, lo9 and some other, unstable N-silyl-tri- and -tetra-silazanes havebeen prepared.l1° It now seems probable that the compound prepared byreaction of silver cyanamide with iodosilane , formulated as disilylcyanamide ,(siH,),N.CN, may be a di-imide, since the analogous reaction with chloro-trimethylsilane gives bistrimethylsilylcarbodi-imide, Me,Si*N :C :N*SiMe, ; thecorresponding sulphur compound has the structure (Me,Si)~*S*N(SiMe,),.lllFurther work on silylphosphines has been carried out; synthesis by thegeneral reaction, LiPR, + R,SiCl,-,, has given, e.g., (Et,P),SiCl andEt,SiH*PEt,, and st phosphonium salt has been obtained by the reaction:112Me,Si*PEt, + EtI -+ (Me,Si*PEt,)I.Silicon halides Six, (X = F, Cl, Br) react with tertiary phosphines and theiroxides to give co-ordination compounds, SiX,,(PR,),, SiX4,(OPR2),, andSiX4,(OPR3)4.113The preparation of black and yellow forms of silicon monoxide, con-densed from the gaseous product of a silicon-silica reaction at 1200°, isreported.114 Condensation of chloromethyl(dimethyl)silanol with dichloro-dimethylsilane in the presence of triethylamine yields the compound (13) ;S i b 2M e Me Me y’ YHI I I I 1Me Me Me HN 0ICIH,C-Si - 0 - S i - 0 - S i -CHICl RZSi S i R ,(13) ‘si/R2 (14)the central silicon atom is replaced by germanium by using dichlorodimethyl-germane in the synthesis.115 Mixed siloxane-silazane ring compounds,e.g., (14; R = Me), have been obtained by reaction of dihalogenopoly-siloxanes, C1(SiR20);SiR,C1 (n = 1, 2, 3), with ammonia in ether.116Several compounds in which silicon and aluminium are linked throughoxygen or nitrogen have been prepared; thus, reaction of the compoundMe,Si*O*AlCl, with methyl-lithium yields Me,Si*O*AlMe,, which is dimeric inbenzene and has the structure (15); it is thermally stable and is not cleavedby trimethylamine at 3Oo.ll7 Similar compounds, in which the aluminium-lo8 W. Sundermeyer, Angew.Chem., 1962, 74,717, 875; idem, 2. anorg. Chem., 1962,313, 290; R. West and J. S. Thayer, J. Amer. Chem. SOC., 1962, 84, 1763; J. W. Con-nolly and G. Urry, Inorg. Chem., 1962, 1, 718.log P. J. Wheatley, J., 1962, 1721; cf. Ann. Reports, 1961, 58, 90.110 W. Fink, Helv. Chim. Acta, 1962, 45, 1081.J. Pump and U. Wannagat, Annalen, 1962, 652, 21; idem, Angew.Chem., 1962,74,117 ; E. A. V. Ebsworth and M. J. Mays, ibid., p. 117 ; U. Wannagat and H. Kuckertz,ibid., p. 117; cf. Ann. Reports, 1961, 58, 90.112 G. Fritz, G. Poppenburg, and M. G. Rocholl, Nuturwiss., 1962, 49, 255; G. Fritzand G. Poppenburg, ibid., p. 449.113 K. Issleib and H. Reinhold, 2. anorg. Chem., 1962, 314, 113.l14H.-H. Emons and H. Boenicke, 2. Chew., 1961, 1, 370.115 M. Wicber and M. Schmidt, Angew. Chern., 1962, 74, 903.116 C. R. Kriiger and E. G. Rochow, Angew. Chem., 1962, 74, 491.11’ H. Schmidbaur and M. Schmidt, J. Anzer. Chem. SOC., 1962, 84, 1069HOLLIDAY TYPICAL ELEMENTS 141attached methyl groups are replaced by -OSiR, groups, have also been pre-pared; further reaction gives anionic species, thus (with R = Me) :118R,SiONa + AlC1, + [(R,SiO),Al],+N1(R,SiO) 1 MI[ (R,SiO) ,Al(OSiR,) 2].The reaction of aluminium chloride with tetrameric dialkylcyclosiloxanesalso leads to the formation of Si-0-A1 bonds, e.g., in structure (16),119 andSiMe, (16) (17) SiMe3the silazalane (17) has been prepared by reaction of hexainethyldisilazaaewith aluminium chloride .I20 Reaction of sodium triphenylsilyl oxide andmercuric chloride gives (Ph,SiO),Hg as an unstable intermediate, whichspontaneously rearranges, with migration of a phenyl group from silicon tomercury, and yields Ph,Si*O*HgPh ; the latter, when heated, gives diphenyl-mercury and polymeric phenyl-silicones.121 The new compound, methyl silylsulphide, H,Si*SMe, has been prepared from methanethiol and the trimethyl-amine adduct of iodosilane; as a donor molecule to borine it is weaker thandimethyl sulphide but comparable to disilyl sulphide, (H3Si),S.122 Thereaction of chlorodimethylsilylmethanethiol and sulphuryl chloride is2C1SiMe2.CH,*SH + SO,Cl2 -+ ClSiMe,-CH,.S*S*CH,SiMe,Cl + SO, + 2HC1.The reactions of some nitrogen donor molecules (e.g., pyridine, trimethyl-amine, and 2,2'-bipyridyl) with the tetrahalides of silicon, germanium, andtita,nium, and with chloromethylsilanes, have been investigated. 124Germane has been prepared by reduction ofaqueous germanate solutions with alkali borohydrides, and higher germanesby decomposition of germane in an ozoniser.125 The formation of hexa-aryldigermanes from germanium tetrachloride and arylmagnesium halidehas been shown to proceed via the germyl Grignard reagent, Ar,Ge*MgX;hydrolysis of the latter (Ar = o-, m-, or p-C,H,Me) yields the hydrideAr,GeH.Tri-iodatrifluoromethylgermane, CF,*GeI,, has been preparedby the reaction of trifluoroiodomethane with germanium(rr) iodide ; treat-ment with the appropriate silver halide, AgX, replaces the iodine by thehalide, and with X = F, aqueous potassium fluoride dissolves the compound11* H. Schmidbaur and M. Schmidt, Angew. Chem., 1962, 74, 328, 589.llS A. A. Zhadanov, K. A. Andrianov, and A. A. Bogdanova, Izvest. AEad. Nauk1 2 * H . Schmidbaur and M. Schmidt, Angew. Chem., 1962, 74, 327.121 A. K. Ghosh, C. E. Hansing, A. I. Stutz, and A. G. MacDiarmid, J., 1962, 403.lZ2 B. Sternbach and A. G. MacDiarmid, J .Inorg. Nuclear Chem., 1961, 23, 225.123M. Wieber and M. Schmidt, Angew. Chem., 1962, 74, 002.124 I. R. Reattie and G. J. Leigh, J . Inorg. Nuclear Chem., 1961, 23, 55.125 J. E. Drake and W. L. Jolly, J., 1962, 2807.126 F. Glockling and K. A. Hooton, J., 1962, 3509.Germanium, tin, and lead.S.S.S.R., Otdel. khim. N a u k , 1961, 1261 (1172)142 INORGANIC CHEMISTRYto give the salt K,(CF,*GeP,). 12' Some germyl pseudohalides, e.g., GeH,*NCO,have been prepared by reaction of germyl bromide with the silver pseudo-halide ; however, silver thiocyanate yields the isothiocyanate GeH,*NCS. 128The difluorides of germanium and tin are readily prepared by reaction ofthe metal (M) with hydrofluoric acid; in presence of an excess of fluoride ion,complex anions MF3- are formed, GeF3- being more stable to hydrolysisthan SnF3-.129 Germanium tetrafluoride has been shown to be a powerfulacceptor molecule, forming both 1 : 1 and 1 : 2 addition compounds withmethyl cyanide, and 1 : 1 compounds with, e.g., ammonia, piperidine, phos-phine, and trimethylphosphine.l30 An examination of the microwavespectrum of germyl fluoride (first reported last year) suggests some degreeof a-bonding in the Ge-F bonds.131The occurrence of tin(@ has been detected in the oxidation of tin(I1)compounc@ by trioxalatocobaltate(rn) ions in aqueous s01ution.l~~ Alkyl-stannanes have been prepared by reaction of the appropriate tin(rv) halidewith alkylaluminium compounds; good yields are obtained by " binding "the aluminium chloride also produced, e.g., by addition of an amine orlithium chloride.l33 Tetrakisiodomethylstannane, Sn(CH,I),, has been pre-pared from the corresponding br0mide.13~ Interest in the various formsof diphenyltin continues; a six-membered ring of tin atoms is suggested asthe nucleus of the hexamer (SnPh,),, prepared by decomposition of diphenyl-stannane in ~yridine.1~5 Many new compounds containing Sn-N bondsare now reported; methods of preparation of these compounds, of generalformula R,Sn(*N<),-, (z = 1, 2, 3, or 4), from the corresponding alkyl-chlorostannanes, R,SnCl,, include treatment with a Grignard reagent (e.g. ,Et,N*MgBr), reaction with a lithium alkylamide, LiNR,, or reaction withthe corresponding organosilicon compound; in the latter case, 1 : 1 additionof a secondary silylamine, R,Si*NHR, to the tin compound (e.g., Me,SnBr)is followed by elimination of bromotrimethylsilane, on heating, to giveMe,Sn*NHR.136 With a tertiary silylamine, the 1 : 1 addition compound isstable to heat and in these compounds (18) the tin is five-co-ordinated; astructural investigation of the 1 : 1 addition compound of pyridine andtrimethylchlorostannane, Me,Sn(py)Cl, indicates that here also tin is fiveco-ordinate.137 I n ultraviolet light, tetrafluoroethylene has been shown tolZ7 H.C. Clark and C. J. Willis, J . Amer. Chem. SOC., 1962, '84, 898.lZ8 T. N. Srivastava, J. E. Griffiths, and M. Onyszchuk, Canad. J . Chem., 1962, 40,129 E. L. Muetterties, Inorg. Chem., 1962, 1, 342.lS0 R.C. Aggarwal and M. Onyszchuk, Proc. Chem. SOC., 1962, 20.739.J. E. GrifEths and K. B. McAf'ee, jun., Proc. Chem. SOC., 1961, 456; cf. Ann.Reports, 1961, 58, 91.132 W. C. E. Higginson, R. T. Leigh, and R. Nightingale, J., 1962, 435.133 W. P. Neumann and H. Niermann, Annalen, 1962, 653, 164; W. P. Neumann,ibid., p. 157; J. C. vaa Egmond, M. J. Jamsen, J. G. A. Luijten, G. J. M. van derKerk, and G. M. van der Want, J . Appl. Chem., 1962, 12, 17.134 K. Hoppner and D. Walkiewitz, 2. Chem., 1962, 2, 23.135 W. P. Neumann and K. Konig, Angew. Chem., 1962, 74, 215.136 G. J. M. van der Kerk, J. G. A. Luijten, and M. J. Janssen, Chimia (Switz.),1962, 16, 10; E. W. Abel, D. Brady, and B. R. Lerwill, Chem. and Ind., 1962, 1333;K. Sisido and S.Kozima, J . Org. Chem., 1962, 27, 4051; K. Jones and M. F. Lappert,Proc. Chem. SOC., 1962, 358.137 I. R. Beattie, G. P. McQuillan, and R. Hulme, Chem. and Ind., 1962, 1429HOLLIDAY : TYPICAL ELEMENTS 143add across the Sn-Sn bond of substituted distannanes to give R,Sn*C,F,*SnR(R = Ph, Me).l3* In the hydrolysis of dialkyl-tin(1v) compounds, dimericintermediates, R4Sn,X,02 (X = halogen, CO,-), are formed; suggestedalternative structures for these are (19) and (20).139R,SnX R2SnX2I mMe ,S i-NEt 0J RzSnX / o ~ SnR,X R,Sn’ ‘SnR2‘o/ * (20)R2SnX2\?’ (19)Br Sn Me3(18) R2SnXThere is evidence that in trimethylplumbane, Me,PbH, the lead-attachedhydrogen is acidic, and the equilibrium 2Me,PbH + Me,Pb- + Me,PbH,+is postulated. 140Active nitrogen reacts with boron trichloride andwith germane to form diboron tetrachloride and germanium(n) nitride,respectively; in the reaction with ammonia a t -196”, active nitrogen yieldshydrazine as an unstable intermediate.141 The formation of NH radicals asintermediates in the Raschig synthesis of hydrazine has been suggested.lg2Substantial amounts of hydrazine are obtained by glow-discharge electrolysisof ammonia-water mixtures (<50% of water) ; the mechanism of formationof hydrazine from ammonia by this method appears to involve formationof NH, radicals.lg3 Hydrazinolysis of trialkylchlorosilanes in the gas phaseyields bistrialkylsilyldiazanes, R,Si*NH*NH*SiR,, which on oxidation givenitrogen and hexa-alkyldisilanes ; di-alkyldichlorosilanes give chains,( *SiR,*NH*NH*),, but, if 1,2-dirnethylhydrazine is used, the compoundR,ClSi*NMe*NMe*SiClR, (R = Me) is obtained.The existence of thehydrazinium cation N2HG2+ is confirmed by preparation of the saltsN,H6(SbC16)2,N,H6(BP4),. 144 The reaction of alkali amides with someimides of elements in Group-111, -IV, and -V, in liquid ammonia as solvent,have been studied conductometrically ; imido- rather than amido-anions,e.g., [B(NH),]- and [P(NH)3]3--,P are formed.145 The reactions of nitricoxide with some organometallic compounds have been investigated ; withthe alkyls of Group-I1 or -111 eleme5ts (M), addition to the metal is followedby rearrangement to give M-0-( R)N* and addition of another NO moleculeto yield M-O-N(R)-NO, but with the alkyls of Group V, addition of thesecond NO molecule is followed immediately by splitting-out of nitrousoxide and formation of R-MzO ; with dimethylphosphine, the reaction is :1464NO + Me,PH--+ 2N,O + Me,PO,H.Group V.--Nitrogen.138M. A.A. Beg and H. C. Clark, Chem. and Ind., 1962, 140.139 D. L. Alleston, A. G. Davies, and B. N. Figgis, Proc. Chem. SOC., 1061, 457.140 C. Duffy, J. Feeney, and A. K. Holliday, J . , 1962, 1144.141 E. R. Zabolotny and H. Gesser, J . Phys. Chem., 1962, 66, 408; R. Storr, A. N.Wright, and C. A. Winkler, Canad. J . Chem., 1962, 40, 1296.142 J. Fischer and J. Jander, 2. anorg. Chem., 1961, 313, 14, 36.la3A. Hickling apd G. R. Newns, J . , 1961, 5177, 5186.144 H. Bock, 2. Naturforsch., 1962, lYb, 423, 426.145P.W. Schenk and J. B. P. Tripathi, Angew. Chem., 1962, ‘94, 116.146 M. H. Abraham, J. H. N. Garland, J. A. Hill, and L. F. Larkworthy, Chem.and Ind., 1962, 1615; M . Halmmm and L. Kugel, J., 1962, 3272144 INORGANIC CHEMISTRYNo addition of nitric oxide to metallic sodium (to form NaNO) occurs be-tween 190" and 230"; instead, sodium oxide is first formed, and this thenadds on nitric oxide to give mixtures of Na,NO, and Na,N,O,; the infraredspectrum of the hyponitrite ion N,0,2- has been further ~tudied.l4~Vapour-phase oxidation of hydrogen cyanide by nitrogen dioxide a t 200-350 Oover a suitable catalyst yields cyanogen :2HCN + NO,+ (CN), + NO + H,O.The nitric oxide is oxidised and then re-cycled and the reaction is a usefulmeans of synthesising cyan0gen.1~~ Azide dimethylamine, Me,N*N3, hasbeen prepared by reabtion of sodium azide and dimethylchloroamine in aninert solvent a t ordinary temperature.149 Further spectroscopic studies ofthe isomers of dinitrogen tetrafluoride suggest that these are the cis- andtrans-l,2-forms ; the nature of the more reactive cis-isomer was previouslyuncertain. 50 Nitrogen fluorides and their organic derivatives have beenreviewed. 151 The reactions of the nitrosyl fluoride-hydrogen fluorides,NOF,3HF and NOF,5HF, with many elements and compounds have beenstudied ; the usual products are the metal fluoride and nitrosyl fluoride.Nitryl fluoride-penta( hydrogen fluoride), N02F,5HF, has been obtained fromnitryl fluoride and hydrogen f l ~ 0 r i d e .I ~ ~ The reaction of dinitrogen tetra-fluoride and nitric oxide a t 300" yields the intensely-coloured nitroso-di-fluoramine F,N*NO-it is suggested that the pink colour of N,F, is due tothis as jmpurity.153Phosphorus. A survey of structure and reactions in phosphorus chem-istry has a p ~ e a r e d . 1 ~ ~ A new method of preparing metallic phosphides, byreduction of the oxides with phosphine, is suggested.155 The structures ofthe pentaphenyls of phosphorus, arsenic, and bismuth have been studied ;a square-pyramidal configuration of the phenyl groups, with the Group-Vatom within the pyramid, is postulated.156 The " hybrid '' diphosphine,Me,P*P(CF,),, has been prepared; it is less stable than either Me,P-PMe,or (CF,),P*P(CF,),, and can act both as an acceptor (e.g., to trimethylamine)or as a donor (e.g., to borine).157 The reaction of bistrifluoromethylphos-phorus( III) iodide with silver carbonate yields the diphosphoxane,(CF,),P*O*P(CF,), ; the corresponding Me,P*O*PMe, undergoes immediaterearrangement and disproportionation.158 Trisilylphosphine, P( SiH,),, hasbeen prepared as a colourless, inflammable liquid by the reaction of mono-14' E.Eachbaur, Monatsh., 1962, 93, 129.148 W. L. Fierce and W. J. Sandner, I n d . Eng. Chem., 1961, 53, 985.lasH. Bock and K. L. Kompa, Angew. Chem., 1962, 74, 327.I5O J. H. Noggle, J. B. Baldeschwieler, and C. B. Colburn, J . Chem. Phys., 1962,151 C. J. Hoffmann and R. G. Neville, Chem. Rev., 1962, 62, 1.152 F. Seel and H. Semmler, Chimia (Switz.), 1962, 16, 290; F.Seel, W. Birnkraut,153 C. B. Colburn and F. A. Johnson, Inorg. Chem., 1962, 1, 715.154 N. L. Paddock, Roy. Inst. Chem. Lectures, 1962, No. 2.155 G. V. Samsonov, L. L. Vereikina, and Yu. V. Titkov, Zhur. neorg. Khim., 1961,156 P. J. Wheatley and G. Wittig, Proc. Chem. Xoc., 1962, 251.15' L. R. Grant, JU"., and A. B. Burg, J . Arner. Chem. SOC., 1962, 84, 1834.158 J. E. GriEiths and A. B. Burg, J . Amer. Chem. SOC., 1962, 84, 3442.37, 182.and D. Werner, Angew. Chem., 1961, 73, 806.6, 749 (382)HOLLIDAY: TYPICAL ELEMENTS 145bromosilane with potassium dihydrogen phosphide in dimethyl ether atlow temperature.Several new aminophospliines of the types ArP(NR,), and ArP(NR',)*NR,have been prepared; they form 1 : 1 addition compounds with methyl iodide,and complexes with mercuric iodide.160 Compounds of similar type, e.g.,P(NMe2)3 and MeP(NMe,),, form 1 : 1 addition compounds with substitutedborines; from these, aminoborines, Me,N*BX, (e.g., X =Me, F, Cl), areobtained by heating.161 Reaction of phosphoryl chloride and an excess ofmethylamine gives PO(NHMe),, phosphoric tri-N-methylamide, and this,when heated to 300°, eliminates amine to give first the diphosphoryl com-pound, P,O,(NMe),, and finally a substance of composition PN0.16, Ifchlorodiphenylphosphine is allowed to react with ammonia or chloramine intetrachloroethane as solvent, a solvated compound, (Ph2PN),, is formed andthis, when heated, loses solvent and gives a mixture of (Ph,PN), and(Ph,PN), ; the same compounds are obtained if hydrazine hydrochloride isused instead of amrn0nia.16~ Triphenylphosphine imine, Ph,PNH, reactswith substituted borines to give 1 : 1 addition compounds.164 Interestcontinues in the phosphonitrilic compounds (phosphazens) and the subjecthas been reviewed;l65 routes from phosphorus pentachloride to phosphazenshave also been discussed.166 A novel P-N 'ring compound (21) has beenE tsynthesised by reaction of an N-alkylbistrimethylsilylamine with phosphorustrichloride.167 Phosphonitrilic bromides have been prepared by methodsanalogous to those used for chlorides,16s and reaction of phosphonitrilicchlorides with thiols has yielded mercaptophosphazens, e.g.compound (22) ;the structures of several of these have been e1~cidated.l~~ The reaction ofbenzoyl chloride effects conversion of alkoxycyclophosphazens into 1,3,5-triazines.170 The basicity of some aminophosphazens has been measured;several of these, e.g., N,P,(NH,),, are comparable in base strength withfree amines.171 Reaction of phosphorus trichloride with tetrasulphurtetranitride yields the compound (P2NC17), ; the structures of this and159 E. Amberger and H. Boeters, Angew. Chem., 1962, 74, 32.l 6 0 G. Ewart, D. S. Payne, A. L. Porte, and (in part) A. P. Lane, J., 1962, 3984.161 R. R. Holmes and R. P. Wagner, J. Amer. Chem. SOC., 1962, 84, 357.162 R. R. Holmes and J. A. Forstner, Inorg. Chem., 1962, 1, 89.163 H. H. Sisler, H. S. Ahuja, and N. L. Smith, Inorg. Chem., 1962, 1, 84.164R. Appel and F.Vogt, Chem. Ber., 1962, 95, 2225.165 R. A. Shaw, B. W. Fitzsimmons, and B. C. Smith, Chern. Rev., 1962, 62, 247.l a 6 M . Becke-Goehring and E. Fluck, Angew. Chem., 1962, 74, 382.16' E. W. Abel and G. Willey, Proc. Chem. Xoc., 1962, 308.168 K. John and T. Moeller, J. Inorg. Nuclear Chem., 1961, 22, 199.169 A. P. Carroll and R. A. Shaw, Chem. and Ind., 1962, 1908; N. Boden, J. W.170 B. W. Fitzsimmons, C. Hewlett, and R. A. Shaw, Proc. Chem. SOC., 1962, 340.l7ID. Feakins, W. A. Lust, and R. A. Shaw, Chem. and Ind., 1962, 510.Emsley, J. Feeney, and L. H. Sutcliffe, ibid., p. 1909146 INORGANIC CHEMISTRYof the related P3NCI12 have been investigated and are shown to be(Cl,P:N*PCl,:N*PCl,)(PCl,) and (Cl,P:N*PCl,)(PCl,) respectively; theseappear to be members of a general class, [Cl,P:N~(PCl,N),*PCl,](PCI,),obtainable from reactions of phosphonitrilic chlorides with phosphorus penta-chloride. Treatment of (P2NC1,), with sulphur dioxide gives POCl,,SOCl,and P3N,0C1,.172 A similar compound, P,NOCl,, is obtained by reaction ofphosphorus trichloride with dinitrogen tetroxide, and has the structureCl,P:N*P( O)Cl,.Several oxy- and thio-chlorobromides of phosphorus (e.g., POClBr, andPSC1,Br) have been prepared by reaction of phosphorus pentoxide or penta-sulphide with phosphorus(v) chlorobr~mides.~~~ The subject of condensedphosphates and arsenates has been reviewed.17, Although the reaction oftri-n-butylphosphine with sulphur has long been known, isolation of theproduct, Bun3PS, has only recently been achieved; reaction of Bun,PBr, withhydrogen sulphide gives the related Bun,PS,HBr.l76 Substituted diphos-phine disulphides , RR'P( S) *P( S)RR', can be used to synthesise substituteddiphosphines by reaction with alkylphosphines, R",P ; with R" = Bu,equimolar amounts of two isomericl diphosphines are obtained. WithR = R', reaction of the disulphide with a halogen (X) gives R,P(S)X andthen R,PCI,, formulated as (R,PC1,)(R,PCl4) for X = C1; for X = Br,further addition gives R,PBr,, i.e. (R,PBr,)Br,. l77 Reaction of bis(trifluor0-methy1thio)- or bis(trifluoromethylse1eno)-mercury with iodobis( trifluoro-methyl)-phosphine or -arsine gives the compounds (CF,),X*YCF, (X = P,As; Y = S, Se).178 Diphosphoryl tetrafluoride, P&F4, has now beenprepared by dehydration of difluorophosphoric acid with phosphorus(v)oxide; a comparison of the Raman spectrum with that of the correspondingtetrachloride suggests the structure 0:PF2*0*PF,:0.179 Fluorophosphor-anes, RPF,, are now conveniently prepared by fluorination of alkyldichloro-phosphines with either arsenic or antimony trifluoride.lSo Triferrocenyl-phosphine, P[Fe(C,H,),],, has been prepared by a Friedel-Crafts reaction offerrocene and phosphorus trichloride.Arsenic, antimony, and bismuth. Diarsine may be prepared by distillingarsenic trichloride into ethereal lithium aluminium hydride at -190" andwarming slowly. lS23SiH,Br + 3KAsH, + As( SiH,), + 3KBr + 2AsH,Trisilylarsine has been prepared by the reaction,172 E. Fluck, 2.anorg. Chem., 1962, 315, 181, 191; M. Becke-Goehring, E. Fluck,173 M. Becke-Goehring, A. Debo, E. Fluck, and W. Goetzee, Chem. Ber., 1961, 94,17* W. Kuchen, H. Ecke, and H. G. Beckers, 2. anorg. Chem., 1962, 313, 138.175 E. Thilo, Adv. Inorg. Chem. Radiochem., 1962, 4, 1.176 R. A. Zingaro and R. E. McGlothlin, J. Org. Chem., 1961, 26, 5205.177 L. Maier, J. Inorg. Nuclear Chem., 1962,24, 275; W. Kuchen and K. Strolenberg,Angew. Chem., 1962, 74, 27; W. Kuchen, H. Buchwald, K. Strolenberg, and J. Matten,Annalen, 1962, 652, 28.17* H. J. EmeMus, K. J. Packer, and N. Welcman, J., 1962, 2529.179E. A. Robinson, Canad. J. Chem., 1962, 40, 1725.lSo R. Schmutzler, Chem. and Ind., 1962, 1868.lS1 G. P. Sollott and E. Howard, jun., J. Org. Chem., 1962, 27, 4034.lS2 P.J. Fensham, J. Inorg. Nuclear Chem., 1961, 23, 139.and W. Lehr, 2. Naturforsch., 1962, 17b, 126.1383; E. Fluck, ibid., p. 1388HOLLIDAY : TYPICAL ELEMENTS 147in dimethyl ether a t low temperature; the product is colourless and burns inair.ls3 The reaction of some amines with trisdimethylaminoarsine yieldscompounds of type (23; X = Bu, Ph, NMe,).ls4 Ring structures are sug-gested for condensed polyfluoroarsenates obtained by heating K(AsF,OH), 185and decomposition of triphenylarsenic( m) azide yields the tetrameric cyclicdiphenylarsenonitride (24 ; R = Ph) .I86 Isopropenyl and vinyl derivativesMe,N -As -N-XI I(23) XN -As - NMezof antimony, R,SbX, (R = CH,:CH, CH,:CMe; X = C1, Br, I), have beenisolated.187 A soluble polymeric form of antimonic acid has been obtainedby ion-exchange methods, and complexes of the acid with polyhydroxy-compounds have been investigated.188 Evidence that fluorination by anti-mony trifluoride is initiated by a free electron-pair on the antimony has beenpresented.189 In liquid sulphur dioxide as solvent, the compound SbCl,F,exists also in the form (SbC1,)(SbF6), and hence addition of sodium fluorideyields the salt Na( SbCl,F,), whereas reaction with arsenic trifluoride gives(AsCl,)(SbF,) and SbF3.1g0The structure of " bismuth monochloride " is notable, being made up oflarge Big5+ cations and (Bi,C1,)2- and (BiC1J2- as anions.lgl Perfluoro-alkylbismuth compounds, e.g. Me,(CF,)Bi and Me(CF,),Bi, have been pre-pared by treating trimethylbismuth with a perfluoroalkyl iodide. 192Group V1.-Oxygen.Reviews on compounds of the oxide-water sys-tem lg3 and on oxide melts have appeared.194 The new compound ammon-ium ozonide has been prepared by the low-temperature ozonisation ofammonia ; it displays the characteristic absorption spectrum of an ozonide,but decomposes above -126" to give ammonium nitrate, oxygen, andwater.lg5 If ammonia is absorbed on the surface of anhydrous lithiumhydroxide, reaction with ozonised oxygen produces Li(NH,),O,, which isvery soluble in liquid ammonia but decomposes when the ammonia isremoved. 196lE3 E. Amberger and H. Boeters, Angew. Chem., 1962, '94, 293.lS4 H. J. Vetter and H. Noth, Angew. Chem., 1962, 74, 943.185 L. Kolditz and B. Nussbucker, 2.anorg. Chem., 1961, 312, 299; L. Kolditz andlE6 W. T. Reichle, Tetrahedron Letters, 1962, 51.D. Renno, ibid., 1962, 315, 46.S.S.S.R., Otdel. khim. Nauk, 1961, 1578 (1473).A. N. Nesmeyanov, A. E. Borisov, and N. V. Novikova, Izvest. Aka&. NaukS. H. Gate and E. Richardson, J . Inorg. Nuclear Chem., 1961, 23, 257, 265.R. Muller and C . Dathe, 2. anorg. Chem., 1961, 313, 207.lQo L. Kolditz, D. Weisz, and U. Calov, 2. anorg. Chem., 1962, 316, 261.lgl A. Hershaft and J. D. Corbett, J . Chem. Phys., 1962, 36, 90.lD2 T. N. Bell, B. J. Pullman, and B. 0. West, Proc. Chem. SOC., 1962, 224.lD3 0. Glemser, Angew. Chem., 1961, 73, 785.lD4 J. D. Mackenzie, Adv. Inorg. Chem. Radiochem., 1962, 4, 293.lD5 I. J. Solomon, K. Hattori, A. J. Kacmarek, G.M. Platz, and M. J. Klein, J .Amer. Chem. Soc., 1962, 84, 34.A. J. Kacmarek, J. M. McDonough, and I. J. Solomon, Inorg. Chem., 196?, 1,659148 INORGANIC CHEMISTRYSulphur. The reaction of elementary sulphur with a diaryldiazomethanegives a tetra-arylethylene sulphide in good yield : I 9 72Ar,CN, + S-+Ar,C-CAr, + 2N,.When tetraphenyltin and sulphur are heated together a t 190", the principalproduct is the trimer, (Ph,SnS),, which has a cyclic structure of alternatetin and sulphur atoms analogous to that of the (R,SnS), compounds.198Tetrasulphur tetranitride has been prepared by heating ammonium chloridewith sulphur monochloride vapour, and trisulphur dinitrogen tetroxide,S3N204, by reaction of thionyl chloride vapour with a heated mixture ofsulphur and ammonium chloride.lg9 An electron-spin resonance spectralstudy of sulphur nitride anions, e.g., S4N4-, indicates delocalisation of then-electrons over the ring.200 The existence of sulphur nitride cations,e.g., S4N,f, is suggested by cryoscopic and conductivity measurements onS4N3C1 in solution. ,01 Reaction of trithiazyl chloride with dimethyl sul-phoxide yields an alkylated disulphur nitride; this forms a conducting solu-tion and is probably dissociated, in the excess of dimethyl sulphoxide usedas solvent :202(NSCl), + 6Me,SO -+ 3(Me2S*N:SMe,)C1 + 3S0,.Addition of chloramine to dialkyl sulphides gives sulphiminium salts, e.g.,(R,S*NH,)Cl (R = Me, Et) ; de-protonation of the corresponding sulphate(R2NH,),SO4 gives a sulphimine, R,S:NH, stable below 30°.203 Imido-bisulphuryl chloride, ClSO,*NH *SO,Cl, is prepared by reaction of phosphoruspentachloride with sulphamic acid, and subsequent treatment of the initialproduct, Cl,P:N*SO,Cl, with chlorosulphonic acid ; the same compound isformed directly by reaction of this acid with urea; fluorosulphonic acid withurea gives the fluoride, HN( SO,F),.204 A thiohydroxylamine-S-sulphonate,H,N*S*SO,-, is obtained by reaction of a thiosulphate with a hydroxylamine-0- sulphonate ; it gives unstable thiohydroxylamine on acid hydrolysis. 205Reaction of ammonia with SOF, in presence of sodium fluoride in etheryields the etherate of iminosulphuroxydifluoride, HN :SOF,, as a colourlessliquid ; removal of ether, and dehydrofluorination, gives a rubbery poly(oxy-fluorosulphur nitride), ( *N:SOF*),, apparently analogous to rubbery phos-phonitrilic chloride polymer.206 The ring structure of a-sulphanuricchloride, (=N:SOCl*),, is now found to be a non-planar chair form withapproximately tetrahedral bonding around the sulphur, and the S-N-Sangle -120°.207 An extensive study of reactions of sulphides in liquid'S/197 A.Schonberg and E. Frese, Chem. Ber., 1962, 95, 2810.198 M. Schmidt, H.-J. Dersin, and H. Schumann, Chem. Ber., 1962, 95, 1428.lS9 W. L. Jolly and M. Becke-Goehring, Inorg. Chem., 1962, 1, 76.2oo D. Chapman and A. G. Massey, Trans. Faraday Soc., 1962, 58, 1291.2 0 1 M. Becke-Goehring and H. P. Latscha, 2. Naturforsch., 1962, 17b, 125.202 M. Recke-Goehring and H.P. Latscha, Angew. Chenz., 1962, 74, 695.203 R. Appel and W. Buchner, Chem. Ber., 1962, 95, 849.204 R. Appel and G. Eisenhauer, Chem. Ber., 1962, 95, 246; R. Appel, M. Becke-205 R. Gosl and A. Meuwsen, 2. anorg. Chem., 1962, 314, 334.206 G. W. Parshall, R. Cramer, and R. E. Foster, Inorg. Chem., 1962, 1, 677.107 A. J. Banister and A. C. Hazell, Proc. Chem. SOC., 1962, 382.Goehring, G. Eisenhauer, and J. Hartenstein, ibicl., p. 625HOLLIDAY : TYPICAL ELEMENTS 149ammonia has been continued; silicon disulphide yields compounds such asSiS(NH,), and SiS :NH, whereas germanium disulphide gives ammoniumsalts such as NH4( GeS,*NH,) which gives (NH,),(Ge,S,) when heated ;stannic sulphide behaves similarly.208 Some isothiocyanates, e.g., P(NCS),and As(NCS),, have been prepared in acetonitrile or liquid .sulphur dioxideas solvent by reaction of a metal thiocyanate with the appropriate chlor-ide.209 The reaction of phenylphosphine with sulphur monochloride yieldsthe compound (C,H,PS,), for which a cyclic structure is suggested.210A method for the preparation of disulphur monoxide, S,O, by heating aheavy-metal oxide with sulphur in vacuo, has been reported.211 Furtherstudies of the sulphuric acid solvent system have been made; Raman spectralstudies of sulphuric acid-sulphur trioxide and deuterium sulphate-sulphurtrioxide mixtures give evidence for the existence of species such as H,S4013at high sulphur trioxide concentrations, and for the non-ionic dissociation ofoleum to give H2S3010 and sulphuric acid. Similar studies of solutions ofsulphur trioxide in fluoro- and chloro-sulphuric acids give evidence for, e.g.,H,S20,F and HS,O,Cl.In concentrated solutions of tetra(hydrogen sul-phato)boric acid, HB(HSO,),, in sulphuric acid, elimination of disulphuricacid gives polymers containing B-O-B bonds; attempts to produce salts ofthe acid by metathesis of potassium hydrogen sulphate and H(BHSO,),gave instead polysulphatoborates containing six-membered rings of alternatesulphur and oxygen atoms.212The chemistry of sulphur tetrafluoride has been reviewed,213 and bondlengths and angles, and the dipole moment have been determined.214Alkyl-, fluoroalkyl-, and aryl-sulphur trifluorides have been synthesised byfluorination of the appropriate disulphides with silver difl~oride.21~ Thepreparation of disulphru.decafluoride by photochemical reduction of sulphurchloride pentafluoride by hydrogen is reported, and some reactions of thedecafluoride in sealed glass tubes a t 150-200 O have been investigated ;halogens (X) yield SF,X, but SF,CN is not formed with cyanogen; ammoniagives NSF, and S,,N, when in excess.216 It is suggested that Lewis acidsmay attack sulphur hexafluoride by co-ordination to a fluorine atom; insupport of this, a slow reaction with anhydrous aluminium chloride occursa t 180-200" to give some aluminium fluoride, chlorides of sulphur, andchlorine; sulphur trioxide at 250" gives some SO,F,.217 New methods ofpreparing sulphur chloride pentafluoride have been described, e.g., by re-action of chlorine trifluoride with sulphur, or chlorine monofluoride withsulphur tetrafluoride. 218 Reactions of SClF, with some metal carbonyls are208 H.Behrens and J. Ostermeier, Clzem. Ber., 1962, 95, 487.209 D. B. Sowerby, J. Inorg. Nuclear Chern., 1961, 22, 205.210E. Fluck and R. M. Reinisch, Chem. Ber., 1962, 95, 1388.211 A. R. Vasadeva Murthy, Nature, 1962, 193, 773.212 R. J. Gillespie and E. A. Robinson, Cunad. J . Chem., 1962, 40, 658, 675, 784,213 W. C. Smith, Angew. Chem., 1962, 74, 742.214W. M. Tolles and W. D. Gwina, J . Chem. Phys., 1962, 36, 1119.215 W. A. Sheppard, J . Arner. Chem. Xoc., 1962, 84, 3058.216 B. Cohen and A. G. MacDiarmid, Chem. and I n d . , 1962, 1866; H. L. Roberts,217 J. R. Case and F.Nyman, Nature, 1962, 193, 473.218F. Nyman and H. L. Roberts, J., 1962, 3180.1009.J., 1962, 3183150 INORGANIC CHEMISTRYreported, e.g., with nickel carbonyl, nickel chloride difiuoride is obtained.210Pentafluorosulphuroxyaryl compounds, ArO-SF, have been prepared byreaction of, e.g., toluene or chlorobenzene with bispentafluorosulphur per-oxide, F,S*0*0*SF,;220 the latter compound, SF,Cl, and S2F1, all reactphotochemically with sulphur dioxide to give pentafluorosulphur fluoro-sulphate, F,S*0*S02F.221 Some reactions of pentafluorosulphur hypofluoriteare also reported; it decomposes a t 210" to give oxygen and sulphur hexa-fluoride, and reacts with sulphur tetrafluoride to give a mixture of SF6, SOP,,F,S*O*O*SF,, and F,S*O*SF,, .and with carbon mon-F oxide to give F,CO and Peroxydisulphurylfluoride, F02S*O*O*S02F, can behave as an oxygenat-ing agent (e.g., to carbon monoxide and trifluoro-O-i-F (25) phosphine), or as a fluorosulphonating agent (e.g.,to HgO, C5H8), or as both (e.g., to SOClF).Re-action at ordinary temperature with tetrafluoro-ethylene gives tetrafluorobis(fluorosulphonato)ethane, C2F4(S03F),, andwith sulphur tetra fluoride, tetra fluoro bis (fluor osulp hona t 0) sulphur ( VI) ,SF4(S0,F),, is obtained; this has the structure (25).223Xelenium and tellurium. Perfluoroalkyl silyl selenides, SiH3*SeRF(RF = CF,, C3F,), have been prepared by reaction of iodosilane with bis(per-fluoroalkyl)selenomercury, Hg( SeRF), ; they decompose slowly at ordinarytemperatures to give fluorosilanes and other pr0ducts.22~ Salts of imido-selenic acids, M,(O,Se*N*SeO,) (M = K, Ag), have been prepared by reactionof SeO,F, with ammonia and then treatment with alkali.3Z5 Fluoroselenicacid, HSeO,F, may be prepared by reaction of anhydrous hydrofluoric acidwith selenium trioxide.226 Raman spectral studies of selenious acid indicatethe presence of the species SeO,2- and HSe0,- only when alkali is added;in water alone, dissociation of H2Se03 is negligible.227An extensive study of complexes of both tellurium-(n) and -(Iv)? withvarious urea derivatives as ligands, has been continued ; with ethylene-thiourea (etu) many complexes, Te(etu),X,, have been prepared; and withX = Br, two forms, probably cis and trans, have been isolated.228Group VII.-Reviews have been published on halogen cations,22g organo-silicon compounds of fluorine, 930 new fluoroalkyl c0mpounds,23~ and the8 .\ !...I ...... 4 o-:-F:;s, ' : o oI 0FF' .. . . . . . . . .219 A. G. Massey and K. J. Packer, J., 1961, 5554.220 J. R. Case, R. Price, N. H. Ray, H. L. Roberts, and J. Wright, J., 1962,221 H. J. Emelbus and K. J. Packer, J., 1962, 771.222 S. M. Williamson and G. H. Cady, Inorg. Chem., 11962, 1, 673.223 J. M. Shreeve and G. H. Cady, J. Amer. Chem. SOC., 1961, 83, 4521.224 E. A. V. Ebsworth, H. J. Emelkus, and N. Welcman, J., 1962, 2290.225 A. Engelbrecht, Monatsh., 1961, 92, 1269.226 H. Bartels and E. Class, Helv. Chim. Acta, 1962, 45, 179.227 G. E. Walrafen, J. Chem. Phys., 1962, 36, 90.228 0.Foss and W. Johannesen, Acta Chem. Scand., 1961, 15, 1939, 1940, 1941;0. Foss and 1.-J. Johannesen, ibid., p. 1943; 0. Foss and S. Hauge, ibid., pp. 1615,1616, 1623; 0. Foss and S. Fossen, ibid., pp. 1618, 1620; 0. Foss and K. Marpy, ibid.,pp. 1945, 1947.S2Q J. Arotsky and M. C. R. Symons, Quart. Rev., 1962, 16, 282.aso 0. V. Odabashyan, V. A. Ponomarenko, and A. D. Petrov, Uspekhi Khim.,1961, 30, 941 (407).231 H. J. Emelbus, Angew. Chem., 1962, 74, 189.2107HOLLIDAY : TYPICAL ELEMENTS 151fluorides of the actinides.232 The reaction of many chloro-compounds, e.g.,CCl,, COCl,, S02C1,, RSiC1, and PCl,, with molten alkali or alkaline-earthfluorides affects quantitative exchange of halogens to give the correspondingfluoro-compounds.233 The reabtion of fluorine with halides of rubidiumgives fluorohalogenates, e.g., RbBrF4.2s4 A large number of stable mole-cular complexes of interhalogen compounds with pyridine and its derivativeshave been prepared.235 The structure of the compound KF,2A1Et3 hasnow been cofimed as KEt3A1*F*A1Et,; the A1-C bond lengths are normalfor sp3-hybrid bonds, and the Al-F distance is the same as in cryolite;sp-hybridisation of the fluorine atom is suggested, with some A1-F n- bondingby overlap of fluorine 2 p with vacant aluminium 3d-orbitals.236 Thereaction of trifluoromethyl iodide with nitric oxide and dinitrogen tetra-fluoride is activated thermally and by ultraviolet radiation, and the productis 2-fluoro-l-trifluoromethyldiazen 1 -oxide, F,C*NO :NF.237Further studies have been made in liquid hydrogen chloride as a solvent;solubilities and reactions of compounds containing doubly-bonded oxygenhave been studied, and also compounds containing multiple bonds, e.g.,acetylenes, olefins, and nitriles ; all these act as solvo-bases.238 The effectof strong acids on periodic acid has been studied spectrophotometrically; instrong aqueous acids, there is evidence for the cation [I(OH),]+, but in 65%oleum an orange solid, probably 120,, is The colour of solutionsof iodine in sulphuric acid and oleum has been confirmed as due to I+,and there is evidence for the existence here of Is+, 13f, and H2103+ also;from 65% oleum, white crystals of the iodyl compound, (IO)HS,O,, can beobtained."O The reaction of iodine with an excess of silver perchlorate inether at low temperatures yields the complex, AgC10,,I(C104) and someI(C10J3; in ethyl alcohol, the monoperchlorate, I(C104), is the only pro-d ~ & ~ ~ ~ An infrared study of the structure of iodine dioxide has confirmedthe structure (10) +( 10,) -.242 In methylene dichloride as solvent, iodineand hydrogen sulphide form a 1 : 1 addition compound; there is evidencefor the equilibrium z43H,S,I, + (H,SI)+ + I-.A. K. H.232 N. Hodge, Adv. Fluorine Chem., 1961, 2, 138.233 W. Sundermeyer, 2. anorg. Chern., 1962, 314, 100.234 H. Bode and E. Klesper, 2. unorg. Chem., 1961, 313, 161.235 M. T. Rogers and W. K. Meyer, J . Phys. Chem., 1962, 66, 1397.236 G. Natta, G. Allegra, G. Perego, and A.Zambelli, J. Amer. Chem. SOC., 1961,237 J. W. Frazer, B. E. Holder, and E. F. Worden, J. Inorg. Nuclear Chem., 1962,23* M. E. Peach and T. C. Waddington, J., 1962, 600, 2680.238 H. C. Mishra and M. C. R.. Symons, J., 1962, 1194.a40 J. Arotsky and M. C. R. Symons, Nature, 1962, 193, 678; J. Arotsky, H. C.Za1N. W. Alcock and T. C. Waddington, J., 1962, 2570.242 J. H. Wise and H. H. Hannan, J . Inorg. Nuclear Chem., 1961, 23, 31.243 J. Jander and G. Tiirk, Chem. Ber., 1962, 95, 881.83, 5033.24, 45.Mishra, and M. C. R. Symons, J., 1962, 2582152 INORGANIC CHEMISTRY3. THE TRANSITION ELEMENTSONCE again a large number of publications have been concerned with com-plexes of the transition elements, As in .previous years, organometalliccompounds and complexes not conveniently discussed under the particulargroups will be treated separately. Great advances have been made in thehalogen chemistry of the transition metals, and the preparations of previouslynon-existent halides will be mentioned in the particular groups.The chem-istry in the groups will be described, wherever possible, in order of ascendingoxidation numbers of the elements, and within each oxidation state theorder will be that of ascending atomic weights. General reviews publishedduring the year have been concerned with the cyanide complexes of thetransition metals and with the use of nuclear magnetic resonance spectro-scopy in inorganic chemistry.2Scandium, Yttrium, and the Rare Earths.-Zerovalent tris( bipyridyls) ,Sc(bipy),, and Y(bipy),,STHF are obtained upon reduction of the corre-sponding trichlorides with lithium in tetrahydrofuran (THF) in the presenceof 2,2'-bip~idyl.~ I n the absence of the reducing agent, the complexesScCl,(bipy), and ScCl,(phen), (phen = 1 ,lo-phenanthroline) can be isolated.*Thermal-stability studies a t 340-440 " on the light rare-earth oxalates givethe following relative order of stabilities : Gd > Sm > Nd > La > Pr > Ce.Erbium and lutetium oxalates are stabilised by traces of water, and decom-position a t 350" begins only after a long induction period.5 In the scan-dium( 111) chloride-caesium chloride phase diagram there is a congruently-meking phase of composition cs3scc16, and a 3 : 2 compound, cs,sc,c1,,with a peritectic point a t 619".6 The composition and solubility of cerium-(111) chloride alcoholates have been investigated; one to four molecules ofaliphatic alcohols co-ordinate, and solubilities have been determined forCeCl,(EtOH),, CeCl,(PrOH),, and CeCl,( BuOH),.The solid acid chelatesformed by tripositive rare-earth ions from cerium to samarium with theprotonated EDTA ligand are monohydrated, while the rest are anhydrous.Infrared studies indicate that the change in hydration number is accom-panied by a change in co-ordination of the EDTA ligand from penta- tohexa-dentate. * Numerous papers have appeared on the thermodynamics offormation of rare-earth chelates with amino-acid ligands.9 Colourless,diamagnetic, complex fluorides, M,CeF, and M2CeF6 (M = Na, Rb, Cs),have been obtained from the fluorination of mixtures of cerium(rv) oxide1 W.P. Griffith, Quart. Rev., 1962, 16, 188.2 E. L. Muetterties and W. D. Phillips, A d v . Inorg. Chem. Radiochem., 1962, 4,3 S. Herzog, G. Byham, and P. Wulfert, 2. Chem., 1961, 1, 370; S. Herzog and4 E. N. Ivanov-Emin, L. A. Nisel'son, and L. A. Larionova, Zhur. neorg. Khim.,5 A. Glasner and M. Steinberg, J . Inorg. Nuclear Chem., 1961, 22, 39, 156.6R. Gut and D. M. Gruen, J . Inorg. Nuclear Chem., 1961, 21, 259.7 F. R. Hartley and A. W. Wylie, J., 1962, 679.8 R. S, Kolat and J. E. Powell, Inorg. Chem., 1962, 1, 485.9 T. Moeller and R. Ferrus, J . Inorg. Nuclear Chem., 1961, 20, 261; idem, Inorg.Chem., 1962, 1, 49; T. Moeller and L. C.Thompson, J . Inorg. Nuclear Chem., 1962,24, 499; L. C. Thompson, Inorg. Chem., 1962, 1, 490; J. L. Mackey, M. A. Hiller, andJ. E. Powell, J . Phys. Chem., 1962, 66, 311.231.K. Gustav, 2. Nuturforsch., 1962, 17b, 62.1961, 6, 170 (334)NICHOLLS : THE TRANSITION ELEMENTS 153and alkali-metal chlorides ; Na,CeF, is tetragonal while Cs,CeF7 andRb,CeF, have cubic structures. Przeseodymium fluorides are preparedsimilarly.10 The separation of the rare earths by volatilisation of theiroxides at 2500" in a solar furnace has been investigated; cerium(1v) oxidecan be separated pure from its mixtures with lanthanum(II1) oxide in thisway. l1The Actinides.-The actinide oxides have been the subject of a review.12Hydrolysis of uranium monocarbide gives gelatinous hydrous uranium( ~ v )oxide together with gaseous products consisting of methane (86 vol.o/o),hydrogen (1 1 vol. yo) and other c2-c6 hydrocarbons. l 3 Salts containingthe pentacarbonatothorate(Iv) ion have been prepared. They can beprecipitated quantitatively with hexa-amminecobalt(II1) chloride as[CO(NH,)~],[T~(CO,),],~H~~. l4 Thorium(m) chloride reacts with carboxylicacids to form tetracarboxylates with monobasic acids and bisdicarboxylateswith dibasic acids.15 While uranium(1v) perchlorate is unstable and cannotbe isolated, a dimethylacetamide complex, U( ClO,),,GAcNMe,, is formedwhen the chloride analogue is treated with silver perchlorate in acetone andthe ligand added.l6 Uranium(1v) oxide cannot be used as a refractory inview of its reaction, and consequent swelling, with oxygen, forming U,O,.The fluorite structure can, however, be stabilised by forming solid solutionswith tervalent oxides of lanthanum or yttrium.17 The oxidation of theU4+aq. ion has been studied by l80 tracer techniques.With oxygen orozone only one of the oxygens in the U0,2+ product is derived from theoxidising agent, but with lead and manganese dioxides both oxygens arederived from the oxidiser.ls In view of the short U=O distance in uranylcompounds it has been suggested that there is interaction between the lonepairs on the oxygens and the vacant orbitals on uranium.19 Ammoniumdiuranate is very variable in composition but, from a comparison of theinfrared spectra of various uranium oxide hydrates, its structure appears tobe UO,( OH),,xNH,,yH,0.20 Plutonium(1v) complex halides can be pre-pared by the chlorination of melts containing plutonium(II1) chloride andan allCali-metal chloride at 0.8 atm.at 50" above the melting point.2l Someevidence has been found for plutonium(vI) fluoride in the high-temperatureoxidation of plutonium(m) fluoride with dry oxygen.22 Quadrivalentlo R. Hoppe and K.-M. Rodder, 2. anorg. Chem., 1961, 313, 154; R. Hoppe andl1 I. Trombe and M. Foex, Compt. rend., 1962, 255, 1447, 1516.l2 L. E. J. Roberts, Quart. Rev., 1961, 15, 442.l3 M. J. Bradley and L. M. Ferris, Inorg. Chem., 1962, 1, 683.l4 I. I. Chernyaev, V. A. Golovnya, and A. K. Molodkin, Zhur. neorg. Khim.,l5 S. Prasad and S . Kumar, J . Indian Chem. SOC., 1962, 39, 444.l6 K.W. Bagnall, D. Brown, and A. M. Deane, J., 1962, 1655.l7 W. B. Wilson, C. A. Alexander, and A. F. Gerds, J . Inorg. Nuclear Chern., 1961,G. Gordon and H. Taube, Inorg. Chem., 1962, 1, 69.l9 M. E. Dyatkina, V. P. Markov, I. V. Tsapkina, and Yu. N. Mikhailov, Zhur.2o A. M. Deane, J . Inorg. Nuclear. Chem., 1961, 21, 238.21 R. Benz and R. M. Douglass, J . Inorg. Nuclear Chem., 1961, 23, 135.22 C. J. Mandleberg, D. Davies, and K. E. Francis, J . Inorg. Nuclear Chew, 1961,W. Liebe, ibid., p. 221.1961, 6, 394 (200); 809 (413).20, 242.neorg. Kfim., 1961, 6, 575 (293).21, 92154 INORGANIC CHEMISTRYamericium has been stabilised by co-ordination with fluoride ions. On dis-solution of americium(1v) hydroxide in ammonium fluoride solutions, no dis-proportionation occurs ; by using rubidium fluoride, Rb,AmF, can be pre-cipitated.23 The compound UCl,,PCl,, prepared a t room temperature fromphosphorus pentachloride and uranium( v1) oxide, dissociates in phosphorusoxychloride to form PCI,+ and UcI6-q Electrolysis of the solution givesuranium(n) chloride a t the anode and phosphorus tri- and penta-chloridea t the cathode.24 The chemistry of uranium fluorides has been re~iewed.~5The oxide U308 is converted into uranium(@ fluoride by fluorine a t1000 lb./in.2.26 Hydrogen chloride reacts with mono- and poly-uranates ofpotassium to give the uranyl chlorides, K,UO,Cl,, K,(UO,),Cl,, K,(U0,),C18,and K,(U0,),C110.27 Contrary to earlier reports, the reduction of neptun-ium(vI) in chloride media is very slow a t room temperature, and a satis-factory absorption spectrum of this ion can thus be obtained.The acceler-ated reduction in the presence of platinum is not due to a catalytic effect butt o reduction by the platinum itself.38 The chemistry and structure ofperoxouranates has been reviewed. 29Titanium, Zirconium, and Hafnium.-Absorption spectra studies of thehydrates formed by Ti3+ in low or moderate concentrations show that thesehave tetragonal bipyramidal and not octahedral ~yrnrnetry.~O The firsthydrolysis constant for the aquotitanium( 111) ion has been measured potentio-metrically.31 Tervalent and bivalent chlorides of titanium are antiferro-magnetic with ,ueff. = 1.31 B.M. for titanium(1n) chloride and 1.08 B.M.fortitanium(I1) chloride. Magnetically-dilute complexes, e.g., Ti(Urea),(ClO,),,show the expected moment, ,u = 1.72 B.M. Antiferromagnetic interactionprobably occurs also in the lower-Talent chlorides of zir~onium.3~ Reduc-tion of zirconium(1v) iodide with aluminium yields zirconium(II1) iodide ;33zirconium( 111) bromide has been prepared by reduction of zirconium(Iv)bromide with finely powdered zirconium.34 Electromigration studies oftitanium(1v) ions in hydrochloric acid show that anionic complexes arepredominantly formed only a t concentrations greater than 1 0 ~ ;35 the solidphases H,[Ti(OH),Cl,] and H,[Ti(OH),Cl,] have been detected in theTiC14-HC1-H,0 system.36 Hexafluorotitanates(1v) have been prepared fromtitanium( 1v) fluoride and amines in acetone solution saturated with hydrogen23 L.B. Asprey and R. A. Penneman, Inorg. Chem., 1962, 1, 135; F. H. &useand L. B. Asprey, ibid., p. 137.24 R. E. Panzer and J. F. Suttle, J. Inorg. Nuclear Chem., 1961, 20, 229.26 I. V. Tananaev, N. S. Nikolaev, Yu. A. Luk'yanychev, and A. A. Opalovskii,Uspekhi Khim., 1961, 1490 (654).26 R. E. Greene and G. S. Petit, J. Inorg. Nuclear Chem., 1962, 24, 393.27 J. Lucas, Compt. rend., 1962, 255, 313.2s D. Cohen and B. Taylor, J. Inorg. Nuclear Chenz,., 1961, 22, 151.29 I. I. Chernyaev, V. A. Golovnya, and G. V. Ellert, Zhur. neorg. Khim., 1961, 6,80 I. I. Antipova-Karataeva, E. E. Vainshtein, and Yu. I. Kutsenko, Zhur. neorg.31 R. L. Pecsok and A. N. Fletcher, Inorg. Chem., 1962, 1, 155.32 J.Lewis, D. J. Machin, I. E. Newnham, and R. 8. Nyholm, J., 1962, 2036.33 G. W. Watt and W. A. Baker, J. Inorg. Nuclear Chem., 1961, 22, 49.34 H. L. Schlafer and H. Skoludek, 2. anorg. Chem., 1962, 316, 15.3 5 B. I. Nabivanets, Zhur. neorg. Khim., 1962, 7, 412 (210).36 G. M. Toptygina and I. S. Morozov, Zhur. neorg. Khim., 1961, 6, 1685 (861).790 (403).Khim, 1961, 6, 2329 (1181)NICHOLLS : THE TRANSITION ELEMENTS 155fluoride; their X-ray d spacings and infrared spectra are reported.37 Whiletrimethylamine rapidly reduces titanium(1v) chloride, pyridine formsTiC14,2py which is stable in the absence of excess of ~yridine.~* The firstaminolyses of titanium( IT) fluoride have been reported ; with di-n-propylaminethe products are R2NTiF, and (R2NH,+),TiF62 -.39 Several new additioncompounds of titanium(1v) chloride with esters have been reported; theyare of the types TiCl,,PhCO,Me and TiC14,2Me*C6H,*C0,Me.40 Titanium(1v)alkoxides yield mono-, di-, tri-, and tetra-substituted derivatives with2-hydroxyethylamine ; Ti( OR),( 0 *C,H,*NH,) and Ti( OR),( O*C,H,-NH,), aredimeric in benzene.41 Biscyclopentadienyltitanium dichloride is ammono-lysed in liquid ammonia, (n-C,H,),TiCl(NH,) and (n-C,H,),Ti(NH,), beingprobable products. 42 Reaction of cyclopentadienylsodium with dichloro-diethoxytitanium(1v) yields (n-C,H,)Ti( OEt), which is monomeric in benzeneand yields (n-C,H,)TiCl, upon treatment with acetyl chloride.43 The yellow,solid oxychloride, TiOCl,, is formed in reactions between titanium(1v)chloride and arsenic, antimony, and bismuth trioxides.44 Only one peroxidephase, Ti(O*OH)(OH),, is formed when hydrated titanium dioxide is treatedat 0" or -20" with hydrogen peroxide of a wide variety of concentration^.^^Complex peroxy-compounds with oxalic acid, Ti02(C20,),3H,0, can beisolated in the solid state.46 Titanyl bisacetylacetonate, prepared by reac-tion of acetylacetone with titanyl di-n-propoxide, has been shown to bemonomeric and hence five-co-ordinate in benzene.47 Other five-co-ordinatetitanium complexes prepared include the products of the reactions oftitanium(1v) alkoxide with the chelating agents salicylaldehyde and methylsalicylate;48 these contain three alkoxide groups and one chelate. Acrystallographic study of the titanium-sulphur system has been reported. 49Tetranitratozirconium( 1v) has been prepared as colourless, sublimablecrystals by means of the reaction:50ZrC1, + 4N,O, + Zr(NO,), + 4N0,Cl.It is very hygroscopic and rapidly reacts with toluene at room temperatureto give nitro-compounds.Treatment of zirconium tetra-acetylacetonate87 J. A. Chandler, R. S. Drago, and R. Latham, jun., J . Inorg. Nuclear Chem.,s8 I. R. Beattie and G. J. Leigh, J . Inorg. Nuclear Chem., 1961, 23, 55.3g J. A. Chandler, J. E. Wuller, and R. S. Drago, Inorg. Chem., 1962, 1, 65; J. A.4 0 B. Mori, J. Gohring, D. Cassimatis, and B. P. Susz, Helw. Chim. Acta, 1962,41 D. M. Puri and R. C. Mehrotra, J . Indian Chem. SOC., 1962, 39, 447.4 2 R. S. Dickson and B.0. West, Austral. J . Chem., 1962, 14, 555.43A. N. Nesmeyanov, 0. V. Nogina, and A. M. Berlin, Izvest., Akad. Nauk44 P. Ehrlich and W. Engel, 2. anorg. Ch.em., 1962, 317, 21.4 5 S. 2. Makarov and L. V. Ladeinova, Izvest., Akad. Nauk S.S.S.R., Otdel. chim.46 G. V. Jere and C. C. Patel, J . Inorg. Nuclear Chem., 1961, 20, 343.4 7 A. N. Nesmeyanov, 0. V. Nogina, and IT. A. Dubovitskii, Izvest., Akad. Nauk48A. Yamamoto and S. Kambara, J . Inorg. Nuclear Chem., 2961, 21, 58.4g Y. Jeannin, Ann. Chim. (France), 1962, 7, 57.6 o B. 0. Field and C. J. Hardy, Proc. Chem. SOC., 1962, 76.1961, 21, 283.Chandler and R. S. Drago, ibid., p. 356.45, 77.S.S.S.R., Otdel. chim. Nauk, 1961, 804 (743).Nauk, 1961, 958 (889).S.X.X.R., Otdel. chim. Nauk, 1961, 437 (403)156 INORGANIC CHEMISTRYwith carboxylic acids yields tetra-acyloxyzirconiums, [X( CH,),CO,],Zr(X = H, Cl).51 The infrared spectrum of ZrC1,,2EtOAc shows it to have thecis-octahedral structure while TiBr4,2EtOAc and Ti14,2EtOAc are probablytrccns-o~tahedral.~~ Hydrolysis of zirconium alkoxides, Zr( OR),, withsecondary or tertiary alkoxide groups leads to polymeric zirconium oxidealkoxides having low number-average degrees of polymerisation. 53 Withhydrazine, alkoxides form the complexes Ti( OPri),,N,H,, Zr( OPrI),,N,H,,and Ti(OEt),,iN,H, of unknown str~cture.~, In weakly acid media, electri-cally neutral sulphate complexes are formed by the addition of sulphate ionsto polymeric zirconium cations; when an excess of sulphate is present thepoly-ion chain is ruptured with the formation of anionic complexes.55Vanadium, Niobium, and Tantalum.-The solid portion of the V-VCphase diagram shows that the VC phase does not extend to VC1.oo, termin-ating a t vcO.88 a t 1000 o.56 The phase VSl.02-VS1.22 exhibits antiferromag-netism owing to vanadium(I1)-vanadium(rn) intera~tion.~' Tris-B,B'-bi-pyridylniobium(0) is obtained as violet crystals upon reduction of niobium(v)chloride in tetrahydrofuran with lithium and 2,2'-bipyridyl; it has the ex-pected magnetic moment of 1.75 B.M.58 Vanadium(I1) chloride does notdissociate or disproportionate a t 900-1 100 * ; disproportionation of vana-dium(m) chloride becomes appreciable at 425" in an atmosphere of argon.59Hydrates of vanadium(@ halides, e.g., VF2,4H,0 and V12,6H,0, can beisolated when solutions of vanadium(v) oxide in the respective acids arereduced cathodically.60 Some new five-co-ordinate vanadium(II1) com-pounds, VC13,2SMe2, VC13,2SEt2, and VBr3,2NMe,, have been isolated.Dipole-moment measurements strongly suggest that these have the trans-trigonal bipyramidal structure.61 Lower aliphatic alcohols co-ordinate withvanadium(rr1) chloride to give green solid alcoholates, e.g., VC13,4MeOH, andvanadium(II1) alkoxides can be prepared by using lithium methoxide andethoxide on the trichloride.62 The reaction of an excess of formic acid withvanadium(=) and vanadium(1n) chlorides yields vanadium(1v) formate ; thiscompound decomposes, when heated in an inert atmosphere, to give vana-dium( 1v) oxide.63 Disproportionation of vanadium( m) bromide has pro-vided the first route to the hitherto unknown tetrabr~mide.~, The phasesNbC13.1-3.2 and TaC13.1--3.2 appear upon disproportionation of the tetra-5 1 E.M. Brainina, R. Kh. Freidlina, and A. N. Nesmeyanov, Izvest., Akad.5 2 M. F. Lappert, J., 1962, 542.63 D. C. Bradley and D. G. Carter, Canad. J . Chem., 1962, 40, 15.54 M. S. Bains and D. C. Bradley, Canad. J . Chem., 1962, 40, 1350.5 5 B. I. Nabivanets, Zhur. neorg. Klzim., 1961, 6, 1319 (677).56 E. K. Storms and R. J. McNeal, J . Phys. Chem., 1962, 66, 1401.57 G. M. Loginov, Zhur. neorg. Khim., 1961, 6, 261 (133).58 S. Herzog and R. Schuster, 2. Naturforsch., 1962, 17b, 62.59M. A. Oranskaya and I. L. Perfilova, Zhur.neorg. Khim., 1961, 6, 257 (131);60 H.-J. Seifert and B. Gerstenberg, 2. anorg. Chem., 1962, 315, 56.61 M. W. Duckworth, G. W. A. Fowles, and R. G. Williams, Chem. and Ind., 1962,6aD. C. Bradley and M. L. Mehta, Canad. J . Chem., 1962, 40, 1710.6 3 P. H. Crayton and R. N. Vance, jun., J . Inorg. Nuclear Chem., 1961, 23, 154.64 S. A. Shchukarev, T. A. Tolmacheva, and V. M. Tsinsius, Zhzcr. neorg. Khwn.,Nauk X.S.X.R., Otdel. chim. Naulc, 608 (560).M. A. Oranskaya, Yu. S. Lebedev, and I. L. Perfilova, ibid., p. 259 (132).1285.1962, 7, 679 (345)NICHOLLS : THE TRANSITION ELEMENTS 157halides at 290" ; at higher temperatures the niobium phase forms a hexagonalNbC12.66 with NbCl,, but TaC1,.1-3.2 forms only TaC1, and TaC1,.65 Primaryand secondary amines solvolyse vanadium(1v) chloride at room temperature,two V-C1 bonds being broken;66 with vanadium(1v) fluoride, the adductsVF,,NH,, VP,,pyridine, and VP4,SeF4 have been isolated.67 Reaction ofpotassamide with K,VO( SCN), in liquid ammonia yields VO(NH,), whichundergoes deammoniation at room temperature to give the imide VO(NH).68The bonding in VO(H,O),2+ has been described in terms of molecularorbitals. The most significant feature of the electronic structure of V02+seems to be the existence of considerable oxygen-to-vanadium n-bonding.69The reduction of vanadium(v) by an excess of stannous ions in dilute hydro-chloric acid yields a mixture of vanadium(II1) and vanadium(1v) uia aninitial step involving a two-equivalent change in oxidation states.70 Thefluorometallates, M,VOF,, M,NbOF,, and M3TaOF6 (M = K, NH,), havebeen prepared by bromination of the transition metal in methanol andaddition of the resultant solution to the alkali-metal fluoride solution inmethanol. The charge-transfer spectra of vanadium(v) oxychloride inhydrocarbon solvents have been reported and complexes isolated withbenzophenone [VOCl,,PhCOPh], camphor [VOC!,,(C10H160),], quinoline[VOCl,,C,H,N], and acridine [VOCl,,C1,HgN].72 The oxyiodides of niobium,NbOI, and NbOI,, have been isolated from mixtures of niobium, niobium(n1)oxide, and iodine in a temperature gradient.73 The phosphorus oxychloridecomplexes, NbCl,,POCl, and TaCl,,POCl,, are unimolecular in benzeneand partly dissociated in nitrobenzene.74 The amine derivatives of nio-bium(v) and tantalum(v) chlorides and bromides have received extensivestudy. When secondary aliphatic amines react with these halides, mono-meric aminolysis products, e.g., NbCl,(NEt,),,NHEt,, TaBr,(NMe,),,NHMe,,are obtained.Complete replacement of the halogen atoms in these halideshas been achieved by reaction with lithium dialkylamides, giving, e.g.,Ta(NR,),. The reaction with niobium(v) chloride, however, results in somereduction of the niobium especially as the lengths of the alkyl chains on thenitrogen increase ; distillation of an NbC1,-LiNEt, mixture gives Nb(NEt,)4.With the sulphur donors dimethyl and diethyl sulphide, niobium(v) andtantalum(v) halides give 1 : 1 adducts but with tetrahydrothiophen 1 : 2 com-plexes are formed.,, It is not yet known whether these are seven-co-ordinate or possess the ionic structure [MX,,S(CH,),S] fX-.Anion-exchangestudies, and potential measurements with a, quinhydrone-calomel cell onperchloric acid solutions of tantalum(v) in hydrofluoric acid, have been6 5 P. FrGre, Ann. Chim. (France), 1962, 7, 85.6 6 M. W. Duckworth and G. W. A. Fowles, J . Less-Common Metals, 1962, 4, 338.6 7 R. G. Cave11 and H. C. Clark, J., 1962, 2692.6 8 0. Schmitz-Dumont and R. Eickermann, 2. anorg. Chein., 1962, 313, 241.6 9 C. J. Ballhausen and H. B. Gray, Inorg. Chem., 1962, 1, 111.'OD. 5. Drye, W. C. E. Higginson, and P. Knowles, J., 1962, 1137.71 A. E. Baker and H. M. Haendler, Inorg. Chem., 1962, 1, 127.72H.-L. Krauss and G.Gnatz, Chem. Ber., 1962, 95, 1023.73 H. Schafer and R. Gerken, 2. anorg. Chem., 1962, 317, 105.7 4 B. A. Voitovich and A. S. Barabanova, Zhur. neorg. Khim., 1961, 6, 2098 (1073).7 5 P. J. H. Carnell and G. W. A. Fowles, J. Less-Common Metals, 1962, 4, 40.7 6 D. C. Bradley and I. M. Thomas, Canad. J. Chem., 1962, 40, 449, 1355.7 7 F. Fairbrother and J. F. Nixon, J., 1962, 180158 INORGANIC CHEMISTRYinterpreted in terms of the species TaF,-, TaF,2-, TaFS3-, and TaFg4-;evidence for the co-ordination number nine in TaF9*- is discussed.78Chromium, Molybdenum, and Tungsten.-The diamagnetic complex,K,Cr( CN),, containing zerovalent chromium is obtained as a green precipitateupon reduction of potassium hexacyanochromate(II1) with potassium inliquid ammonia.79 Reduction of [Mo( bipy),]Cl, with the lithium salt of2,2’-bipyridyl in tetrahydrofuran results in the formation of tris-2,2’-bipyridylmolybdenum(0).80 Several new routes to chromium(n) fluoridehave been investigated ; in the chromium difluoride-chromium trifluoridesystem, the existence of a single fluoride covering the solid-solution range,CrF2.40-2.45, has been established. The oxidation of chromium(n) per-chlorate by sodium azide gives the complex hexa-aquochromiumIm) andpenta-aquomonoarnminechromium(m) ions, and a binuclear chromium( 111)ammine which is probably (H,0),Cr*NH*Cr(H20),.82 Molybdenum@)bromide and iodide can be obtained from molybdenum(@ chloride byreaction with the appropriate fused lithium halide. They yield derivativesof the types [(&t~,Br,)x,]~- and [(Mo618)X4] (x = c1, Br, I, or OH), in&-cating that bromo- and iodo-molybdenum(n) compounds are likely to containthe polynuclear groups Mo,Br8 and Mo,18 which are structurally similarto Mo,C~,.*~ The o-phenylenebisdimethylarsine complexes, Mo( diars),X,(X = C1, Br, I), are isomorphous with the corresponding rhenium com-pounds and have magnetic moments in the range 2.8-2.9 B.M.; they appeart o be the first known examples of octahedral bivalent molybdenum havingthe de4 configuration.84 The spectroscopic and magnetic properties of somemolybdenum complexes in oxidation states of +3, +4, and +5 have beenstudied. The visible spectra of the chloride and cyanide complexes arisefrom d-d-transitions, while the spectra of thiocyanate complexes and ofcomplexes of molybdenum( v) with organic ligands arise from charge-transfertransitions.The low magnetic moments of molybdenum(v) complexes areattributed to dimerisati~n.~~ Two new bromides of tungsten have beenprepared; tungsten(n1) bromide from the dibromide and liquid bromine in asealed tube at 50°, and tungsten(rv) bromide from the pentabromide andtungsten metal in a temperature gradient.86 I n the fluorides, K2NaCrF,and K2NaFeF,, the potassium and fluorine ions are in cubic close-packedarray with the smaller chromium or iron and sodium ions in octahedralholes.87 New tervalent cationic complexes includ6 those with picolylamine[Cr(pic),]3+ and [Mo(pic),13+, diethylenetriamine [Cr(dien),13+, and tri-ethylenetetramine [Cr(trien)Cl,] +.88 In the violet [CrA,C13] (A = N -substituted amide) there is considerable evidence to support the view that78L. P.Varga and H. Freund, J . P h p . Chem., 1962, 66, 21, 187.7 9 E . A. Heintz, J . Inorg. Nuclear Chem., 1961, 21, 262.8 0 S. Herzog and I. Schneider, 2. Chem., 1962, 2, 24.81 B. J. Sturm, Inorg. Chem., 1962, 1, 665.82M. Ardon and B. E. Mayer, J., 1962, 2816.a3 J. C. Sheldon, J., 1962, 410.84 J. Lewis, R. S. Nyholm, and I?. W. Smith, J., 1962, 2592.8 s P. C. H. Mitchell and R. J. P. Williams, J., 1962, 4570.a 7 K. Knox and D. W. Mitchell, J . Inorg. NucEeur Chem., 1961, 21, 253.R. E. McCarley and T. M. Brown, J . Amer. Chem. rSoc., 1962, 84, 3216.0. Kling and H.-L. Schlafer, 2. anorg.Chem., 1961, 313, 186; G. J. Sutton,Austral. J . Chem., 1962, 15, 232NICHOLLS : THE TRANSITION ELEMENTS 159the amides are co-ordinated through oxygen. 89 Whereas molybdenum( v)chloride is reduced by alkali-metal halides in iodine monochloride, molyb-denum(&) chloride is oxidised ; in both cases tetra-halogenomolybdates(1v)are formed, M,MoX, (M = K, Rb, Cs, Te; X = C1, Br).90 The quinque-valent oxychlorides, CrOC1, and MoOCl,, have been isolated. The chromiumcompound is stable at low temperatures in the absence of light, but above 0"it gradually disproportionates into chromium( VI) oxychloride and a chrom-ium(m) comp~und.~l The structural unit of molybdenum pentafluoride isa tetramer with molybdenum atoms at the corners of a square; the metalatoms are linearly linked by bridging fluorine atoms.92 The first complexhalides of molybdenum(v) have been precipitated from liquid sulphurdioxide solutions of molybdenum(v) chloride with rubidium and caesiumchlorides.The dark green RbMoC1, and CsMoC1, have magnetic momentsof 2.1-2.2 B.M.93 The hydrolysis of the MoOC~,~- ion in 5-6~1-hydro-chloric acid involves dimerisation, with the production of hydrogen andchloride ions :94MoOC1,2- + H,O + [MoOCl,],04- + 2H+ + 2C1-.The reflectance spectra of (NH,),CrOCl, and (NH,),MoOCl, have beenmeasured. The charge-transfer transitions involve the excitation of anelectron from the metal-oxygen n-bonding orbital into orbitals locatedmainly on the metal atom.95 Molybdenum(v) chloride is capable of abstract-ing the oxygen from triphenylphosphine oxide to form molybdenum(v)oxychloride which then complexes with excess of the ligand to giveMoOC1,,2Ph3PO; with a large excess of ligand, oxidation to MoO,Cl,occurs.96 Tungsten(vI) chloride gives aminobasic halides, T;lrCl,(NHR),,upon reaction with primary aliphatic amines ; secondary and tertiary aminesinitially co-ordinate but in the presence of an excess of the amine thetungsten is reduced to the quadrivalent state. The products identified are(NH,R,),WCl, and WC1,(NR2),2NHR, with secondary amines, andWCI,*NR, and (NHR,),WCl, with tertiary arnh~es.~' The chemical proper-ties of molybdenum(vr) fluoride have been investigated. The reaction withphosphorus trifluoride is2MoF, + PF, ---+ 2MoF, + PF,and nitric oxide causes reduction to NO+MoF,- (probably via NOF andMOP,).98 Tungsten(vI) oxychloride forms addition compounds with ethers,ketones, methyl cyanide, and pyridine ; solvolysis occurs with alcohols,&ketones, and carboxylic acids, typical products being WOCl,( OMe),89 C. L. Rollinson and R. C. White, Inorg. Chem., 1962, 1, 281.90 A. J. Edwards, R. D. Peacock, and A Said, J., 1962, 4643.91 H.-L. Krauss and G. Munster, 2. Naturforsch., 1962, 17b, 344; I. A. Glukhovg 2 A. J. Edwards, R. D. Peacock, and R. W. H. Small, J., 1962, 4486.9 3 E. Allen, D. A. Edwards, and G. W. A. Fowles, Chem. and Ind., 1962, 1026.9 4 G. P. Haight, jun., J. Inorg. Nuclear Chem., 1962, 24, 663.g 5 H. B. Gray and 0. R. Haze, Inwg: Chem., 1962, 1, 363.96 S.M. Horner and S. Y . Tyree, jun., Inorg. Chem., 1962, 1, 122.9 7 B. J. Brisdon, G. W. A. Fowles, and B. P. Osborne, J., 1962, 1330.98 J. R. Geichman, E. A. Smith, S. S. Trond, and P. R. Ogle, Inorg. Chem., 1962,1, 661; T. A. O'Donnell and D. F. Stewart, J. Inorg. Nuclear Chem., 1962, 24, 309.and S. S . Eliseev, Zhur. neorg. Khim., 1962, 7, 81 (40)160 INORGANIC CHEMISTRYWOCl,( *O*CMe:CH*CO*Ph), and WOC1( *O*C,H,*CO,)( *O*C6H4*C02H).99 Thebasic formula of the perchromate ion has been established as [CrO(OJ,OH]-;several salts have been isolated, and all are violently explosive. 100 Adductsof chromium oxide diperoxide, CrO,, with pyridine, 2,2’-bipyridyl, and1,lO-phenanthroline have low magnetic moments (p = 0-4-0-9 B.M.) show-ing that they contain chromium(vI).The magnetic moments of chromiumdiperoxide (CrO,) adducts are in the range 2-7-24 B.M. indicating chrom-ium to be in the oxidation state +4.1°1 Two main products, Mo40,,2- andH~MO~OO,,, are obtained upon acidification of molybdate Mo0,2- ions.102The preparation and properties of 12-tungstochromic, 12-tungstoarsenic,and 12-tungstomanganic acids have been described, and the thermal deconi-position of 12-heteropolytungstates studied.103Manganese, Technetium, and Rhenium.-The visible and ultravioletspectra of the green tetrahedral [MnX,12- anions (X = C1, Br, I) have beensystematically studied ; qualitative interpretations of the spectra are in agree-ment with the predictions of the ligand-field theory. lo4 The colourlessmanganese( 11) complexes with the chelating ligand 2-picolylamine7 Mn pic, X,(X = C1, Br, I), (Mn pic3)Iz, and ( M i pic,)(ClO,),, have six-co-ordinate struc-tures; for one other complex, Mn pic Cl,, the structure is unknown.lo5 Rhen-ium(=) is stabilised by co-ordination with cyanide ion in Na31.Re(CN),,H20] ;it is prepared by the sodium amalgam reduction of perrhenate in the presenceof excess of sodium cyanide.lo6 Five-co-ordination of rhenium(1r) occurs inReX,(TAS) [X = C1, Br, I ; TAS = bis-(o-diphenylarsinopheny1)phenyl-arsine] ; the quadridentate tris- (o-diphenylarsinopheny1)arsine (&AS) formsReX2(QAS).lo7 The spin-free manganese(@ complexes, [Mn(bipy O,),](C104)3 and [Mn(bipy 02)3](s208)1.5, are obtained from aqueous mangan-ese(rI1) sulphate in the presence of 2,2‘-bipyridyl 1,l-dioxide upon oxidationwith perchlorate or persulphate.lo8 The existence of at least three classesof complex of tertiary monophosphines with rhenium halides has beenestablished.In the solid state [ReX3,PR,], are probably halogen-bridgedpolymers containing octahedral rhenium(=) ; [ReX,(PR,)] only exists whereX = C1, and the compounds [ReX,(PR,),] are polymers containing rhenium-rhenium bonds in the solids.109 The previously reported bis( triphenyl-phosphine)rhenium(m) chloride has been shown, by infrared measurements,to contain oxygen.1l0 Manganese(rv) fluoride can be prepared by heatingthe trifluoride in fluorine at 400°, and, by heating an equimolar mixture oflithium and manganese(=) fluorides in a stream of fluorine at 350°, LiMnF,99 H.Funk and G. Mohaupt, 2. anorg. Chem., 1962, 315, 204.l o o W. P. GrifZth, J., 1962, 3948.lox J. E. Fergusson, C. J. Wilkins, and J. F. Young, J., 1962, 2136.l o z M. K. Cooper and J. E. Salmon, J., 1962, 2009.lo8D. H. Brown and A. J. Hyde, J., 1962, 3186; D. H. Brown, ibid., pp. 3189,104 F. A. Cotton, D. M. L. Goodgame, and M. Goodgame, J. Amer. Chem. SOC.,lo5 G. J. Sutton, Austral. J. Chem., 1962, 14, 550.lo6 S. Sen, 2. anorg. Chem., 1962, 315, 315.R. J. Mawby and L. M. Venanzi, J., 1962, 4447.lo* R. S. Nyholm and A. Turco, J., 1962, 1121.loo J. Chatt and G. A. Rowe, J., 1962, 4019.I1O C. J. L. Lock and G. Wilkinson, Chem. and Ind., 1962, 40.3322, 4408.1962, 84, 167NICHOLLS : THE TRANSITION ELEMENTS 161is obtained.l'l Crystalline hydrates of the acids H2ReX, (X = F, C1, Br)and of salts of these acids and the iodo-acid, H2Rd6, with the cations[Co(NH3),ISS and [Cr(NH,),],+, have been described.112 Potassium tetra-cyanodioxorhenate(Iv) is reduced in solution by borohydride ion to the darkblue K,Re(OH),(CN),.l13 Several new halides of rhenium have beenisolated.114 Rhenium(vI) chloride is a dark solid which hydrolyses torhenium(1v) oxide and perrhenate : SRe(vr) + Re(Iv) + 2Re(v11).Brominereacts with rhenium at 650" to give the pentabromide; the tribromide isobtained on heating the pentabromide in vacuo or in an inert atmosphere.Rhenium heptasulphide is reduced by hydrogen to rhenium(vI) sulphide. 115In 65% oleum, permanganates and chromates evolve oxygen ; the resultingsolutions (blue with manganese and green with chromium) contain man-ganese(1v) and chromium(v) respectively.Iron, Ruthenium, and Osmium.-A new class of iron isocyanide complexeshave the structure [ (RCH,*NC),FeCN]Br, and studies of their reactions withnucleophiles and alkyl halides have been made.117 Tris-(o-diphenylarsino-pheny1)arsine reacts with nitrosylruthenium compounds to give RuX2( &AS) ;in these compounds six-co-ordination appears to be preserved despitestringent steric requirements of the chelating agent.118 The quadrivalentferrocyanide ion, Fe( CN),4-, is virtually absent in acid solution, whereprotonation occurs to HFe(cN)63- and H2Fe(CN),2-.119 The previouslyreported hydrazine complex, [Ru2C12(N2H,),]C14, has been proved to be[RuCl(NH,),]Cl,, and its crystal structure has been determined.120 Severalnew osmium halides have been prepared;l21 these are the three iodides,OsI, OsI,, and OSI,, and two bromides, OsBr, and OsBr,. Heptavalentosmium has been reported from two sources. The emerald green, para-magnetic OsOF, has been prepared by fluorination of osmium(1v) oxide;it hydrolyses to osmium(vIn) oxide, and gases smelling of ozone areevolved.122 Characterisation of the compounds A2BB10, (A = Ca, Sr, Ba,B = a variety of uni-, bi-, and ter-valent cations and B1 = 0 s or Re) showsthat many of thein have the ordered perovskite structure; in Ba,LiOsO,there is some evidence for osmium(vn) .I23Cobalt, Rhodium, and Iridium.-Finely divided cobalt, nickel, and palla-dium react at 200 O with o-phenylenebis( diethylphosphine), forming thezerovalent M[C,H,(PEt,),] ; the neighbouring Group VIII metals do notI l l R.Hoppe, 'W. Dahne, and W. Klemm, Annalen, 1962, 658, 1.112 G. Brauer and H. D. Allardt, 2. anorg. Chem., 1962, 316, 134.113 P. H. L. Walter, J. Kleinberg, and E. Griswold, Inorg. Chem., 1962, 1, 10.l14R. Colton, Nature, 1962, 194, 374; idem, J., 1962, 2078.115 K. Traore, G. Coeffier, and J. Brenet, Compt. rend., 1962, 491; idem, Bull. SOC.116 H. C. Mishra and M. C. R. Symons, Proc. Chem. SOC., 1962, 23.117 W. Z. Heldt, J . Inorg. Nuclear Chem., 1961, 22, 305; ibid., 1962, 24, 73, 265.ll* J. G. Hartley and L. M. Venanzi, J., 1962, 182.119 J. Jordan and G.J. Ewing, Inorg. Chem., 1962, 1, 587.1 2 0 C. K. Prout and H. M. Powell, J., 1962, 137.1 2 1 J. E. Fergusson, B. H. Robinson, and W. R. Roper, J., 1962, 2113; S. A.Shchukarev, N. I. Kolbin and I. N. Semenov, Zhur. neorg. Khim., 1961, 6, 1246 (638);I. N. Semenov and N. I. Kolbin, ibid., 1962, 7, 219 (111).1z2 N. Bartlett, N. K. Jha, and J. Trotter, Proc. Chem. Soc., 1962, 277.123 A. W. Sleight, J. Longo, and R. Ward, Inorg. Chem., 1962, 1, 245.china. France, 1962, 361.I62 INORGANIC CHEMISTRYreact except in the presence of hydrogen, in which case iron gives the dihy-dride ~~~~S-{F~H,[C~H,(PE~,),],~.~~~ Two rhodium(1) complexes with 2,2'-bipyridyl have been described. It is suggested that the diamagneticRh(bipy),C104,3H20 is the perchlorate of the tetragonal trans-[Rh(bipy),(H,O),] + cation, but the structure of the paramagnetic Rh(bipy),N0,,3H20is less certain.125 Detailed studies have been made of the effect of addingchloride, bromide, and thiocyanate ions t o solutions of cobalt(I1) in aceticacid and ethanol.From ion-migration and spectrophotometric measure-ments the ionic species present are postulated to be (Cox)+, (Cox,), (COX,)-,and COX^)^-.^^^ In other solvents, e.g., nitromethane, acetone, and di-methylformamide, there is considerable interaction between the solutecobalt (II) chloride and the solvent. 127 Complexes containing the tetrahedral[CoX,I2- ion (X = C1, Br, I) can be isolated from ethanolic solution; theirRacah parameters (B') and spin-orbit coupling constants (A') show thatappreciable overlap of metal and ligand orbitals occurs.128 Magnetic andspectrophotometric measurements indicate that cobalt(I1) complexes withN-substituted salicylaldimines are tetrahedral in the solid state and inbenzene solution; in pyridine they take up two molecules of solvent andbecome 0ctahedral.1~~ The ultraviolet spectra of these complexes, however,show that the N-methyl derivative has a configuration different from theothers ; it is probably planar.130 Tetramethylene sulphone forms the un-stable compounds Co(C,H8S0,)C1, and CO(C,H~SO,)~(C~O~),, in which thesulphone presumably is bidentate through the two oxygen atoms.131 Withpyrazine and some methylpyrazines cobalt(I1) halides form several halogen-bridged dimers, [LCoX,],, in which the cobalt atom is tetrahedral, and poly-meric complexes, [LCoX,], or [L2CoX2],, in which the cobalt is usually0ctahedral.1~2 There has been little evidence that oxyacids can form four-membered rings with elements of tetrahedral symmetry; methyl- and ethyl-phosphinic acids, however, form blue cobalt@) salts with the strain-freepolymeric structure ( l).133 Reactions of cobalt(@ halides with amines,124 J.Chatt, F. A. Hart, and D. T. Rosevear, J., 1961, 5504.125 B. Martin, W. R. McWhinnie, and G. M. Waind, J . Inorg. Nuclear Chem., 1961,lea P. J. Pro11 and L. H. Sutcliffe, J . Phys. Chem., 1961, 65, 1993; S. A. Shchukarev12'S. Buffagni and T. M. Dunn, J., 1961, 5105; D. A. Fine, J . Amer. Chem. SOC.,128 F. A. Cotton, D. M.L. Goodgame, and M. Goodgame, J . Amer. Chem. SOC.,Iz9 B. 0. West, J., 1962, 1374; L. Sacconi, M. Ciampolini, F. Maggio, and F. P.I3O H. Nishikawa, S. Yamada, and R. Tsuchida, 2. anorg. Chem., 1962, 316, 278.I3l C. H. Langford and P. 0. Langford, Inorg. Chem., 1962, 1, 184.132A. B. P. Lever, J. Lewis, and R. S. Nyholm, J., 1962, 1235.133 G. E. Coates and D. S. Golightly, J., 1962, 2523.23, 207.and 0. A. Lobaneva, Zhur. neorg. Khim., 1961, 6, 804 (410).1962, 84, 1139.1961, 83, 4690.Carasino, J . Amer. Chem. Soc., 1962, 84, 3246NICHOLLS : THE TRANSITION ELEMENTS 163phosphines, and arsines have been extensively investigated. 134 Tetrahedralcompounds, CoX2,2EtNH2, CoX2,2Et2NH, CoX2,3EtPH2, and CoX2,2Et2PH,are formed with primary and secondary aliphatic amines and phosphines ;aromatic phosphines can form the octahedral (PhPH,),,CoI,.With tri-ethylamine the complex formed, CoCl,,Et,N, may contain doubly halogen-bridged dimers, while, with triethyl-phosphine and -arsine, tetrahedralCoX,,2PEt3 and CoX2,2AsEt3 are formed. The bright blue CoC1,,2A1C13,formed when the chlorides are melted together and cooled, is, structurally,cobalt(I1) chloroaluminate, Co(AlCl,),. The crystal structure of this com-pound shows, surprisingly, that the cobalt is octahedrally co-ordinated. 135Infrared spectra of the binuclear M6[Co,(CN),,],4H,0 (M = Nay K) indicatesimilar metal-metal bonding in the [Co2(CN),,]6- ion as in the isoelectronicmolecule Mn2( CO),,. l36 The f i s t well-characterised rigorously square-planarand spin-free complex of cobalt(I1) has been formed with the ligand maleo-nitriledithiolate (MNT) (2) ; [Bun4NfI2Co(MNT), has acomplexes studied during the year include those withmethyl isocyanide,138 benzimidazole, l39 the enolateanion of dipivaloylmethane,l40 and o-phenylene-mination of carbonatotetra-amminecobalt(m) bromideshows that the carbonate group acts as a chelate to form a four-memberedring.The cobalt atom is thus surrounded by two oxygen and four nitrogenatoms at the corners of a somewhat distorted 0ctahedron.1~2 The thermal de-composition of hexa-amminecobalt(m) azide yields a diammine of cobalt(=)azide :143magnetic moment of 3.92 B.M.13' Other cobalt(=) 2 - [ N;>c = ::.]bisdimethylarsine. 141 The X-ray structure deter- (2)[CO(NH3)61(N3)3 * Co(NH3)2(N3), + 4NH3 + 1'5N2.The synthesis and properties of the new nitritopenta-ammines,[ (NH3),M*ONO]"+ [M = Rh(nI), Ir(Irr), Pt(w)], have been described.144The reaction of trisethylenediamineiridium( III) iodide with potassamide inliquid ammonia leads to a sequence of products corresponding to the succes-sive removal of protons from the ligand nitrogen atoms.Of these products,[Ir(en-H),(en)]I and K,[Ir(en-2H),(en H)] have been isolated and char-acterised; the former also results from the reduction of Ir(en),I, withpotassium in ammonia.145134 W. E. Hatfield amd J. T. Yoke, tert., Inorg. Chern., 1962,1,463, 470,475; D. M. L.Goodgame, M. Goodgame, and F. A. Cotton, ibid., p. 239; K. Issleib and G. Wilde,2. anorg.Chem., 1962, 312, 287.135 J. A. Ibers, Ada Cryst., 1962, 15, 967.136 R. Nast, H. Ruppert-Mesche, and M. Helbig-Neubauer, 2. anorg. Chem., 1961,312, 314.13' H. B. Gray, R. Williams, I. Bernal, and E. Billig, J . Amer. Chern. SOC., 1962,84, 3596.138 A. Sacco and F. A. Cotton, J . Amer. Chern. SOC., 1962, 84, 2043.139 M. Goodgame and F. A. Cotton, J . Amer. Chem. Soc., 1962, 84, 1543.l40F. A. Cotton and R. H. Soderberg, J . Amer. Chem. SOC., 1962, 84, 872.lalT. M. Dunn, R. S . Nyholm, and S . Yamada, J., 1962, 1564.142 G. A. Barclay and B. F. Hoskins, J., 1962, 586.143 T. B. Joyner and F. H. Verhoek, Inorg. Chern., 1962, 1, 557.144 F. Basolo and G. S . Hammaker, Inorg. Chern., 1962, 1, 1.145 G. W. Watt, L. E. Sharif, and E. P. Helvenston, Inorg.Chem., 1962, 1, 6164 INORGANIC CHEMISTRYNickel, Palladium, and Platinum.-Zerovalent nickel and palladium com-plexes, [ML,], [MLL’], and [ML’], [M = Ni, Pd; L = chelate ditertiaryphosphine, e.g., Me,P*CH,*CH,*PMe,; L’ = ditertiary arsine, e.g., o-C,H,(AsMe,),, or tritertiary phosphine], have been isolated by reduction ofthe corresponding nickel(@ and palladium(I1) complexes with a variety ofreducing agents. 146 Nuclear magnetic resonance and infrared spectroscopyshow no evidence of hydrogen bound to platinum in tris(tri-p-fluorophenyl-phosphine)platinum, so that this can be considered to be a true platinum(0)compound. 14’ Nickel dissolves anodically in acetonitrile and dimethyl-formamide containing tetramethylammonium chloride, as a mixture ofnickel(1) and nickel@).Nickel(1) is stable enough to be titrated againstiodine. 148 Two reviews have appeared concerning the stereochemistry ofcomplexes of nickel(=), palladium(n), and platinum(II).149 The phasediagram of the system nickel chloride-cesium chloride shows two con-gruently-melting compounds, CsNiC1, and Cs,NiCl,. In the latter, thenickel is surrounded by four chloride ions tetrahedrally, the fifth chlorinebeing considerably more distant. l50 Complex nickel(I1) fluorides can beclassified according to their magnetic behaviour. Normal paramagneticcompounds include Li,NiF, and (NH,),NiF,,2H20, while KNiF, and M,NiF,(M = K, Rb, NH,, T1) are antiferromagnetic; MNiF, (M = Na, NH,, Rb)are weakly ferromagnetic.151 In bis(thiosemicarbazidato)nickel(n) thenickel atom co-ordinates two sulphur and two nitrogen atoms in a trans-planar configuration.152 The paramagnetic [NiN02en,]C104 contains octa-hedrally-co-ordinated ni~ke1.1~~ The reflection spectra of nickel(=) com-plexes of the bidentate 1 -amino-1 -aminoethylcyclohexane (am) show thatthere is slight distortion from octahedral in the violet Ni am,Br, while thepale blue Ni am,(CCl,*CO,), is strongly di~torted.1~4 There are two newtypes of tetrahedral nickel(I1) complexes.Dark green di-iodabis(pyridine) -nickel(=) and light green di-iodobis-(p-picoline)nickel(r) contain nitrogenbonded tetrahedrally to nicke1,155 and isopropyl- and s-butyl-salicylaldi-minonickel(rc) are the first tetrahedral nickel@) chelates.156 The relation-ship between solution paramagnetism and solute association in certainnickel(rr) complexes is now well established.In solvents of low co-ordin-ating power, monomers interact to form an associated species, thereby pro-ducing effective five- or six-co-ordination of some or all of the nickel atomsin the aggregate. Solutions of nickel@) acetylacetonate in benzene containtrimeric units of Ni(acac),, and the solution paramagnetism of the bis-146 J. Chatt, F. A. Hart, and H. R. Watson, J., 1962, 2537.147 A. D. Allen and C. D. Cook, Proc. Chem. SOC., 1962, 218.148 T. C. Franklin and C. R. Parsons, J . Electrochem. SOC., 1962, 109, 641.149 C. M. Harris and S. E. Livingstone, Rev. Pure Appl. Chem., 1962, 12, 16; J. R.150 E. Iberson, R.Gut, and D. M. Gruen, J. Phys. Chem., 1962, 66, 65.151 W. Rudorff, J. Kandler, and D. Babel, 2. anorg. Chem., 1962, 317, 261.152 L. Cavalca, M. X’ardelli, and G. Fava, Acta Cryst., 1962, 15, 1139.lS3 F. J. Llewellyn and J. M. Waters, J., 1962, 3845.154 C. K. Jorgensen, 2. anorg. Chem., 1962, 316, 12.lS5 M. D. Glonek, C. Curran, and J. V. Quagliano, J. Amer. Chem. Soc., 1962, 84,156 L. Sacconi, P. L. Orioli, P. Paoletti, and M. Ciampolini, Proc. Chem. SOC., 1962,Miller, Adv. Inorg. Chem. Radiochem., 1962, 4, 133.14.255NICHOLLS : THE TRANSITION ELEMENTS 165(R ON-salicylaldimine)nickel( 11) complexes is dependent upon the nature ofthe substituent R Complexes of palladium(I1) halides with second-ary and tertiary phosphines have been investigated.Those complexes, offormula PdXPR,L, (X = C1, Br, I, SCN; R = Et, Ph; L = secondary ortertiary phosphine), have the novel phosphorus-bridged structure (3). 15* Inyellow crystalline trans- (Et,N,O),PdCl,, co-ordina-(3) / x tion is from the oxygen at0ms.1~~ Five-co-ordin- L,pd, PhZ pate complexes of palladium(I1) with tris-o-diphenyl- x' " p A p d K Larsinophenylarsine, of the type [PdX(QAS)] +, Ph2are probably trigonal bipyramidal. 160stitution reactions of palladium(I1) complexes have been studied. Ethylene-ag-bis(dipheny1arsine) (EDA) reacts with the compounds [Pd en X,](X = Cl, Br), to give [Pd(EDA)X,] and [Pd(en),]X,, while [Pd en 12]gives only [Pd(EDA)I2].1G1 Interaction of unidentate ligands (L),e.g. , ammonia and pyridine , with halogen-bridged anionic complexes,(NEt4)2(Pt,X,) (X = Br, I), has led to isolation of [NEt4][PtLX,].162 Frompure quadrupole resonance of the halogens in K,PdX, (X = C1, Br) andK,MBr, (M = Pd, Pt), aiid use of Townes and Dailey's relationship, it isconcluded that the former compounds have 60% covalent character and thelatter 40y0.163 A large amount of work on the preparation and isomerismof platinum complexes has been published, particularly in the Russianjournals, e.g., ref.164. Isomerisation of solutions of cis- and trans-bis(tri-ethylphosphine)dichloroplatinum( II) is rapid in sunlight ; the very differentdipole moments of the isomers are reflected in the solvent dependence ofthe steady state.165 Two remarkable oxidations with platinum hexa-fluoride have been discovered.With oxygen, a compound of compositionF,o,Pt can be obtained either on mixing oxygen and platinum(v1) fluorideor by fluorination of platinum in a glass or silica apparatus. Upon hydrolysisthis compound gives the PtF,,- ion (which cannot be otherwise synthesisedin aqueous media), and, in view of its magnetic properties (p = 2-84 B.M.)and X-ray powder photograph (which is very similar to that of NOOsF,), it isformulated as dioxygenyl hexafluoroplatinate(v). This formulation stimu-lated the discovery of XePtF,, an orange solid, stable at room temperatureand sublimable in vacuo.166Some sub-15' J. P. Fackler, J . Amer. Chem. SOC., 1962, 84, 24; H. C. Clark, K. MacVicar, andR. J. O'Brien, Canud. J . Chem., 1962, 40, 822; R.H. Holm, J . Amer. Chem. SOC., 1961,83, 4683; R. H. Holm and K. Swaminathan, Inorg. Chem., 1962, 1, 599.158 R. G. Hayter, Nature, 1962, 193, 872; idem, J . Amer. Chem. SOC., 1962, 84,3046.159 R. D. Brown and G. E. Coates, J., 1962, 4723.160 C. A. Savage and L. M. Venanzi, J., 1962, 1549.161 G. W. Watt and R. Layton, Inorg. Chem., 1962, 1, 496.162 S. E. Livingstone and A. Whitley, Awtral. J. Chem., 1962, 15, 175.K. Ito, D. Nakamura, Y. Kurita, K. Ito, and M. Kubo, J . Amer. Chem. SOC.,1961, 83, 4526.164 V. I. Belova, Ya. K. Syrkin, and L. I. Baranova, Zhur. neorg, Khim., 1961,6, 625 (319); A. V. Babaeva and N. I. Ushakova, ibid., p. 151 (297); L. N. Essen andD. P. Alekseeva, ibid., p. 857 (436); B. Ud-Din and J. C. Bailar, j u ., J . Inorg.Nuclear Chem., 1961, 22, 241.165P. Haake and T. A. Hylton, J . Amer. Chem. SOC., 1962, 84, 3774.166 N. Bartlett and D. H. Lohmann, Proc. Chem. SOC., 1962, 115; N. Bartlett,ibid., p. 218166 INORGANIC CHEMISTRYCopper, Silver, and Gold.-A mass-spectrometric examination of theabsolute isotopic abundance ratio in natural silver has led to the valuefor the atomic weight of silver, on the unified scale (12C = 12), of107.8694 & 0-0026.167 Compounds containing triphenylgermyl groupsbonded to copper, silver, and gold have been prepared by reaction of thecomplexes R,PMX [M = CU(I), Ag(I), Au(I)] with triphenylgermyl-lithium.The gold compound, Ph,GeAuPPh,, is stable to air and water but the stab-ility falls off in the series Au > Ag > C U .~ ~ ~ Adducts of silver perchlorateand borofluoride with triphenyl derivatives of some Group V elements havebeen synthesised ; they are of the types Ph,N,AgClO,, (Ph3Sb),,AgC10,, andPh,Bi,AgClO,. Azobenzene forms 3PhN2Ph,2AgC10,, PhN2Ph,CuC10,, and3PhN2Ph,2AgBF,. 169 In (AgCl),en, the ethyleiiediamine acts as a bridginggroup between the two silver ions, while Ag en C1 is probably dimeric, havinglinearly co-ordinated silver.170 Stability constants of copper(1) and cop-per(@ complexes with several nitrogen donors have been measured, andelectrode potentials for the Cu2f-Cu+ complexes calculated; in every casethere is preferential stabilisation of the cuprous state. 171 Copper(=) bromideis reduced upon reaction with potassium diphenylphosphide, forming red-violet CuPPh, and tetraphenyldiphosphine.Treatment of copper( I) bromidewith an excess of KPPh, results in the formation of K(c~PPh,).l7~ Unlikesilver@) complexes with oxine, 2-hydroxyquinoline forms a 1 : 1 complex,Ag( C,H,*NO). 1 7 3 Pyridine and quinoline N-oxides co-ordinate with cop-per(@ salts to give a variety of products. The mono-complexes,Cu(C,H,*NO)X, (X = C1, Br), have the unusually low magnetic moments of0.4-0.8 B.M. This has led to their being formulated as binuclear oxygen-bridged structures in which electron-exchange demagnetisation can occurbetween pairs of adjacent copper atoms Wia the oxygens.17, Two types ofchelate are formed with copper(n) and pyrazinylmethyl 2-pyridyl ketone.One type consists of a six-membered chelate ring in which the pyrazine(4) HcyN] Nnitrogen is bonded to copper (4), and in the other type, ( 5 ) , the pyridinenitrogen is bonded to copper forming a five-membered chelate ring.175167 E.A. C. Crouch and A. K. Turnbull, J., 1962, 161.168 F. Glockling and K. A. Hooton, J., 1962, 2658.169 R. H. Nuttall, E. R. Roberts, and D. W. A. Sharp, J., 1962, 2854.170 0. Newmann and D. B. Powell, J., 1962, 3447.171 C. J. Hawkins and D. D. Perrin, J., 1962, 1351.173 K. Issleib and H.-0. Frohlich, Chem. Ber., 1962, 95, 375.173 W. W. Wendlandt and J. Haschke, Nature, 1962, 379.174 C. M. Harris, E. Kokot, S. L. Lenzer, and T. N. Lockyer, Chem. and Ind., 1962,176 N. Naqui, E. L. Amma, and Q. Fernando, J. Inorg. Nuclear Chem., 1962, 24,651; K.Issleib and A. Kreibach, 2. anorg. Chem., 1962, 313, 338.609NICHOLLS : THE TRANSITION ELEMENTS 167Studies on copper(n)-a-amino-acid chelates indicate that three differentenvironments of copper atoms can be found depending upon the amino-acid.In copper(n) a-amino-a-methyl-propionate and l-aminocyclopentane-l-carboxylate, the copper atoms appear to be truly four-planar co-ordinate. 170Copper(@ N-arylglycinates have two structures ; the usual chelate amino-acidstructure (6) is more stable than the type (7) in which nitrogen no longeracts as a donor. The addition compounh (Me*CO*CH*CO,Et),Cu(C,H,N),ArIOC-0, ,NH-CH, I cu IHC-HN' 'o-coand (MeCO *CH 430 2Et) 2Cu( C5H5N) are probably five - co -ordinate, theadditional molecule of heterocyclic base being free in the crystal 1atti~e.l'~The addition of nitrate ions to copper(=) salts in acetonitrile andethylacetateresults in the formation of nitrato-complexes according to a concentration-dependent equilibrium :I78Cu2+ + 2N03- + &(NO3)+ + NO,- + Cu(NO,),.The polarographic behaviour of copper ions in a number of non-aqueoussolvents has been studied.The copper(1) ion is stable with respect to dis-proportionation in propan-1-01, propan-2-01, acetone, and nitromethane ; itsstability appears to be due to a lower solvation energy of the copper(=)ion in these solvents.17B A review has appeared dealing with the higheroxidation states of silver.l*oZinc, Cadmium, and Mercury.-The cadmium(1) ion, Cd22+, has beenidentified by Raman spectroscopy on molten 0-67Cd2( AlC1,),-0-33Cd( AlC1,) 2.l8 Four - co -ordinat e non-electrolytes, [ M( diars) X,] (X = C1,Br, I, ClO,), are formed by all three metals in this group with o-phenylene-bisdimethylarsine. In solution, some formation of a salt [M1l(diars),](M1lX,)occurs; this is most evident for the complexes [Hg(diars)12].182 Ceramictechniques being used, three compounds can be prepared in the CdO-B,03system; they are 3CdO,B,O,, 2Cd0,B20,, and 2Cd0,3B203.183 The degreeof complex halide formation of cadmium salts in molten sodium nitrate-potassium nitrate increases in the series C1- < Br- < I-.184 The action of17% D. P. Graddon and L. Munday, J. Inorg. Nuclear Chem., 1961, 23, 231; D. P.177D. P. Graddon and E. C.Watton, J. Inorg. Nuclear Chem., 1961, 21, 49.1'8B. J. Hathaway and A. E. Underhill, J., 1962, 2256.L7B I. V. Nelson, R. C. Carson, and R. T. Iwamoto, J. Inorg. iluclear Chem., 1961,lSo J. A. McMillan, Chem. Rev., 1962, 82, 65.J. D. Corbett, Inorg. Chem., 1962, 1, 700.ls2 J. Lewis, R. S. Nyholm, and D. J. Phillips, J., 1962, 2177; G. J. Sutton, Austral.lS3 P. B. Hart and E. G. Steward, J. Irwrg. Nuclear Chem., 1962, 24, 633.184 D. Inman and J. O'M. Bockria, Trans. Faraday Soc., 1961, 57, 2308.Graddon, ibid., 1961, 22, 85.22, 279.J . Chem., 1962, 14, 545168 INORGANIC CHEMISTRYanhydrous hydrogen chloride on bispyridinecadmium chloride produces(pyH),CdCI, ; in aqueous hydrochloric acid (pyH)CdCl, is formed.185Cadmium(=) forms 1 : 1, 1 : 2 and 1 : 3 complexes with amino-acids; themost stable are those involving ligands capable of forming five-memberedchelate rings, e.g., glycinate, a-alaninate.la6 Some new complexes of mer-cury@) with oxygen donors are unusual in being six-co-ordinate ; whitecrystals, (HgL6)(C1o4),, have been isolated (with L = pyridine N-oxide,dimethyl sulphoxide, tetrahydrothiophen oxide, and thioxan oxide).ls7 Acrys t a1 - s tru ct ure examination of bisme t h y It hiomer cury shows it to containsimple molecules of (MeS),Hg in which the S-Hg-S group is linear.188Trip hen y lphosphine reacts with quaternary iodomer curat e s in acetone orethanol, giving iodo(triphenylphosphine)mercury(n:) together with either aquaternary iodomercurate (with a higher I : Hg ratio than the reactant) ora quaternary iodide. (Ph,P)2HgX, and (Ph3PHgX,), (X = C1, Br) areconverted by methyl iodide into the corresponding trimethylphosphoniumiodomercurates.The reaction involves halogen exchange as well asquaternisation :(Ph3P).HgX2 + (n + 2)MeI -+ (Ph,PMe).HgI(,+,) + 2MeX.General reviews appearing during the yearhave been concerned with polymeric co-ordination compounds, 1 the presentstate and future development of co-ordination chemistry,2 and with thecoupling of vibrational and electronic motions in degenerate electronic statesof inorganic complexe~.~There has been a rapid exploitation of Mossbauer spectra (resonant y-rayabsorption in solids) in physicochemical investigations ; most of the spectraso far recorded are for iron compounds.Of particular interest from thechemical point of view is the attempt to correlate the “isomer shift ”observed in various compounds with a detailed formulation of the electronicenvironment of the iron nucleus, In potassium ferrate, the isomer shift issmaller than predicted for a 3&2 electron configuration, presumably becausethe 3d electron density is augmented by d3s hybridisation in the tetrahedralFeOa2- ion. The data on the cyclo-octatetraeneiron carbonyls, C,H,Fe,(CO),and c8H8Fe( Go),, suggest essentially completely covalent bonding betweenthe iron atom and the n-electron distribution in the cyclo-octatetraene ring.The charge density of the delocalised n-electrons is essentially the same inthe C4 residue of C,H,Fe(CO), as in the two C, residues in C,H,Fe,(CO),t o which the iron atoms are bonded.This is consistent with earlier X-raydata showing iron to have a quasi-octahedral configuration comprising threeComplexes.-( a) General.lE5 H. Buss, H. W. Kohlschutter, and D. Maulbecker, 2. Naturforsch., 1962, 17b,lE6 J. H. Smith, A. M. Cruickshmk, J. T. Donoghue, and J. F. Pysz, jun., Inorg.R. L. Carlin, J. Roitman, M. Dankleff, and J. 0. Edwards, Inorg. Chem., 1962,lssD. C. Bradley and N. R. Kunchur, Chern. and Ind., 1962, 1240.lag G. B. Deacon and B. 0. West, J., 1961, 5127; idem, J . Inorg. Nuclear Chem.,485.Chem., 1962, 1, 148.1, 182.1962, 24, 169.I. Haiduc, Uspekhi Khim., 1961, 1124 (498).A. A. Grinberg, Uspekhi Khim., 1961, 755 (334).A. D. Liehr, Progr.Inorg. Chem., 1962, 3, 281NICHOLLS : THE TRANSITION ELEMENTS 169CO groups and three of the eight carbon-carbon bonds.* The lattice energiesand crystal-field stabilisation energies have been presented for some oxidesand halides of metals in the first and second transition series. It is shownthat some further stabilisation (“ metal lattice stabilisation ”) is present inthe metal lattice which masks the effect of the crystal field upon the experi-mental enthalpies of formation of these compounds. From a comparisonof the variation of lattice energy with atomic number in the actinide oxidesand halides it appears likely that the 5f shell rather than the 6d is progres-sively filled in these compounds. Simple relationships have been derivedfor lattice energies and heats of hydration of bivalent cations in the calciumto zinc series.The lattice energies ( U ) of octahedrally co-ordinated com-pounds in this series are represented by: - U = C + I - n,A, where C is aconstant, I is the ionisation potential of the atom, n, the number of 3delectrons in e, antibonding orbitals, and A is a constant numerically com-parable with the spectroscopic ligand-field splitting factor.6 There has beena revival of interest in the study of rotatory dispersion curves, i.e. molecularrotation plotted against wavelength, as a tool for structural and stereo-chemical investigations of complexes. A dissymmetric d 3 or d6 complexwith C, symmetry may give two or three circular dichroism bands in thewavelength region of the higher energy ligand-field absorption band, whereasthe corresponding D, complex can give no more than one such absorption inthat region.The observation that the (-)-trisoxalatocobalt(m) ion givestwo circular dichroism bands in the 4000-5000 A region indicates that someof the ions have approximate C, symmetry.7 While cis- and trans-isomersof the inert chromium(III), cobalt(m), and rhodium(m) benzoylacetonatescan be separated, only the more stable trans-isomers can be isolated from thelabile complexes of tervalent aluminium, manganese, and iron : the con-figurations of these cis- and trans-isomers have been established by use ofproton magnetic resonance.* In the tervalent transition-metal acetylaceton-ates from titanium to cobalt, the n +n* transition energy increases withincreasing number of de electrons and this is attributed to metal-ligandn-interaction.In order to explain the ‘( normal ” value of the ligand-fieldsplitting parameter, A, it is suggested that the metal-ligand n-interactionoccurs between the d, orbitals of the metal and both higher, empty 7c*orbitals and lower filled n orbitals of the ligand~.~ An unusual spectraleffect observed in the proton magnetic resonance spectra of diamagneticsubstituted cobalt(m) and rhodium(II1) acetylacetonates suggests that thechelate rings give rise to long-range magnetic anisotropic shielding normallyassociated with aromatic systems. This could represent the first physicalG. K. Wertheim and R. H. Herber, J. Chem. Phys., 1962, 36, 2497; idem,J .Amer. Chem. SOC., 1962, 84, 2274; G. K. Wertheim, W. R. Kingston, and R. H.Herber, J. Chem. Phys., 1962, 37, 687; cf. Ann. Reports, 1961, 58, 464.M. F. C. Ladd and W. H. Lee, J . Inorg. Nuclear Chem., 1961, 23, 199; idem,J., 1962, 2837.G. C. A. Schuit, Rec. Trav. chim., 1962, 81, 21, 481. ’ J. G. Brushmiller, E. L. Amma, and B. E. Douglas, J. Amer. Chem. SOC., 1962,84, 3227; R. E. Ballard, A. J. McCaffery, and S. F. Mason, Proc. Chem. SOC., 1962,331; A. J. McCaffery and S. F. Mason, ibid., p. 388. * R. C. Fay and T. S. Piper, J. Amer. Chem. Soc., 1962, 84, 2303.D. W. Barnum, J. Inorg. Nuclear Chem., 1961, 22, 183, 221; T. S. Piper andR. L. Carlin, J. Chem. Phys., 1962, 36, 3330170 INORGANIC CHEMISTBYevidence for aromaticity in such chelate rings.l0 The contributions ofn-bonding in the silver-nitrogen bond to the stabilities of silver complexeswith substituted pyridines have been discussed by means of a relationshipbetween the stabilisation factor Sf (log K,., - log Kmn, where L’, is an-bonding ligand), and Hammett’s o factor for the substituents.1l Thenuclear spin coupling constants between platinum and phosphorus in square-planar platinum(I1) complexes appear to be largely determined by thestrength of the bond between these two elements.In the compounds[(EtO),P],,PtCl,, and [(Bun3 P),PtCI,], the triethyl phosphite ligand hassmaller o-bond donor power than tri-n-butylphosphine, and consequentlythe acceptor properties of the phosphorus d orbitals in this complex arestronger and the coupling constant larger.12 A thermodynamic study ofthe solubilities of dimethylglyoximenickel and ethylmethylglyoximenickelshows that the crystal energy of the former is about 10 kcal.more than thatof the latter. A large part of this difference is attributed to nickel-nickelbonding in the dimethylglyoximenickel. l3 The stabilities of bivalent-metalalkanedicarboxylates are in the Irving-Williams stability order for chelatecomplexes, and it seems likely therefore that chelation forces predominatein aqueous solutions of these salts.14A general theory has been formulated to account for the number-averagedegree of polymerisation of metal oxide alkoxides; it provides a rationalinterpretation of some oxide alkoxides of tin, cerium, and ursnium.15 Ageneral paper has dealt with the classification of inorganic co-ordination *polymers. Measurements of melt viscosity and conductivity as a functionof temperature indicate that monoamminedichlorozinc( 11) is polymeric ;depolymerisation occurs in co-ordinating solvents.A co-ordination polymerhaving an inorganic backbone has been prepared by reaction of chromium(rn)acetylacetonate with diphenylphosphinic acid. The structure of theproduct, (AcCHAc),Cr( OPPh,O) ,Cr( AcCHAc),, probably involves doublediphenylphosphinate bridges. l6 The polyfunctional ligand naphthazarinforms 1 : 1 polymers (containing two molecules of water) with bivalentcobalt, nickel, and zinc, in which the metals are octahedrally co-ordinated;with copper, Cu, naph, contains four-co-ordinate copper.l7 Studies onmetal-amine complexes in ion-exchange show that complexes of 2-amino-ethanol with silver(I), nickel(II), and copper@), and of ethylenediamine withnickel(n), copper(n), and zinc(=) are much more stable in the resin than insolution. Cross-linking by the diamine binding the metal ions togetheroccurs much more readily on the resin where the metal ions are closertogether than in dilute solutions. l8 A new chromatographic technique,l o J. P. Collman, R. L. Marshall, and W. L. Young, Chem. and Ind., 1962, 1381.l1 H. Irving and J. J. R. F. da Silva, Proc. Chem. Soc., 1962, 250.l2 A. Pidcock, R. E. Richards, and L. M. Venanzi, Proc. Chem SOC., 1962, 184.l4 R. H. Jones and D. I. Stock, J., 1962, 306.16D.C. Bradley and H. Holloway, Canud. J. Chem., 1962, 40, 1176.l6 B. P. Block and G. Barth-Wehrenalp, J . Inorg. Nuclear Chem., 1962, 24, 365,371; B. P. Block, J. Simkin, and L. R. Ocone, J . Amer. Chem. SOC., 1962, 84, 1749.l7 R. S. Bottei and P. L. Gerace, J . Inorg. Nuclear Chem., 1961, 23, 245.L. Cockerel1 and H. F. Walton, J . Php. Chem., 1962, 66, 75; M. G. SunjaramanC . V. Banks and S. Anderson, J . Amer. Chem. Soc., 1962, 84, 1486.and H. F. Walton, ibid., p. 78NICHOLLS : THE TRANSITION ELEMENTS 171“ ligand exchange,” has been used to separate compounds that form com-plexes with metal ions. The ion-exchanger containing the complexingmetal ion effects the separation of ligands having different co-ordinativevalencies.19 In an interesting low-temperature application of zone melting,the separation of solutes differing in solubility (especially diastereoisomers)is achieved by freezing the solution and causing a molten zone to traversethe charge.20 Further studies have been made on the photoracemisation ofoctahedral chelates.The complexes [Co en,13+ and [Co en2(C20,)] + arestable to both photoracemisation and photodecomposition but [Co en(C,O,),]-photoracemises and [CO(C,O,),]~- photodecomposes with some photo-racemisation.21 The energy spectrum resulting from the 5d8 configurationin a square-planar ligand-field has been calculated; the ordering of thed orbitals is d, = d, < dz2 < d,, < dz8-y2.22 The spectra of transition-metal oxyanions , in particular permanganate and chromate, have beenstudied and the effect of the solvent and of complex-forming ions (e.g.Ag+)disc~ssed.~3 The l7O magnetic resonance of a number of oxyanions shows ahigh degree of paramagnetic shielding of the oxygen nuclei; the relationbetween the 170 chemical shifts and the ultraviolet and visible spectra ofthese anions is accounted for theoreti~ally.2~ Thermally stable, zerovalent,complexes with the diphosphine, Me2P*CH2*CH2*PMe2, have been isolatedwith all members of the first transition series except titanium and manganese.Octahedral M(diphosphine), (M = V, Cr, Mo, or W) and tetrahedral M(di-phosphine), (M = Fe or Co) are obtained by the reduction of higher-valentcomplexes with sodium naphthalide in tetrahydrofuran. 25 The metals frommanganese to zinc react with suspensions of nitrosyl tetrafluoroborate inmethyl cyanide or ethyl acetate to give solutions of bivalent-metal tetra-fluoroborates.From these solutions complexes can be prepared, e.g.,Cu( BF4),,4MeCN and Fe( BF4),,6MeCN.26 Dimethyl sulphoxide formssolvates with many transition-metal halides, e.g. , CrC13,5DMS0 andFeC1,,4DMSO ; in some cases autocomplexing occurs :272CoC1, + 6DMSO + Co(DMSO),++ + CoC1,- -.Views concerning the structure of EDTA complexes of bivalent cations havebeen summarised and it is concluded that these complexes are quinque-dentate in aqueous solution.28 For chelates of EDTA, diethylenetriamine-penta-acetic acid and triethylenetetraminehexa-acetic acid a correlation hasbeen established between the charge : size ratio of the metal ion and thedegree of covalency in the metal-oxygen bond.29 Several new ligandsl9 F.Helfferich, J . Arner. Chem. SOC., 1962, 84, 3237, 3242.2o V. F. Doron and S. Kirschner, Inorg. Chem., 1962, 1, 539.a1 S. T. Spees and A. W. Adamson, Inorg. Chem., 1962, 1, 531.22 R. F. Fenske, D. S. Martin, jun., and K. Ruedenberg, Inorg. Chem., 1962, 1, 441.23 M. C. R. Symons and P. A. Trevalion, J., 1962, 3503.2 4 B. N. Figgis, R. G. Kidd, and R. S. Nyholm, Proc. Roy. SOC., 1962, A , 269, 469.2 5 J. Chatt and H. R. Watson, J., 1962, 2545.B. J. Hathaway, D. G. Holah, and A. E. Underhill, J., 1962, 2444.H. L. Schlafer and H. P. Opitz, 2. anorg. Chem., 1961, 313, 178; V. Gutmannand L. Hubner, Monatsh., 1961, 92, 1261; V.Gutmann and G. Schober, ibid., 1962,93, 212.28 W. C. E. Rigginson, J . , 1962, 2761.2 9 R. E. Sievers and J. C. Bailar, jun., Inorg. Chem., 1962, 1, 174172 INORGANIC CHEMISTRYhave been described during the year. The chelate dimethyl-3-methylthio-propylarsine (8) forms crystalline complexes, M(As-S)X, (X = C1, Br, I),.with copper(I), palladium(n), and p l a t i n u m ( ~ ~ ) . ~ ~ The ligand 2-2’-hydroxy-ethylpyridine is for the most part bidentate; cobalt(@ and nickel(=) chlor-ides, however, yield co-ordination compounds in which only the nitrogenatom of the pyridine ring acts as a d0nor.~1 Very stable complexes (9) areformed by almost all transition metals with 1 -2’-pyridyl-2-2’-pyridyl-methylenehydrazine ; their stability constants are sufficiently high to enabletransition aetals to be extracted from their EDTA complexes.32 TheH H,O*CH2,1 CHI- SMe @yyJ ”qO.CH2;;CMe\ N+M+N / CH2O.CH2 ‘CHI- **Me2(8) (9) (‘0)effect of reducing steric hindrance to co-ordination, with respect to theadditional effect of low ligand-ligand repulsion, has been demonstrated forthe constrained phosphite ester 4-methyl-2,6,7-trioxa-l-phosphabicyclo-[2,2,2]octane (10).The bicyclic base forms tetrahedral complexes, (CuL,),ClO,, and (AgL,)NO,, in which the maximum co-ordination number isachieved with only ligand molecules.33 The reaction of metal ions [Co(n),CO(III), Ni(n), Cu(n), and Z~(II)] with the zwitterion betaine have beenstudied and the infrared spectra of the complexes produced have beena~signed.~4 The first complexes in which a transition metal is co-ordina-tively saturated with nitrate ligands have been ~repared.~5 Tetramethyl-ammonium tetranitratocobaltate(n) is obtained from nitromethane solutionsof tetramethylammonium and cobalt(=) nitrates.Magnetic studies indicatethat the [Co(ONO,),]2- ion is tetrahedral. Oxidation of potassium tetra-nitropalladate(n) with concentrated nitric acid yields K,Pd(NO,), as anorange-red solid stable in air but immediately hydrolysed in aqueous solu-tion. There has been considerable interest shown in reactions of co-ordin-ated ligands. Ethylenediamine- and propylenediamine-nickel( 11) complexesreact with acetone to form Schiff-base complexes, e.g. (ll), with two, three,and four N-isopropylidene groups. With triethylenetetraminecopper( TI)or -nickel( 11) complexes and acetone, co-ordination compounds are obtainedhaving three secondary amine and one azomethine donor groups.36 Some-times metal ions can facilitate the formation of an organic molecule thatotherwise cannot be isolated because of competing reactions.Thus attemptsto prepare Schiff bases between or-diketones and 2-mercaptoethylamineresult in the production of thiazolines; in the presence of nickel(=) ions,30 B. Chiswell and S. E. Livingstone, J . Inorg. Nuclear Chem., 1961, 23, 37.31 E. Uhlig and H. Schon, 2. anorg. Chem., 1962, 316, 25.32 J. F. Geldard and F. Lions, J . Amer. Chem. SOC., 1962, 84, 2262.33 J. G. Verkade and T. S. Piper, Inorg. Chem., 1962, 1, 453.34 J.V. Quagliano, S. Kida, and J. Fujita, J . Amer. Chem. SOC., 1962, 84, 724.35 F. A. Cotton and T. G. Dunne, J . Amer. Chem. Soc., 1962,84,2014; R. Eskanazi,36M. M. Blight and N. F. Curtis, J., 1962, 1204, 3016; D. A. House and N. F.J. Raskovan, and R. Levitus, Chem. a d Id., 1962, 1327.Curtis, J . Amer. Chem. SOC., 1962, 84, 3248NICHOLLS : THE TRANSITION ELEMENTS 173however, Schif€-base complexes (12) are formed which contain a novel tetra-dentate ligand.37 The chelate trisacetylacetonates of chromium(m),cobalt(In), and rhodium(m) can be nitrated by treatment with copper(rr)nitrate and acetic anhydride, and formylated with dimethylformamide inthe presence of phosphorus oxychloride. 38The ligand-field splitting of d orbitals in eight-co-ordinate complexes ofdodecahedral structure has been deduced from the known order of theseMe 2CIICMe2IIorbitals in a cube, by considering the effect on individual d orbitals of thedistortion of the cube into the dodecahedron.The most stable orbital isd,, and this orbital is not used in dodecahedral d4sp3 hybridi~ation.,~ Infra-red spectra in the C-N stretching region provide a means of distinguishingbetween terminal and bridging cyanide groups in complex cyanides; thebridging cyanides exhibit the higher absorption frequency. 40 Infra-red spectra also clearly distinguish between a unidentate and a bidentatecarb~nato-group.~~ Trends found in the infrared spectra of trans-[MX(COR)(PEt,),] (M = Pt, Pd; X = NO,, NCS, NO,, halogen; R = Me, Ph)have been explained with the help of resonance structures, and the spectra oftrans-[PtCl(CX,)(PMe,),] and cis-[Pt(CX,),(PMe,),] (X = H, D) have beenused to confirm the previous assignment of the Pt-C stretching modes.42Changes in the electronic structures of chelate acetylacetonate rings throughsubstitution in the ligand have been observed in their infrared spectra, andmore quantitative information deduced from force-constant calculationsusing the perturbation method.43 Investigations of metal-ligand n-bondingin octahedral complexes of bivalent cobalt, nickel, and iron with 2,3-bis-methyliminobutane (BMI), 1 ,2-dihydro-2-methyliminopyridine, and 1,2,3,6-tetrahydro-2,6-bismethyliminopyridine (TBMI) show that conjugativedn-pn bonding is greatest in complexes of BMI particularly with iron(@.The stereochemical relationships associated with the planar tridentateligand TBMI favour spin pairing in the d7 cobalt(=) ion.44(b) Mechanisms of reactions of inorganic complexes.Only the brief-est review can be made of the large number of publications in thisfield. The oxidation of vanadium(m) by iron(n1) in aqueous perchloricacid paoceeds by two distinct routes.45 First a single-stage reaction,37 M. C. Thompson and D. H. Busch, J . Amer. Chem. SOC., 1962, 84, 1762.38 J. P. Collman, R. L. Marshall, W. L. Young, and J. D. Goldby, Inorg. Chem.,39 M. Randic, J . Chem. Phys., 1962, 36, 2094.4 0 D. A. DOWS, A. Haim, and W. K. Wilmarth, J . Inorg. Nuclear Chem., 1961,41 J. Fujita, A.E. Martell, and K. Nakamoto, J . Chem. Phys., 1962, 36, 324.4aD. M. Adams and G. Booth, J., 1962, 1112; D. M. Adams, J., 1962, 1220.43 K. Nakamoto, Y. Morimoto, and A. E. Martell, J . Phys. Chem., 1962, 66, 346.4 4 P. E. Figgins and D. H. Busch, J . Phys. Chem., 1961, 65, 2236.4 5 W. C. E. Higginson and A. G. Sykes, J., 1962, 2841.1962, 1, 704.21, 33174 INORGANIC CHEMISTRYFeIII + VII1 --+ FeII + VIV, occurs and this is followed by the secondaryreactions, FeIII + VIV + FeII + Vv and Vv + V"I -+ 2VIV. The replace-ment of an ammonia molecule in [GO(NH,)~(OAC)]~+ by a second carboxylategroup results in a hundred-fold increase in the uncatalysed rate of reductionby Cr2+aq. It seems likely that this replacement by a ligand producing aweaker field increases the probability of electron transfer by lowering theenergy of the acceptor antibonding d orbital of cobalt.46 Studies on free-radical reactions of co-ordination compounds show that, in the pentane-2,4-dione chelates, co-ordination changes the site of radical attack.The increasein the rate of attack with increasing number of d electrons of the metalion suggests that the back-donation of electrons from the metal to theorganic ligand is very important in determining the relative rea~tivities.~~A method for the kinetic study of moderately fast reactions uses a non-complexing salt to depress the freezing point of water to a temperature lowenough to increase the reaction ha1f;time to a t least twenty seconds.48The stopped-flow method has been used to study the rates of dissociation inacid solution of nickel@) and copper(n) complexes with a series of nitrogen-containing ligands; the importance of the dissociative process in deter-mining the stability of nickel(rr) complexes has been further e~tablished.~sIn the acid-catalysed aquation of [Co(CN),N,I3-, and in the substitution ofwater in [CO(CN),OH,]~- by azide ions, there is strong evidence for S,1mechanisms involving the pentaco-ordinate intermediate, [Co(CN),]2-.50The equilibrium between cis- and trans-[Co en2C12]C104 in dimethylformamideand dimethylacetamide has been studied spectrophotometrically.Theamount of cis-isomer at equilibrium increases with chloride concentrationin a way that is consistent with the formation of a strong ion-pair betweenchloride and the cis-isomer and a weak one with the trans-isomer.51 Theisomerisation of hydroxoamminecobalt(1n) complexes, e.g., trans-[Co en2(NH,)( 0H)l2 +, probably occurs via an intramolecular mechanisminvolving a unimolecular dissociation of one end of an ethylenediarninechelate ring under the labilising influence of the hydroxyl gr0up.52 Thekinetics of the reactions of ethylenediamine with Co(EDTA)- andCo(PDTA) - (PDTA = propylenediaminetetra-acetate) have been investi-gated.The determination of the absolute configurations of Co(EDTA) -,[Co(EDTA)XI2-, Co(PDTA)-, and [Co(PDTA)X]2- (X = C1, Br) consti-tute the first examples of unequivocal deduction of configuration from thekinetics and stereochemistry of a reaction of an octahedral ion.53 Theracemisation of d-[Co(EDTA)]- proceeds very slowly in acid media by apH-independent path with a high activation energy and a positive entropy46 K.D. Kopple and R. R. Miller, Proc. Chem. SOC., 1962, 306; R. T. M. Fraser,4 7 R. J. Gritter and E. L. Patmore, Proc. Chem. SOC., 1962, 328.4 8 C. S. Garner and J. Bjerrum, Acta Chem. Scand., 1961, 15, 2055.4 9 R. G. Wilkins, J., 1962, 4475; G. A. Melson and R. G. Wilkins, ibid., p. 4208.60A. Haim and W. K. Wilmarth, Inorg. Chem., 1962, 1, 573, 583.61M. L. Tobe and D. W. Watts, J., 1962, 4614.6sD. F. Martin and M. L. Tobe, J., 1962, 1388.63 D. H. Busch, K. Swaminathan, and D. W. Cooke, Inorg. Chem., 1962, 1, 260;D. H. Busch and K. Swaminatham, J. Inorg. Nuclear Chern., 1961,23, 150; D.H. Buschand D. W. Cooke, ibid., p. 145.J . Amer. Chem. SOC., 1961, 83, 4920NICHOLLS : THE TRANSITION ELEMENTS 175change; this rules out a dissociative (XN1) mechanism. A strong basecatalysis of racemisation is observed ; its path probably involves nucleophilicattack by a hydroxyl ion with the formation of a symmetrical seven-co-ordinate intermediate. 54 A seven-co-ordinate intermediate in which fiveligands form a symmetrical square pyramid with the remaining two situatedabove the base in the (z + y)x-plane has been discussed theoretically. Thetwo models considered are those in which the angle between the two ligandsabove the base is the tetrahedral angle and An attempt has beenmade to measure the extent to which the co-ordination of a ligand to ametal affects the ionisation of acid side-groups on the ligand.56 WhenFe2+ forms a complex with pyridine-2-aldoxime7 the acid strength of theoxime groups increases from pK" = 10.22 (free ligand) to pK" = 7.13 inthe tris-complex at 25 ".From reaction rates of diethylenetriamineaquo-platinum(@ with various ligands it is concluded that an aquo-complexformed by an Lj"2 reaction with water is the principal intermediate in thetotally first-order reactions of platinum(@ There is goodkinetic and spectral evidence that association between nitrite ion andcis- [ Pt( NH,) ,( NO,)Cl] gives a transient intermediate, [Pt (NH,) 2( NO,),Cl]-,which probably has a tetragonal pyramidal structure ; elimination of chlorideion then occurs to give ~is-[Pt(NH,),{N0,),].5~ In the base hydrolysisof chloroamineplatinum(1v) complexes, the predominant species formedare amido-complexes, e.g., [Pt(NH,),(NH2)C1]2 +, but considerable reduc-tion to platinum(I1) occurs in those complexes containing trans-chloro-groups.59A molecular-orbital energy-level scheme has been pre-sented for the large class of metal carbonyls and nitrosyls in which oneparticularly strong M-CO or M-NO bond dominates the overall ligand-field.60 The Raman spectra of several carbonyls have been measured.Innickel tetracarbonyl there is direct evidence for partial multiple metal-carbon bonding and conjugation between M-C and C-0 bonds. Thecarbonyls, CdCo(CO), and Hg[Co(CO),],, do not contain bridging carbonylgroups but have a three-fold principal molecular axis containing the atomsO-C-Co-Cd( Hg)-Co-C-0 with the staggered D,, configuration for the entiremolecule.61 The photoproduction of group VI metal hexacarbonyl deriva-tives, e.g., M(CO),,CH,CN and Mo(C0),,2pC,H4*(NH,),, has been thoughtto proceed by a mechanism involving the M(CO), radical as initiatingspecies ;62 now tungsten pentacarbonyl has been identified with a half-life54D.W. Cooke, Y. Ae Im, and D. H. Busch, Inorg. Chem., 1962, 1, 13.55N. S. Hush, Austral. J . Chem., 1962, 15, 378.5 6 G. I. H. Hanania and D. H. Irvine, J., 1962, 2745, 2750.5 7 H. B. Gray and R. J. OIcott, Inorg. Chem., 1962, 1, 481.5 8 P. Haake, Proc. Chem. Soc., 1962, 278.59 R. C. Johnson, F. Basolo, and R. G. Pearson, J .Inorg. Nuclear Chern., 1962,24, 59; A. A. Grinberg and Yu. N. Kukushkin, Zhur. neorg. Khim., 1961, 6, 1084 (554).6 0 H. B. Gray, I. Bernal, and E. Billig, J. Amer. Chem. SOC., 1962, 84, 3404.61 H. Stamrnreich, K. Kawai, 0. Sda, and P. Krumholz, J. Chem. Phys., 1961,35, 2168, 2175.6 2 W. Strohmeier and G. Schonauer, Chem. Ber., 1962, 95, 1767; W. Strohmeier,D. Von Hobc, G. Schonauer, and H. Laporte, 2. Naturforsch., 1962, 17b, 502; G. R.Dobson, M. F. A. El Sayed, I. W. Stolz, and R. K. Sheline, Inorg. Chem., 1962, 1,526.(c) Carbonyls176 INORGANIC CHEMISTRYof about two minutes at room temperature, during the ultraviolet irradiationof W(CO), solution.63 That this irradiation is not essential in the produc-tion of these carbonyl derivatives has been demonstrated by the productionof the tris-nitrile compounds, (CH,CN),M(CO), (M = Mo, W, Cr), whichare conveniently prepared by refluxing the carbonyl in an excess of aceto-One or two carbonyl groups in Ni(CO), andMo(CO), are directlyreplaceable by monodentate arsenic ligands.Bidentate nitrogen and s d -phur donors replace two carbonyl groups forming M(CO),L (M = Cr, Mo, W;L = 2,2'-bipyridyl, 2,5-dithiahexane), and tridentate sulphur donors canform LM(CO), (L = 3,6,9-trithiaundecane). The reaction of the bipyridylderivatives of molybdenum and tungsten carbonyls with bromine resultsin the formation of compounds, M(CO),( bipy)Br,, which appear to be seven-covalent derivatives of molybdenum(I1) and t u n g s t e n ( ~ ~ ) . ~ ~ The assign-ment of carbonyl stretching frequencies in the substituted carbonyls,L,M(CO),_,, where M is a d6 atom or ion, has been attempted.66 In thecompounds, MoL,(CO), (L = unidentate sulphur donor), prepared by theaction of the ligands on cycloheptatrienemolybdenum tricarbonyl, the C-0stretching frequencies show that dialkyl sulphides have a substantialtendency to function as macceptors.67 The carbonylation reaction,MeMn(CO), + CO --+ MeCOMn(CO),, is first-order in both reactants.68Thermally-unstable acylcobalt tetracarbonyls (and their perfluoro-analogues)can be isolated as triphenylphosphine derivatives by reaction of sodiumcobalt tetracarbonyl with acyl halides or acyl anhydrides, or with alkylhalides and carbon monoxide. 69A number of transition-metal carbonyls are protonated in strong-acid solu-tions giving species such as [HFe(CO),(PPh,),] +, [H (Mo(CO),(n-C,H,) >,I +,and [HCr( CO),C6H5Me] +.In most cases the presence of a metal-hydrogenbond can be demonstrated only from the nuclear magnetic resonance spectra,but a few salts can be isolated, e.g., [ (n-C,H, l?e(C0)2)2H]PF6, in which theinfrared spectra confirm the presence of the M-H bond. The binuclearcarbonyl-n-cyclopentadienyl-molybdenum and -tungsten compounds areunusual among protonated species in that the hydrogen is associated withtwo metal at0ms.7~ The addition of manganese pentacarbonyl hydride tosome fluoro-olehs gives a-bonded organomanganese compounds, e.g.,HCF,*CF,*Mn(CO), which contains octahedrally co-ordinated manganese.It'is possible to replace two carbonyl groups of perfluoropropyliron tetracar-bony1 iodide with pyridine or 2,2'-bipyridyl, but only one with triphenyl-phosphine.71 Reduction of nickel carbonyl with sodium borohydride in63 I. W. Stolz, G. R. Dobson, and R. K. Sheline, J . Amer. Chem. Soc., 1962, 84,3589.6 4 D. P. Tate, W. R. Knippls, and J. M. Augl, Inorg. Chem., 1962, 1, 433.65G. Bouquet and M. Brigorghe, Bull. SOC. chim. France, 1962, 433; H. C. E.Mannerskantz and G. Wilkinson, J., 1962, 4454; M. H. B. Stiddard, J., 1962, 4712.66 L. E. Orgel, Inorg. Chem., 1962, 1, 25.6 7 F. A. Cotton and F. Zingales, Inorg. Chem., 1962, 1, 145.6 8 F. Calderazzo and F. A. Cotton, Inorg. Chem., 1962, 1, 30.69 R. F. Heck and D. S. Breslow, J.Amer. Chem. Soc., 1962, 84, 2499; W. Hieber70A. Davison, W. McFarlane, L. Pratt, and G. Wilkinson, J., 1962, 3653.71 P. M. Treichel, E. Pitcher, and F. G. A. Stone, Inorg. Chem., 1962, 1, 511;and E. Lindner, Chem. Ber., 1962, 95, 2042.R. A. Plowman and F. G. A. Stone, {bid., p. 518NICHOLLS THE TRANSITION ELEMENTS 177liquid ammonia proceeds according to :722Ni(CO),NH, + 2e- + H2Ni,(CO), + 2NH2-.Several mixed metal carbonyls have been synthesised. A fairly generalmethod seems to involve the reaction of the sodium salt of a metal carbonyl,or a cyclopentadienylmetal carbonyl, with an organometallic or carbonylhalide of the other metal; typical products are (CO),CoMn(CO), andR3SnMn( CO), (R = alkyl or aryl). 7 3 Dicobalt octacarbonyl reacts withtetravinylsilicon to give purple nonacarbonyl(vinylsilicon)tricobalt,Co3(CO),SiCH,:CH2; its structure is unknown but is expected to be similarto that of the known complexes CO,(CO)&R.~~ These latter complexesare obtained as violet crystals from the [Co(CO),]- ion by reaction withcarbon tetrachloride (giving R = Cl), bromoform (giving R = H), andbenzotrichloride (giving R = Ph) .75 By reaction of tetracarbonylferrate,[Fe( C0),l2-, with nitrite or hydroxylamine an orange-yellow carbonylimine,[Fe(CO),NH],, has been obtained. Withnitric oxide this yields [Fe(NO),NH],which contains bridging NH groups. Ammonia co-ordination compounds,Fe(CO),NH3andMn,(CO),NH3, are obtainedupon reaction of hydroxylamine-2-sulphonic R, ,R 0ferrate and pentacarbonylmanganate ions,respectively.76 Dialkylcyanamides react Nsensitive, diamagnetic carbonyl-bridgedcomplexes (13). 7 A convenient synthesis of dicarbonyldinitrosyl-iron(0)uses the reaction of iron pentacarbonyl with nitrosyl chloride; the newderivatives, (Ph,P)Fe(CO)(NO), and (Ph,As),Pe(NO),, have been des-cribed.78 Manganese carbonyl halides react with a variety of unidentateligands giving monosubstituted compounds, Mn(CO),LX (X = C1, Br, I).Disubstituted derivatives are obtained with some unidentate ligands andbidentate ligands; Mn(CO),LX (L = bidentate As, P, S ligand) are mono-meric, octahedral non-electrolytes containing manganese(1). 79 Reductionof Mn(CO),PR, and [Mn(CO),PR,], with alkali-metal amalgam gives phos-phine-substituted carbonylmanganates( - 1) ; these give hydrides, e.g.,HMn(CO),(PR,), upon treatment with acids.80 The infrared spectrum ofMn,(CO),P(CF,),I excludes the possibility of carbonyl bridging so that thebinuclear complex probably contains phosphorus and iodine bridges.81Phosphine-substituted cobalt(1) carbonyl halides, Co(CO),PPh,X (X = I, Br),73 H. Behrens and H. Zizlsberger, J . pralct. Chem., 1961, 14, 249.7 3 R. D. Gorsich, J. Arner. Chem. Soc., 1962, 84, 2486; K. K. Joshi and P. L.Pauson, 2. Naturforsch., 1962, 17b, 565; W. Hieber and T. Kruck, Chem. Ber., 1962,95, 2027.N II acid with alkaline solutions of tetracarbonyl- /, N / C \ ,-AC\, Ni , , Ni +with nickel carbonyl forming orange, air- 5 o R' 'R (13)7 4 S. F. A. Kettle and I. A.Khan, Proc. Chem. Soc., 1962, 82.7 5 G. Bor, L. Mark6, and B. Marld, Chem. Ber., 1962, 95, 333.76W. Hieber and H. Beutner, 2. anorg. Chem., 1962, 317, 63.7 7 H. Bock, Angew. Chem., 1962, 74, 695.7 8 D. W. McBride, S. L. Stafford, and F. G. A. Stone, Inorg. Chem., 1962, 1, 386.7 9 A. G. Osborne and M. H. B. Stiddard, J., 1962,4715; R. J. Angelici and F. Basolo,8 0 W. Hieber, G. Faulhaber, and F. Theubert, 2. anorg. Chem., 1962, 314, 125.8lH. J. Emelkus and J. Grobe, Angew. Chern., 1962, 74, 467.J . Arner. Chem. SOC., 1962, 64, 2495178 INORGANIC CHEMISTRYare obtained upon mild halogenation of [Co(CO),PPh,]- anions with trifluoro-iodomethane and N-bromosuccinimide. 82 The bisphosphineiridium( I) car-bony1 halide, [IrCl(CO)(Ph,P),], shows a striking reactivity towards a largenumber of molecules.Hydrogen reacts with it as a Lewis acid, oxidisingthe iridium to the diamagnetic non-electrolyte, [Ir111H2Cl(CO)(PPh,),I ; thiscompound, when treated with hydrogen chloride in ether, reacts to give[IrDIHCI,(CO)(PPh,),] and hydrogen. 83 Well-defined adducts, of formula[FeCl,(CO),( PEt,Ph,- ,),I, are formed when carbon monoxide reacts undermild conditions with [FeCl,(PEf,Ph,,,),] (n = 1-3). With cobalt(1) onlythose complexes where n = 3 can be isolated, and the corresponding nickel(n)complexes do not form addu~ts.~4The gas-phase reaction between nitrosyl chloride andnickel carbonyl yields the grey-green, paramagnetic nitrosyl dihalides ofnickel, Ni(NO)Cl,. The infrared spectrum of this compound indicates thatin the solid there are co-ordinated NO groups present in two differentenvironments.Nitric oxide is not evolved below 150" but triphenylphos-phine reacts at 100" in a sealed tube forming (Ph,P),Ni(NO)C1.85 Dimericdinitrosylcobalt halides react with organo-phosphines, -arsines, and -stibinesin solution forming diamagnetic monomers, Co(NO),LX. In the moltenstate, disproportionation occurs :Dinitrosylrhodium chloride undergoes a similar disproportionation uponreaction with these ligands a t room temperature.86 The manganese nitrosylcarbonyl derivatives, Mn(NO),L, Mn(NO)(CO),L, Mn(NO)(CO),L,, andMn(NO),L,X (L = PR,, AsR,, SbR,; X = halogen), are considerably morestable than the unsubstituted compounds. Reduction of Mn(NO),(PPh,),Brwith sodium borohydride gives MnH(NO)2(PPh,)2.87 I n nitroso(dimethy1-dithiocarbamato)cobalt, [Co(NO) (S,CN(CH,), I,], the co-ordination roundthe cobalt atom is that of a rectangular-based pyramid with the NO mole-cule a t the apex and the four sulphur atoms a t the corners of the base.Thedithiocarbamate ligands me planar; the N-0 bond is inclined a t 139" tothe pyramidal axis, and the NO group appears to form an unsymmetricaln-complex with the cobalt atom.88 An electron-spin resonance study of the[Fe(CN),N0]3- ion shows that the unpaired electron is delocalised betweenthe iron and the nitric oxide ligand. Experimental data suggest that thesemetal-nitrosyl complexes should be considered as molecular species withelectrons delocalised to different extents rather than as containing chargedligands.89 Oxidation of chromium( IT) by nitric oxide produces threechromium(m) complexes which can be separated by ion-exchange; one ofthese has been identified as [Cr(H,O),N0I2+ and has been isolated as thesulphate.90 Studies on the nitrato-complexes of nitrosylruthenium have(d) Nitrosyb.[CO(NO)~C~]~ + 6PPh3 + Co(NO)(PPh,)s + Co(OPPh3)2C12 + OPPh3 + 14N2-82 W.Hieber and E. Lindner, Chem. Ber., 1962, 95, 273.8SL. Vaska and J. W. Diluzio, J. Amer. Chem. SOC., 1962, 84, 679.8 4 G. Booth and J. Chatt, J., 1962, 2099.8 5 C. C. Addison and B. F. G. Johnson, Proc. Chem. Xoc., 1962, 305.a6 W. Hieber and K. Heinecke, 2. anorg. Chem., 1962, 316, 305, 321.W. Hieber and H. Tengler, 2. anorg. Chem., 1962, 318, 136.P.R. H. Alderman, P. G. Owston, and J. M. Rowe, J . , 1962, 668.8 9 I. Bernal and E. F. Hockings, Proc. Chem. SOC., 1962, 361.M. Ardon and J. I. Herman, J., 1962, 507NICHOLLS : THE TRANSITION ELEMENTS 179shown that the complex most readily extracted in tri-n-butyl phosphate is[Ru(NO)(NO,),( H,O),] ; cationic species isolated by ion-exchange have beenassigned the formuls [Ru(NO)(NO,),( H20),] f, [Ru(NO) (N0,)(H,0)4]2 +,and [RU(NO)(H,O)~]~+.~~(e) OZeJin complexes. A review has appeared concerning olefin, acetylene,and n-allylic complexes of transition metal~.~a Yellow, crystalline bis(tri-pheny1phosphine)ethylenenickel is formed in the reaction of nickel acetylace-tonate with diethylaluminium ethoxide in benzene containing triphenyl-phosphine.Displacement of ethylene -is achieved with other o l e h andacetylene donors forming (PPh,),NiD (D = CH,:CHPh, PhC:CPh, e t ~ . ) . ~ ~Silver-olefin complexes, AgN0,,C4H6 and 2AgNO3,C4H6, are precipitatedwhen butadiene is passed through 8M-silver nitrate solution at 15°.94 Silverfluoroborate absorbs gaseous olefins, e.g. , ethylene, propene, and butenes, atroom temperature forming solid complexes of high stability.95 Copper(1)halides form 1 : 1 complexes with aryl-substituted 1,l-dicyanoethylenes andalso with the chelating olehs norbornadiene, dicyclopentadiene, and cyclo-0ctadiene.9~ A complete crystal-structure study of rhodium(1) chloride-l,5-cyclo-octadiene has confirmed that the rhodium atom is in an approximatelysquare-planar configuration, being bonded to two bridging chlorine atomsand the double bond centres of a cyclo-octadiene The ethylenecomplex, (C,H4),RhC12(C,H,),, which is probably similar in structure, hasbeen prepared from rhodium(1rr) chloride hydrate and ethylene in aqueousrnethan01.9~ The planar platinum complexes, Pt(olefin)(PPh,), (olefin =trans-stilbene, truns-4,4-dinitrostilbeneY and acenaphthylene), are formedfrom cis-[Cl,Pt(PPh,),] in ethanol containing hydrazine hydrate and theolefin at 60°.99 Mesityl oxide derivatives of platinum and palladium halideshave dissimilar structures.The palladium compound, C6H,,C10Pd, hasbeen reformulated as a n-allylic derivative (14) on the basis of its infraredand proton magnetic resonance spectra. In contrast to this palladiumcompound, reagents like dimethyl sulphoxide and triphenylphosphine dis-place the mesityl oxide ligand in the platinum derivative, forming L,PtCl,.High-resolution proton magnetic resonance studies exclude a n-allylicO1 R.M. Wallace, J . Inorg. Nuclear Chem., 1961, 20, 283.O a R. G. Guy and B. L. Shaw, Adv. Inorg. Chem. Radiochem., 1962, 4, 78.O3 G. Wilke and G. Herrman, Angew. Chem., 1962, 74, 693.O 4 J. W. ICraus and E. W. Stern, J . Arner. Chem. Soc., 1962, 84, 2893.O 5 H. W. Quinn and D. N. Glew, Canad. J . Chem., 1962, 40, 1103.*13 G. N. Schrauzer and S. Eichler, Chem. Ber., 1962, 95, 260.97 J. A. Ibers and R. G. Snyder, Acta Cryst., 1962, 15, 923; idem, J . Amer. Chem.O 8 R. Cramer, Inorg. Chem., 1962, 1, 722.SOC., 1962, 84, 495.J.Chatt, B. L. Shaw, and A. A. Williams, J., 1962, 3269180 INORGANIC CHEMISTRYstructure, and the polymer structure (15) is proposed.loO A further exampleof n-allylic bonding in palladium compounds is that presented by therevised structure for " butadiene palladous chloride " ( 16).lo1 The crystal-structure determination on the n-allyl, [PdCl( C3H5),], has confirmed thest'ructure suggested on spectroscopic evidence; the plane of the ally1 groupis approximately perpendicular to the plane of the (PdCl), bridge.1°2 Thefirst perfluoro-n-allylic complex has been isolated from the reaction of tri-carbonyloctafluorocyclohexa-1,3-dieneiron with caesiurn fluoride in tetra-hydrofuran;1°3 n-C,F,Fe(cO), + F- --+ I.n-C,F,Fe(CO),]-. Bis(cyc1openta-dieny1)nickel reacts with tetrafluoroethylene when heated in tetrahydrofuranat SO", giving a new n-allylic derivative log of unusual structure (17).CHlC INi('7)The diamagnetic, octahedral molybdenum complex ( 1 8), prepared fromMo(CO), and ethyl sorbate at 130°, undergoes reaction lo5 with methanol toform the binuclear complex (19).The stable cation, [Re(CO),(C,H,),] +,MeMeOH - Et0,CMeMeMeco ' ' c o('9)has been isolated as its hexafluorophosphate; it is colourless and diamagneticand probably contains n-bonded C,H, ligands in &-octahedral positions.lo6Cations containing penta- and hexa-dienylcarbonium ions as ligands areobtained by hydride abstraction from the corresponding alcohols, e.g.,lo7HFeoc '.I -'cocoHClOaH0 C ' : e ~ C Ocoloo G.W. Parshall and G. Wilkinson, Chem. and Ind., 1962, 261.lolB. L. Shaw, Chern. and I d . , 1962, 1190.Io2 J. M. Rowe, Proc. Chern. Soc., 1962, 66.lo3G. W. Parshall and G. Wilkinson, J., 1962, 1132.lo4 D. W. McBride, R. L. Pruett, E. Pitcher, and F. G. A. Stone, J . Amer. Chem.lo6 R. P. M. Werner and S . Manastyrskyj, J . Inorg. Nuclear Chem., 1961, 21, 278.lo6 E. 0. Fischer and K. Ofele, Angew. Chem., 1962, 74, 76.SOC., 1962, 84, 497.J. E. Mahler and R. Pettit, J . Amer. Chern. SOC., 1962, 84, 1511NICHOLLS : THE TEANSITION ELEMENTS 181Two butadieneiron carbonyls have been prepared from Fe,(CO) in n-hexane.I n C,H,Fe(CO),, an unstable orange liquid, the olefin is readily replaced bytriphenylphosphine ; crystalline C,H,Fe,(CO), is stable in air.10s The co-ordination around the iron atom in tetracarbonyl(acry1onitrile)iron is essen-tially trigonal bipyramidal, the equatorial plane containing two Fe-CObonds and one from iron to the C=C double bond in acry10nitrile.l~~Intramolecular distances (X-rays) in 2,4,6-triphenyltroponeiron tricarbonyl,[C,H30( C,H,),]Fe(CO),, clearly indicate bonding of the Fe{CO), fragmentwith only two of the three double bonds in the ring.ll0 Irradiation ofsolutions of cyclo-octatetraeneiron tricarbonyl in benzene, in the presenceof excess of cyclo-octatetraene, gives rise to yellow complexes which areFe(CO), adducts of hitherto unknown C,Hs dimers.lll The molecularstructure of C,H,Fe(CO), shows that it contains a new form of cyclo-octa-tetraene ring-a distorted tub form in which six of the eight atoms of thering are very nearly coplanar.112 The synthesis of n-bonded metal com-pounds containing the cyclopropene ring has been attempted.l13 Triphenyl-cyclopropenyl bromide reacts with the [Co(CO),]- and [Fe(CO),N0I3-anions giving compounds in which the cyclopropene ring may be intact,e.g.(20) ; an alternative structure for the cobalt compound is that containingthe four-membered ring system (21). Very stable and unreactive compoundsj-+co(co)30(21)$k! 0 ICO) 3(20)result from the interaction of hexafluorobut-2-yne with iron and cobaltcarbonyls and with carbonyl-n-cyclopentadienyl-cobalt and -nickel ; typicalproducts are C9Fl,0Fe(CO), [probable structure (22)], C,F,Co,(CO),,C,F,Ni,( n-C5H5),, and ( n-C5H,)CoC,Fl,.In the last compound, nuclear magnetic resonance spectroscopy clearlyshows two types of CF, groups to be present, and hence its structure is asshown in (23).These are the fist examples of a cyclic carbon system boundto a single metal atom by both G bonds and donor olefinic bonds.ll4lo8 H. D. Murdoch and E. Weiss, Helv. Chim. Actu, 1962, 45, 1156.lo9 A. R. Luxmoore and M. R. Truter, Actu Cryst., 1962, 15, 1117.110 D. L. Smith and L. F. Dahl, J . Amer. Chern. Xoc., 1962, 84, 1743.l l 1 G. N. Schrauzer and S. Eichler, Angew. Chem., 1962, 74, 585.112 B. Dickens and W. N. Lipscomb, J. Amer. Chem. Soc., 1961, 83, 4862.113 C. E. Coffey, J. Amer. Chem. Xoc., 1962, 84, 118.114 J.L. Boston, D. W. A. Sharp, and G. Wilkinson, J., 1962, 3488182 INORGANIC CHEMISTRY(f) Acetylene complexes. The photochemical displacement of a carbonylgroup from a metal complex by diphenylacetylene has been used in thepreparation of n-C,H,Mn( CO),PhCiCPh. 116 Complex acetylides of palla-dium(I1) and palladium(0) have been prepared in liquid ammonia by thereactions :K,Pd(CN), + 2KC:CR -+ K,[Pd(CN),(CiCR),] + 2KCNK,[Pd(CN),(CiCR),] + 2K -+ K,Pd(CiCR), + 2KCN.The platinum compounds are obtained similarly. Ammonia-insolubleK2Pt(CiCR), is diamagnetic and pyrophoric, and can be oxidised with dryoxygen in ammonia to the tetra-alkynylplatinate(n).116 Ethynyl(tertiaryphosphine)copper(I) complexes, RCiCCu(PR,),, are dimeric in nitrobenzeneand rather more associated in benzene when n = 1 ; they are monomerswhen n = 2.A crystallographic investigation of PhCiCCuPMe, shows thatthe complex contains tetrameric units, each with a zig-zag chain of fourcopper atoms. Gold alkynyls, e.g., (PhCiCAu),, (ButCiCAu),, and their com-plexes with donor molecules, have been described ; towards PhCiCAu, theorder of donor strength is PR, > P(OR), > RNC > AsR, > SbR, > Amines.The alkynyls are probably n-bonded between the alkynyl groups and thegold atorns.l17 Diphenylzinc reacts with two moles of phenylacetylenein ether to give Zn(PhCiC),. If a 1 : 1 ratio of reactants is used, the in-termediate formed, PhZnCiCPh, disproportionates in ether and ammoniato ZnPh, and Zn(PhCiC),. Passage of gaseous acetylene through a sus-pension of zinc amide in ammonia produces the soluble non-electrolyte,Zn(CiCH),,2NH,.118Weak complexes are formed be-tween titanium(rv) chloride and benzene, 1,l -diphenylethane, 1,1,3,3-tetra-phenylbut-l-ene, and I-methyl-l,3,3-triphenylindane.There is strongevidence that the titanium(1v) chloride is interacting with the phenyl groupsin the olefins 1 ,l-diphenylethylene and 1 ,1,3,3-tetraphenylbut-l-ene.11sThe reflectance and infrared spectra of [CoHg,(sCN),,C,H,] show that thecobalt is octahedrally co-ordinated and that all six SCN groups serve tobridge the two metal atoms. Since [CoHg,(SCN),] is non-existent, andunlikely therefore to act as a host lattice for benzene, it is suggested that the(g) Complexes with aromatic systems.Ph Ph CI Ph Ph I=[ .-:::: Pd 4P,I APd::.xl )=((24) --.- ’ ‘CI_-.- -Ph Ph . Ph Phbenzene molecule forms n- bonds simultaneously with two mercury atomsbeing the fourth ligand of each.120 Tetraphenylcyclobutadienepalladium(n)chloride (24) is obtained upon treatment of the bisbenzonitrilepalladium(n)115 W. Strohmeier, H. Laporte, and D. Von Hobe, Chem. Ber., 1962, 95, 455.116 R. Nast and W. Horl, Chem. Ber., 1962, 95, 1470; R. Nast and W.-D. Heinz,117 G. E. Coates and C. Parkin, J . Inorg. Nuclear Chem., 1961, 22, 59; idem, J.,118 R. Nast, 0. Kunzel, and R. Muller, Chem. Ber., 1962, 95, 2155.119 B. Elliott, A. G. Evans, and E. D. Owen, J., 1962, 689.120 R. Bauer, M. Schellenberg, and G. Schwatzenbach, Helw. Chim. Acta, 1962,ibid., p.1478.1962, 3220.45, 775NICHOLLS : THE TRANSITION ELEMENTS I83chloride and diphenylacetylene reaction product with hydrochloric acid. 121Some n-complexes of transition metals with heterocycles have been described.With Mn, (CO ) o, p yrrole forms t ricar bonyl- n- pyrr ol y lmanganese ,( n-C,H,N)Mn(CO), ; with nickel carbonyl, duroquinone and an olefin(cyclo-octadiene, bicycloheptadiene, or dicyclopentadiene) forms diamag-netic n-complexes, (olefh)Ni( C6H1202). 122 New carbonylcyclopentadienylcations synthesised during the year include [ (n-C,H,)Fe(CO), olefin] +,[(n-C,H,)Cr(NO),CO] f, [(n-C,H,)Mo(CO),] f, apd [(n-C,H,)W(CO),] + ; theseare isolated as the tetrachl~roaluminates.~~~ Stable cations (26) are pro-duced by hydride abstraction from (n-C,H,)Fe(CO),R (R = Et, Pr", Pri)in a reaction which is reversible; the o-bonded alkyl complexes (25) are-H' -regenerated upon treatment of the ethylenic complexes with sodium boro-hydride. 124 The yellow-brown paramagnetic cation, [Cr(C,H,),] +, can beisolated as its'tetraphenylboron salt from the solution obtained by oxidationof biscyclopentadienylchromium with ally1 iodide. l25 Thorium( IV) anduranium(rv) chlorides react with potassium cyclopentadienide to give then-cyclopentadienyls, Th(n-C,H,), and U(n-C,H,),. Molybdenum(v) chlor-ide, however, gives diamagnetic Mo(C,H,), in which three of the cyclo-pentadiene rings are o-bonded.126 New cyclopentadiene-metal carbonyls in-clude the dimers [(n-C,H, M(CO),], (M = Os, Ru) and n-C,H, Tc(CO),, all ofwhich are obtained by treating the appropriate carbonyl halide with sodiumcyclopentadienide in an ether solvent. 12' Nucleophilic addition of C,H,-to the cation [Co(C,H,),]+ gives a red-brown diamagnetic complex of formulaCo,C,,H,,. There is considerable spectroscopic evidence for formulating thiscomplex as bis-[~-cyclopentadienylcobalt(~)-n-cyclopentadienyl- 1 -endo]-cyclopentadiene (27). 128 Complexes containing cyclopentadienyl and iso-nitrile groups have now been described. Hexakis( pheny1isocyanide)man-121 A. T. Blomquist and P. M. Maitlis, J. Amer. Chem. Xoc., 1962, 84, 2329.122 K. K. Joshi and P. L. Pauson, Proc. Chem. SOC., 1962, 326; G. N. Schrauzerand H. Thyret, 2. Naturforsch., 1961, 17b, 73.123 E. 0. Fischer and P. Kuzel, 2. anorg. Chem., 1962, 317, 226; E. 0. Fischer,K. Fichtel, and K. Ofele, Chem. Ber., 1962, 95, 249; E. 0. Fischer and K. Fichtel,ibid., 2063.lZ4 M. L. H. Green and P. L. I. Nagy, Proc. Chem. Xoc., 1962, 74; idem, J . Amer.Chem. SOC., 1962, 84, 1310.lz6 E. 0. Fischer and K. Ulm, Chem. Ber., 1962, 95, 692.126 E. 0. Fischer and Y. Hristidu, 2. Naturforsch., 1962, lyb, 275; E. 0. Fischerand A. Treiber, ibid., p. 276; E. 0. Fischer and Y. Hristidu, Chem. Ber., 1962, 95, 253.12' E. 0. Fischer and K. Bittler, 2. Naturforsch., 1962, 17b, 274; E. 0. Fischerand A. Vogler, ibid., p. 421; C. Palm, E. 0. Fischer, and F. Baumgarter, Naturwiss.,1962, 49, 279.12* E. 0. Fischer, W. Fellman, ar!d G. E. Herberich, Chem. Ber., 1962, 95, 2254;H. P. Fritz and H. J. Keller, ibid., p. 2259metal bond ; cyclohexyl isonitrile reactswith (C,H,)Pd(C6Hg) to give the novelNICHOLLS : THE TRANSITION ELEMENTS 185accepting capacity of the perfluoro and hydrocarbon derivatives. Thusbis(pentafluoropheny1)mercury (which is thermally stable at 250 ") formsstable neutral co-ordination compounds with 2,2'-bipyridyl and 1,2-bis-(diphenylphosphine)ethane.137 The l9F nuclear magnetic resonance spectraof a variety of fluorocarbon derivatives of metals have been reported. Thelarge shift to low field found for the absorption by a CF, group bondeddirectly to manganese, rhenium, iron, or cobalt is not observed if a carbonylgroup is interposed between the metal and the CF2 group. This magneticscreening effect is probably related to the presence of low-lying excited statesin the metal-carbon bonds so that the paramagnetic contribution to thescreening constants of the fluorine nuclei is substantially increased. 13*Metal-carbon 0- bonds are split by molecular hydrogen ; diphenylman-ganese reacts in tetrahydrofuran at room temperature to give manganeseand benzene. Hydrogenation of (n-C,H,),TiMe, produces methane andleaves (n-C,H,),Ti. 139 Electronic effects due to substituents in complexesof t,he type n-X*C,H,Cr(CO), have been discussed in terms of simple mole-cular-orbital theory and it has been shown that the degree of charge-transferto the central metal atom is related to the electron-donating power of X.140The bisbiphenylchromium(1) cation disproportionates slowly when irradiatedor heated in aqueous or methanolic solution into bisbiphenyl-chromium(0)and -chromium(n) .I41 The benzoic acid-containing cation, [PhCO,H][Ph,]Cr +,has been isolated as its tetraphenylboron salt. 142 The disproportionation oforganomercury halides by tertiary phosphines has been applied to perchloro-vinylmercury chloride :2CC1 ,:CCIHgCl + 2Ph 3P + (Ph 3P) ,HgCl , + (CCl ,:CCl) ,Hg.The reaction is by no means general, however ; addition of triethylphosphineto an ethereal solution of methylmercury bromide results in salt formationand gives [MeHgPEt,]Br. 143 The vapour pressures of dimethyl-zin and-mercury have been measured ; these compounds have Trouton's constantswhich are normal for non-associated liquids. 144Molecular Hydrides of the Transition Elements,-Many of these have beenmentioned in previous sections. A Tilden lecture of the Chemical Societyhas dealt with their chemistry. 145 A single-crystal X-ray determinationof the structure of (n-C,H,),MoH, shows that the molecule is wedge-like,the angle between the eclipsed cyclopentadiene rings being 25 & 3". TheMo-H bond length is approximately 1-1 A and the H-Mo-H bond angleapproximately 90". 146 In octahedral OsHBr(CO)(PPh,),, the Os-P bond13' R. D. Chambers, G. E. Coates, J. G. Livingstone, and W. K. R. Musgrave,J., 1962, 4367.138 E. Pitcher, A. D. Buckingham, and F. G. A. Stone,J. Chem. Phys., 1962,36,121.139 K. Clams and H. Bestian, Annalen, 1962, 654, 8.140 D. A. Brown and H. Sloan, J., 1962, 3849.141 F. R. Hein and H. Scheel, 2. anorg. Chem., 1961, 312, 264.142 T. F. Burger and H. Zeiss, Chem. and Ind., 1962, 183.143 D. Seyferth and R. H. Towe, Inorg. Chem., 1962, 1, 185; R. J. Corss, A. Lander,144 L. H. Long and J. Cattanach, J. Inorg. Nuclear Chem., 1961, 20, 340.146 M. J. Bennett, M. Gerloch, J. A. McCleverty, and R. Mason, Proc. Chem. Soc.,and G. E. Coates, Chem. and Ind., 1962, 2013.J. Chatt, Proc. Chern. Soc., 1962, 318.1962, 357186 INORGANIC CHEMISTRYtrans to the assumed position of hydrogen is longer than expected from thesum of the covalent radii. The other Os-P bonds are shorter and benttowards Os-H, showing analogy with the structure of [PtHBr(Et,P),].147Lithium aluminium hydride reduction of [FeCl,( diphosphine),]( FeCl,) and[FeCl,(diphosphine),] [diphosphine = C,H,(PMe,),, C,H4(PEt,),, and alsoo-C,H,(PEf,),] gives mono- and di-hydrides, [FeHCl(diphosphine),], and[FeH,(diphosphine),]. 14s The reduction of perrhenate in aqueous ethylene-diamine with potassium gives a compound, K,ReH,, which is identical withthose described earlier as KRe,4H20 and KReH4,2H,O, and in view of itsdiamagnetism it may contain a dimeric anion with a rheniurn-rheniumbond.149D. N.A. K. HOLLIDAY.D. NICHOLLS.14' P. L. Orioli and L. Vaska, Proc. Chem. SOC., 1962, 333.148 J. Chatt and R. G. Hayter, J., 1961, 5507.148 A. P. Ginsberg, J. M. Miller, and E. Koubeck, J. Amer. Chem. SOC., 1961, 83,4909

ISSN:0365-6217    

DOI:10.1039/AR9625900129

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

ORGANIC CHEMISTRY1. INTRODUCTIONA SLIGHT alteration has been made in the arrangement of this year's Reportby the introduction of sections on " Physical Properties and Organic Struc-ture " and " Reaction Mechanisms " in place of the customary " Theoreti-cal " section. The change reflects the increasing use and greater power ofphysical methods in structure determination. As a result, this Report con-tains no collected account of the quantitative study of organic equilibria orof theoretical investigations of molecular structure and properties. It ishoped to rectify these omissions on a future occasion.I n recent years the study of stereochemistry has become more and moreintegrated with other aspects of structural investigation and all sections ofthis Report contain material of stereochemical interest.A separate sectionunder this heading has therefore been discontinued, a policy which will besubject to review in future years.It was intended to include a separate section on steroids this year.Owing to illness of a Reporter, this has not been possible. At short notice,Dr. Overton, with the help of Dr. C. J. W. Brookes, Dr. J. Elks, and Pro-fessor w. Klyne, has included in the " Alicyclic '' section a brief summary ofsome of the more important steroid papers published during 1962.The section on " Reaction Mechanisms '' is planned as a representativeaccount of current work and illustrates the extent to which mechanisticstudies of organic reactions are being pursued. Lack of space has preventedthe inclusion, this year, of detailed reports on several important topics, ofwhich the stereochemistry of substitution a t phosphorus and silicon atomsare especially noteworthy and regrettable omissions.Important studieson simple heterolytic reactions have concerned olefin-forming eliminatioruand the clear demonstration of the formation of a tetrahedral intermediatein an electrophilic aromatic substitution. There has been extensive workon intramolecular catalysis of hydrolytic reactions as models for enzymecatalysis. The almost simultaneous appearance of several textbooks onenzyme mechanisms within the general context of organic reaction mechan-isms underlines the importance of this approach.Theoretical problems of general interest have been provided by a challeng-ing attack on the basis for " non-classical " carbonium ions and by a pro-posed re-definition of the concept of aromaticity.Ideas on the latter subjectand consequently on the status of the Hiickel rule have been stimulated byexperimental work on large conjugated rings (annulenes), in particular ontheir nuclear magnetic resonance spectra. Important developments inseveral fields are t o be expected from studies of the chemistry of diazirine,the cyclic isomer of diazomethane.L. Ingraham, " Biochemical Mechanisms," {ohn Wiley & Sons, Inc., New York,1962; E. M. Kosower, " Molecular Biochemistry, McGraw-Hill Publ. Co., New York,1962; S. G. Waley, " Mechanisms of Organic and Enzymic Reactions," Oxford Univ.Press, 1962188 ORGANIC CHEMISTRYThere has again been intensive work on certain general methods such asthe Wittig synthesis, hydroboration, and modified uses of lithium aluminiumhydride, sodium borohydride, and related systems.Aluminium hydrideshows a valuable selectivity and there has been interest in catalytic hydro-genation with catalysts prepared by treating noble metal salts with sodiumborohydride. The methylene-transfer reagents, dimethylsulphonium methyl-ide and dimethylsulphoxonium methylide, have a useful r81e to play insynthesis.Characterisation of natural acetylenes from the Compositz continuesapace and the remarkable structural relations of these to other com-pounds which occur with them in Nature are becoming clearer. Interestin the nature of the insect-attractant substances, many of which are simplecompounds, is widening.The structures of various prostoglandins havebeen cleared up.Photochemical transformations, especially of terpenoids and steroids,have been extensively investigated and many interesting products arereported. Optically active trans-cyclo-octene has been reported and thenonadrides, as represented by glauconic and byssochlamic acid, are anunusual new class of natural product. The past year has seen considerableadvances in the tetracycline antibiotic field : a fully biologically active proto-type of the tetracycline series has been made and there has been progressin biosynthetic studies. A particularly elegant synthesis of griseofulvin hasbeen effected.Progress with the betanidine problem has been reported and a newstructure is proposed for xylindein.4H-Pyran has been obtained. Theyear’s work on alkaloids offers much to the chemical connoisseur and bio-genetic schemes, hypothetical or experimentally supported, are again ofinterest.Study of the nucleic acids has made considerable advance, particularlyfrom a biochemical aspect, since the last Report. The value of nuclearmagnetic resonance spectroscopy in carbohydrate chemistry is being in-creasingly recognised.in organic chemistry which were pub-lished during 1940-1960 has appeared. Its value and continuity is en-hanced by the annual appearance of the “ Bibliography of Chemical Re-views ” which commenced with coverage of the year 1958 and has nowreached 1961.A useful index of review articlesL.c.V. G.N. Kharasch, W. Wolf, and E. C. P. Harrison, ‘‘ Index to Reviews, SymposiaVolumes and Monographs in Organic Chemistry for the Period 1940-1960,” Pergamon,Oxford, 1962MILLEN AND WHITE: PROPERTIES ASD STRUCTURE 1892. PHYSICAL PROPERTIES AND ORGANIC STRUCTURETHIS section of the Report surveys the application of physical methods tothe determination of structures of organic compounds. Attention is devotedmainly to spectroscopic methods including resonance techniques ; diffractionmethods are referred to only occasionally and incidentally, since these arecovered elsewhere ; but optical rotatory dispersion, molecular polarisability,mass spectrometry, and dipole moments are included.No attempt hasbeen made to survey work prior to 1962, except that where recent develop-ments have arisen directly from work in the last few years reference ismade to such papers. New booksl-3 include discussions of the informa-tion which the various techniques may yield. Reviews have appeared onthe use of microwave spectro~copy,~ electron magnetic resonance, nuclearmagnetic resonance,6-8 and optical rotatory dispersion 9, lo for structuraldeterminations. A collection of structures recently determined by micro-wave spectroscopy has also been made.ll Volume I11 of Progress in Xtereo-chemistry l 2 and Volume I11 of Methods of Experimental Physics l3 (whichis devoted entirely to the determination of molecular structure) haveappeared. Varian Associates have published a collection of nuclear mag-netic resonance spectra of organic compounds.l4Bond Distances and Angles-The significance of the variously definedbond lengths re, r,, and rS, in spectroscopy, and rm and rg in electron diffrac-tion, has been discussed.15 Carbon-carbon bond lengths have continuedto be the subject of much discussion,16 and a summary of such distancesfor open-chain molecules has been drawn up.17 Bartell has put forwardthe view that interactions between non-bonded atoms in quite simple mole-cules are important in determining bond angles and distances. Wilson,lgon the other hand, in a critical examination of various theories concerning“ Elucidation of Structures by Physical and Chemical Methods, Part I,” ed.K.W. Bentley, J. F. Macfarlan and Co. Ltd., Edinburgh, and John Wiley, London,1962.“ Determination of Organic Structures by Physical Methods,” ed. F. C. Nachodand W. D. Phillips, Vol. 11, Academic Press, New York, 1962.J. D. Roberts, “ An Introduction to Spin-Spin Splitting in High-ResolutionNuclear Magnetic Resonance Spectra,” Benjamin, New York, 1961.4 E. B. Wilson, Pure Appl. Chem., 1962, 4, 1.J. F. Gibson, Roy. Inst. Chem. Lectures, Monographs, Reports, 1962, 86, 37.J. Delmau, Bull. Soc. chim. France, 1962, 1.R. A. Y. Jones and A. R. Katritzky, Chem. and Ind., 1962, 522.K. Mislow, Ann. New York Acad. Xci., 1962, 93, 457.* R. A. Y. Jones and A. R. Katritzky, Angew. Chem., 1962, 74, 60.lo M. K. Hargreaves, Nature, 1962, 195, 560.l1 W. Maier, Pure Appl.Chem., 1962, 4, 157.l2 “ Progress in Stereochemistry,” Vol. 111, ed. P. B. D. de la Mare and W. Klyne,Butterworths Scientific Publns., London, 1962.l3 “ Methods of Experimental Physics. Vol. 111. Molecular Physics,” ed. D.Williams, Academic Press, New York, and London, 1962.l4 ‘‘ N.M.R. Spectra Catalogue,” compiled by N. S. Bhacca, L. F. Johnson,and J. N. Shoolery, Varian Associates, Palo Alto, Calif.l5 D. R. Lide, Tetrahedron, 1962, 17, 125.l6 Epistologue on Carbon-Carbon Bonds, ed. M. J. S. Dewar, Tetrahedron, 1962,17, 123.l7 B. P. Stoicheff, Tetrahedron, 1962, 17, 135.L. S. Bartell, Tetrahedron, 1962, 17, 177.l9 E. B. Wilson, Tetrahedron, 1962, 17, 191190 ORGANIC CHEMISTRYvariations in bond lengths and angles has concluded that steric repulsionis not an important factor in simple molecules. He further concludes thatthe hybridisation theory does not have predictive status and that, althoughthere i8 good evidence of conjugation (in certain molecules) from barrierheights resisting rotation, evidence of the effect from bond lengths is muchless certain.Lide l5 has argued that the C-C bond distances in the con-siderable number of molecules for which accurate information is now avail-able can be understood on the basis that change of hybridisation is themajor cause of variation. The effect of delocalisation on C-C bonds isregarded as negligible, though where lone pairs may be involved in con-jugation (as in CN, CO, CF, CC1, etc.) it leads to significant bond-shortening.Mulliken 2o has likewise emphasised that isovalent conjugation is expectedto have a larger effect on bond lengths than sacrificial conjugation has.Covalent radii for carbon in different states of hybridisation have been putforward. l5The high-resolution Raman spec-trum of ethane,21 when combined with previous infrared work, leads t othe following parameters: C-C 1.538; C-H 1.106 A, andLH-C-H 108.8".Parameters have also been obtained for hexadeuteroethane. For butadienea trans-structure has been confirmed;22 no evidence of a cis-form was foundin a search for the microwave spectrum.23 The structure of butatriene hasalso been confirmed, and bond distances have been evaluated.24 The struc-tural parameters which have been obtained for t-butylacetylene (3,3-dimethylbut-l-yne) reveal a C-C bond adjacent to the triple bond which is0-02-0.04 A longer than in methylacetylene ( p r ~ p y n e ) .~ ~ A second isomerof 1,3,5-hexatriene has been identified and shown from its infrared spectrumto have the cis-configuration.26Anomalous rotatory dispersion curves associated withxanthates and acylthioureas can be used for stereochemical studies ofalcohols and cc-substituted carboxylic acids. 27, 28 A single conformationhas been suggested for diethyl ether, and rotational isomerism of higherethers has been considered to account for their molecular polarisabilities. 29Three rotational isomers have been suggested to explain the infrared spec-trum of butyl vinyl ether, and energy differences between the isomers havebeen evaluated.30 Rotational isomers have also been reported for trans-2-chlorovinyl methyl ether, but no rotational isomerism is found for the2O R.S. Mulliken, Tetrahedron, 1962, 17, 247.2 l B. P. Stoicheff, Canad. J . Phys., 1962,40, 358; D. W. Lepard, D. M. C . Sweeney,and H. L. Welsh, Canad. J . Phys., 1962, 11, 1567.22 D. J. Marais, N. Sheppard, and B. Stoicheff, Tetrahedron, 1962, 17, 163.23 D. R. Lide, J. Chem. Phys., 1962, 37, 2074.2 4 A. Almenningen, 0. Bastiansen, and M. Traetteberg, Acta Chem. Scand., 1961,a5 L. J. Nugent, D. E. Mann, and D. R. Lide, jun., J . Chem. Phys., 1962, 36, 965.E. R. Lippincott and T. E. Kenney, J . Amer. Chem. SOC., 1962, 19, 3641.2' B. Sjoberg, D. J. Cram, L. Wolf, and C. Djerassi, Acta Chem.Scand., 1962,2B C . Djerassi, K. Undheim, and A. M. Weidler, Acta Chem. Scand., 1962, 16,29 M. J. Aroney, R. J. W. Le FGvre, and J. Saxby, J., 1962, 2886.30 E. M. Popov, N. S . Andrew, and G. I. Kagan, Optics and Spectroscopy, 1962,Aliphatic Compounds.-Hydrocarbons.Oxygen groups.15, 1557.16, 1079.1147.12, 17MILLEN AND WHITE: PROPERTIES AND STRUCTURE 191cis-isomer in any phase.31 Infrared and Raman spectra of dialkoxy- 32 anddialkylthio-methanes 33 have been discussed in terms of rotational isomerism.Temperature-dependences of infrared, Raman and nuclear magnetic reson-ance spectra of diethyl ketone 34 indicate an equilibrium between a t leasttwo conformational isomers. A similar study has been made for unsatur-ated ketones ;35 trans-pent-3-en-2-one exists exclusively in the s-cis-form inthe solid and in equilibrium with the s-trans-form in the liquid state.Molecular polarisabilities of some simple carboxylic esters 36 indicate thatthe C0,R group is non-planar, assumption of 30" rotation of the C-O-Rtriangle about the (C0)-0 bond usually reconciling calculation with obser-vation.On the other hand, a completely planar skeleton has been deducedfor methyl formate 37 in the gas phase from its microwave spectrum. Diethyloxalate 38 is probably a mixture of cis- and trans-isomers, neither of whichis planar, and esters of other dibasic acids probably consist of several forms.Similar studies of cyclic dibasic acid anhydrides 39 indicate that maleic,succinic, citraconic, itaconic, phthalic, and naphthalic anhydride have flatstructures, while glutaric, diphenic, camphoric, and cineolic anhydride havenon-planar structures.The measured molar Kerr constants enable themore appropriate of alternative conformations to be chosen. The nuclearmagnetic resonance spectra 40 of two of the isomers of 3-methyl-5-phenyl-penta-2,4-dienoic acid and the corresponding esters have been observed.These establish the isomers as 2-cis,4-cis- and 2-trans,4-cis ; the 4-cis-isomershave preferred 3-s-trans-conformation. Mass-spectroscopic studies 41 ofnormal long-chain methyl esters and hydrocarbons have been reported.Proton magnetic resonance spectra 42 of phosphorus esters indicate thatthese molecules spend an important fraction of time in a single preferredgeneral conformation. Rotation is considered to be rapid around P-C andP-0-C linkages.Dipole moments 43 of some peroxy-compounds have beenreported and interpreted for esters of aliphatic peracids on the basis of askew conformation about the peroxy-group with the acyl group twisted outof the C-0-0 plane.A re-examination 44 of the microwave spectrum ofchloroform has led to a revised C-H bond length of 1.100 A, not signific-antly different from that for methyl chloride (1.096 A) ; a C-C1 distance of1.758 A is to be compared with 1.781 A for methyl chloride. Structural31 Y. Mikawa, S. Morita, and S. Tsunakawa, Bull. Chem. SOC. Japan, 1962, 35,1109.32 K. Nukada, Bull. Chem. SOC. Japan, 1961,34,1615,1624; 1962,35,3; Spectrochim.Acta, 1962, 18, 745.3 3 D.Welti and D. Whittaker, J., 1962, 4372.34 R. N. Jones and K. Noack, Canad. J . Chem., 1961, 39, 2214.35K. Noack and R. N. Jones, Canad. J . Chem., 1961, 39, 2225.36 R. J. W. Le F'6vre and A, Sundaram, J., 1962, 3904.37 R. F. Curl, J. Chem. Phys., 1959, 30, 1529.38 M. J. Aroney, D. Izsak, and R. J. W. Le FBvre, J., 1962, 3997.39 R. J. W. Le F'6vre and A. Sundaram, J., 1962, 4009.40 R. H. Willey, T. H. Cramford, and C. E. Staples, J . Org. Chem., 1962, 27, 1535.41 D. Nguyh, R. Ryhage, S. Stkillberg-Stenhagen, and E. Stenhagen, Arkiw Kemi,4 4 T. H. Stiddall, tert., and C. A. Prohaska, J . Amer. Chem. SOC., 1962, 84, 3467.43 F. Verderame and J. G. Miller, J . Phys. Chem., 1962, 66, 2185.4 4 M. Jen and D.R. Lide, J . Chem. Phys., 1962, 36, 2525.Halogen compounds.1962, 18, 393192 ORGANIC CHEMISTRYparameters for methylene chloride,45 ethyl chloride,46 chloromethylsilane,47and 1 ,l-dichlorocyclopropane 48 include C-C1 bond distances of 1-77, 1.788,H 1.788, and 1.73 A, respectively. Structural informa-I tion has also been reported for propargyl fluorideY4Qc , H C H z trichlorofluoromethane~50 and for t-butyl cyanide,25chlorideY5l and bromide.52 The microwave spectrum of Ffiuoroprene 23 indicates a trans-planar configuration (1 1.Hydrogen and fluorine nuclear magnetic resonance spectra 53 of poly-substituted ethanes over the temperature range 250450" K have beeninterpreted to provide values of differences between potential-energy minimaof rotamers.The first detailed microwave spectroscopic study of rotationalisomerism has appeared;54 the spectra of the trans- and gauche-forms ofpropyl fluoride have been analysed. The energy minimum for the gauche-form occurs at a dihedral angle of 63" and lies below that of the transformby 0.47 5 0.31 kcal./mole. An approximate estimate has been given ofthe barrier at the cis-configuration and also of the lower barrier separatingthe gauche- and the trans-configuration. Barriers resisting rotation of themethyl groups are included in the Table on p. 195. As a result of a detailedanalysis 55 of infrared spectra of alkyl halides, criteria have been proposedto distinguish, not only between primary, secondary, and tertiary halides,but also between conformations about the adjacent C-C bond.Rotationalisomerism of alkyl halides has also been discussed in relation to molecularpolarisabilities,5* dipole and dielectric relaxation. 58 The pres-ence of five rotational isomers in estimated proportions has been reportedfor n-butyl chloride, and hindered rotation in s-butyl chloride has also beenstudied.59 The nuclear magnetic resonance coupling constants 6o betweenmethine protons of 2,3-disubstituted n-butanes have been used to obtainqualitative estimates of rotamer populations. Formeso-2,3-dibromo-, -2,3-dichloro-, and -2,3-diphenyl-ciiacetoxybutane, conformations with gauche-acetoxy- Mebutane, form (2) is favoured, whilst for meso-2,3-substituents possess a lower energy than those with atrans-arrangement, possibly indicating an electrostaticattraction between acetoxy-groups.H2C *(I)x&: (2)H45W.H. Flygare and W. D. Gwinn, J. Chem. Phys., 1962, 36, 787.46 R. H. Schwendeman and G. D. Jacobs, J . Chem. Phys., 1962, 36, 1245.4 7 R. H. Schwendeman and G. D. Jacobs, J. Chem. Phys., 1962, 36, 1251.4 8 W. H. Flygare, A. Narath, and W. D. Gwinn, J . Chem. Phys., 1962, 36, 200.4 9 B. E. Job and J. Sheridan, Nature, 1962, 193, 677.50 J. H. N. Loubser, J . Chem. Phys., 1962, 36, 2808.51 W. Zeil, M. Winnewisser, and K. Muller, 2. Nuturforsch., 1961, 16a, 1250.5 2 W . Zeil, M. Winnewisser, and W. Huttner, 2. Nuturforsch., 1961, 16a, 1248.53 H. S. Gutowsky, G. G. Bedford, and P. E. McMahon, J . Chem. Phys., 1962,54E. Hirota, J.Chem. Phys., 1962, 37, 283.55 J. J. Shipman, V. L. Folt, and 8. Krimm, Spectrochim. Actu, 1962, 18, 1603.56 M. Aroney, D. Izsak, and R. J. W. Le FBvre, J., 1962, 1407.67 H. Lumbroso, Cmpt. rend., 1962, 254, 2750.68 J. Meinnel and G. Martin, Arch. Sci., 1961, 14 (10th Ampere Colloquium), 56.5 9 T. Ukafi and R. A. Bonham, J . Amer. Chern. SOC., 1962, 84, 3631.60F. A. L. Anet, J . Amer. Chem. SOC., 1962, 84, 747; A. A. Bothner-By and C.36, 3353.Naar-Colin, ibid., 84, 743, 1962MILLEN AND WHITE: PROPERTIES AND STRUCTURE 193It has been shown that formamide 61 has a non-planarequilibrium structure with a low barrier to inversion, the N-H bonds makingangles of about 10" with the N-CHO plane. A similar non-planar equi-librium structure with easy inversion is indicated for cyanamide.62 Adetailed vibrational assignment has been made for N-methylformamide 63on the basis of a trans-structure though the possibility of the presence ofa small proportion of the cis-isomer is not excluded, but it has been suggestedthat neither a trans- nor a cis-structure will, if rigid, account for the com-plexity of the band contours;64 possibly inversion is important here also.The extent of the deviation from a planar configuration about the nitrogenatom has been discussed for various amines and amides in terms of infraredspectra 65 and for cyclic imines in terms of ultraviolet spectra.66 Dipolemoments of imides and amides, including acetamide derivatives, and theirstructural interpretations have also been reported.67 Infrared spectra ofpartially deuterated amides 68 show two N-H stretching frequencies, whichare attributed to bonds cis and trans to the carbonyl group.15N-Substitutedamides69 have been used to provide further evidence on the problem ofthe assignments for the amide group; the view is put forward that, for thesolid phase at least, the usual assignments of C-0 stretch and NH, deforma-tion should be interchanged. N-Methylthioformamide exists in cis- andtrans-forms in solution, but N-methylthioacetamide is found only in thetrans-configuration. 70 The dipole moments of acetanilide 71 derivativesindicate that the phenyl ring is inclined a t 46" & 5" to the plane of theacetyl group.The temperature-dependence of the nuclear magnetic resonance spectra 72of substituted amides has given values of the energy barrier and frequencyfactor for internal rotation about the central C-N bond, the probable errorin the determined energy barriers being less than &O-8 kcal./mole.Theenergy barrier depends on the solvent and also on the concentration of theamide ; in carbon tetrachloride the barrier decreases monotonically withdilution, while in dibromomethane the barrier initially increases to a maxi-mum and then decreases with increasing dilution.Acyclic imides . normally have trans-trans-configurations about theCO-NHCO group in the solid, but in solution in non-polar solvents trans-cis-configurations are found in associated molecules, which are probablyhydrogen-bonded dirners.T3 The infrared spectra of a number of diaminesNitrogen groups.61 C.C. Costain and J. M. Dowling, J . Chem. Phys., 1960, 32, 158.6 2 D. J. Millen, G. Topping, and D. R. Lide, J . MoZ. Spectroscopy, 1962, 8,6 3 I. Suzuki, Bull. Chem. SOC. Japan, 1962, 35, 540.6 4 R. L. Jones, J . Mol. Spectroscopy, 1961, 7, 460.6 5 P. J. Krueger, Nature, 1962, 194, 1077.6 6 A. T. Bottini and C. P. Nash, J . Amer. Chem. SOC., 1962, 84, 734.6 7 C. M. Lee and W. D. Kumler, J . Amer. Chem. SOC., 1962, 84, 565.68 A. G. Moritz, Nature, 1962, 195, 800.6 9 R. N. Kniseley, Spectrochim. Acta, 1962, 18, 1217.70 I. Suzuki, Bull. Chem. SOC. Japan, 1962, 35, 1456.71 M. Gomel, H. Lumbroso, and D. Peltier, Compt. rend., 1962, 254, 3857.7 2 M. T. Rogers and J. C. Woodbrey, J .Phys. Chem., 1962,66, 540; J . C. Woodbrey73 T. Uno and K. Machida, Bull. Chem. SOC. Japan, 1962, 35, 1226.153.and M. T. Rogers, J . Amer. Chem. SOC., 1962, 84, 13.194 ORGANIC CHEMISTRYand salts have been reported and the trans-trans-trans-configuration is sug-gested for NN’ - dimet hylet h ylenediamine hydrochloride. 74Wide-line proton magnetic resonance and infrared spectra 75 of poly-crystalline samples of salts of urea, thiourea, and formamidine disulphide(CC-dithiobisformamidine) have been obtained. If it is assumed that protontransfer has occurred, the nuclear magnetic resonance spectra are consistentwith protonation of the urea and thiourea salts a t oxygen or sulphur; informamidine disulphide dihydrochloride the protons are all located in theNH, groups.Further evidence has been provided for the view that saltsof both acetamide and NN-substituted acetamides have oxonium-typestructures. 76of glycine obtainedfor various orientations of a single crystal inthe magnetic field show that the NH3+ group H2N rJ C H 2 * C)!(3) is a regular tetrahedron whose axis lies alongthe C-N bond; the N-H bond distance wasdetermined to be 1.077 & 0.01 8. The high-resolution nuclear magneticresonance spectrum of the new amino-acid lathyrine shows that it is,!I- (2-aminopyrimidin-4-y1)alanine (3).N-Thiobenzoyl and N-phenylthioacetyl derivatives of a-arnino-acids havedesirable spectroscopic properties for spectropolarimetric studies. 79 TheN-phenylthioacetyl derivatives have strong Cotton effects which are suitablefor establishing absolute configurations.Mass spectra of amino-acids havebeen reported.80 The dipole moment g1 and structure 82 of formaldoximein the vapour phase have been determined; the configuration is found tobe (4), whereas the infrared intensities of hydroxyl bands in some amid-oximes 83 suggest structure (5) rather than (6).The wide-line nuclear magnetic resonance spectraN ,NH2C02H N,cis-trans-Isomerism of 1,l ’-methylenedi- (4-hydroxyiminopyridinium)halides has been reported from an infrared The structure of thezwitterion 85 which results from proton transfer in certain oximes containinga dimethylamine group has been discussed. The proton magnetic resonancespectra 86 of several ketone 2,4-dinitrophenylhydrazones and semicarb-7 4 M.E. Baldwin, Spectrochim. Acta, 1962, 18, 1455.7 5 C. R. Redpath and J. A. S. Smith, Trans. Paraday SOC., 1962, 58, 462.7 6 W. Kutzelnigg and R. Mecke, Spectrochim. Acta, 1962, 18, 549; W. D. Kumler,7 7 W. E. Webb and W. G. Moulton, J . Chem. Phys., 1962, 36, 1911.‘ 8 E. A. Bell and R. 0. Forster, Nature, 1962, 194, 91.7 9 B. Sjoberg, B. Karl&, and R. Dahlbom, Acta Chem. Scand., 1962, 16, 1071.80K. Biemann and J. A. McCloskey, J . Amer. Chem. SOC., 1962, 84, 3192.81 M. G. K. Pillai, J . Phys. Chem., 1962, 66, 179.8 2 I. N. Levine, J . Mol. Spectroscopy, 1962, 8, 276.83 J. Barrans, T. Marty, and R. Mathis, Compt. rend., 1962, 254, 2736.84 J. Tregellas-Williams, Austral. J . Chem., 1962, 15, 150.s 5 J.J. Noman, Canad. J . Chem., 1962, 40, 2023.8 6 G. J. Karabatsos, J. D. Graham, and F. M. Vane, J . Amer. Chem. SOC., 1962,J . Amer. Chem. SOC., 1961, 83, 4983; D. Cook, Canad. J . Chem., 1962, 40, 2362.84, 753MILLEN AND WHITE: PROPERTIES AND STRUCTURE 195azones in different solvents provide information of the stereoisomerism aboutthe C=N group; measurement of peak areas leads to an evaluation of thesyn-anti-composition. Nuclear magnetic resonance and infrared measure-ments 87 indicate that sulphaniloylguanidine has structure (7) rather than (8).Comparison of spectra of free succinonitrile and that bound in metalcomplexes where the gauche-configuration is established supports the con-clusion that the gauche-form of free succinonitrile is the more stable;s8adiponitrile and glutaronitrile have been examined in a similar way.89Other groups.The infrared spectrum of ethane- 1,2-dithiol closelyparallels that of 1 ,2-dichloroethane, showing the presence of a single form(trans) in the solid, and trans- and gauche-forms in equilibrium in the liquid.It seems likely that in di(alky1thio)ethanes the trans-form becomes pre-dominant in the liquid as the size of the alkyl group increases.g0The following three-fold barriers (kcal./mole) to internal rotation in freemolecules (gas-phase) bring up to date a recent survey.98(7) p-NH2.C,H**SO2*N:C(NH,) 2 p-NH,*C,H,*SO ,*NH*C(NH,):NH (8)Ref. Ref.CH,*PH, 1-96 91 truns-CH,CH,*CH,F 2.69 54CH,.SnH, 0.65 92 guuche-CH, CH ,*CH 2F 2.8 7 54CH,Cl.SiH, 2.55 47 CH,*AsF, 1.32 95CH,*CH=C=O 1-20 94CH ,Cl*CH, 3.685' 46 cis-CH,*CH=CHF 1-06 96(CH3)2NH 3-28 93 (CH3)2S 2*17* 97* Revised values.Carbon-carbondistances have been obtained for cyclobutane 99 from its rotational Ramanspectrum, but a definite decision between a planar and a non-planar ringhas not been made though the latter is favoured.For bromocyclobutanethe microwave spectrum 100 establishes a non-planar equilibrium structurewith a low-frequency bending vibration; a detailed structure has beenobtained for the " equatorially "-substituted isomer ; the " axial " isomerwas not detected. Correlations of substituent effects on the C-H stretchingvibration of various cyclopropyl lol and cyclobutyl 102 derivatives have beenHomocyclic Compounds.-3- , 4- , and 5-Membered rings.G.Schwenker, Arch. Pharm., 1962, 295, 753.I. Matsubara, Bull. Chem. SOC. Japan, 1962, 35, 27.3D. Welti and D. Whittaker, J., 1962, 4372.8sI. Matsubara, Bull. Chem. SOC. Japan, 1961, 34, 1710, 1719.91 T. Kojima, E. L. Breig, and Chun C. Lin, J. Chem. Phys., 1961, 35, 2139.9 2 P. Cahill and S. Butcher, J . Chem. Phys., 1961, 35, 2255.93 W. G. Fateley and F. A. Miller, Spectrochim. Acta, 1962, 18, 977.94 B. Bak, D. Christensen, J. Christiansen, L. Hansen-Nygaard, and J. Rastrup-9 6 L. J. Nugent and C. D. Cornwell, J . Chem. Phys., 1962, 37, 523.9 6 R. H. Beaudet and E. B. Wilson, J . Chem. Phys., 1962, 37, 1133.9 7 H. D. Rudolph and H. D. Dreizler, 2. Naturforsch., 1962, Ira, 712.98 D. J. Millen, " Progress in Stereochemistry," ed.W.Klyne and P. B. D. de la Mare,99 R. C. Lord and B. P. Stoicheff, Canad. J . Phys., 1962, 40, 725.Andersen, Spectrochim. Acta, 1962, 18, 1421.Butterworths Scientific Publns., London, Vol. 111, 1962, p. 138.loo W. G. Rothschild and B. P. Dailey, J . Chem. Phys., 1962, 36, 2931.lol H. Weitkamp, U. Hasserodt, and F. Korte, Chem. Ber., 1962, 95, 2280; P. G.lo2 G. Chiurdoglu, T. Doehaerd, and M. Duts, Bull. SOC. chirn. belges, 1961, 70,Gassman, Chem. and Ind., 1962, 740.642196 ORGANIC CHEMISTRYmade and some information obtained on nortricyclene 103 derivatives.Infrared and nuclear magnetic resonance spectra lo4 have been used toestablish structures of cyclobutane derivatives obtained from the reactionof chlorotrifluoroethylene with olefins.The nuclear magnetic resonancespectra of cyclopentane and cyclopentene systems have been reported. 105The microwave spectrum of cyclopentene lo6 shows it to have a non-planarequilibrium carbon skeleton with a dihedral angle between the two skeletalplapes of 22". Cyclopentanol exists at least partly in a non-planar con-formation since two C-0 stretching bands have been observed.107 Thebroad aromatic peak in the nuclear magnetic resonance spectrum of cis-1,2-diphenylcyclopentene has been found to narrow when the sample isheated, which has been interpreted as evidence of restricted rotation of thephenyl groups; there is no evidence of restricted rotation in the stilbenes,diphenylc yclopropanes , or trans- 1,2 - diphenylc yclopent ane.108The main features of the barrier governing thechair-chair conversion of cyclohexane are becoming clear. The activationenergy for the conversion is found to be 11.5 & 2 kcal./mole.log Fromprevious work the energy of the boat form has been estimated as5.5 kcal./mole above that of the chair form.l10 Free-energy changes forthe equatorial-axial conversion have been obtained for methyl, ethyl, iso-propy1,lll and thioalkyl groups. 112 From ultrasonic absorption measure-ments on methylcyclohexane an activation energy of 6.36 kcal./mole hasbeen estimated.113 The diequatorial isomer of trans-4-chlorocyclohexanolis found to be more stable than the diaxial form in carbon disulphide solutionby 0.76 kcal./mole. 114 Chemical-shift differences for isomeric nitrocyclo-hexanes provide information about the axial or equatorial conformation ofthe nitro-group.l15Conformational free-energy differences 116 for substituted cyclohexaneshave been studied by nuclear magnetic resonance spectroscopy. The massspectra of cycloalkane derivatives have been discussed.117 The structuresof cyclohexane- 1,3-diols have been established from the nuclear magnetic6-Membered rings.lo3 0.E. Pollard, Spectrochim. Acta, 1962, 18, 837.lo4 P. Tarrant, R. W. Johnson, jun., and W. S. Brey, jun., J . Org. Cheno., 1962,lo5 J. D. Park, R. L. Settine, B. A. Parkin, jun., and G, W. Hedrich, J . Org. Chem.,lo6 G. W. Rathjens, jun., J . Chem. Phys., 1962, 36, 2401.lo' G. Chiurdoglu and W. Masschelein, Bull.SOC. chim. belges, 1962, 71, 59.lo* D. Y. Curtin, H. Grun, Y. G. Hendrickson, and H. E. Knipmeyer, J . Amer.Chem. Xoc., 1961, 83, 4838.log F. R. Jensen, D. S. Noyce, C. H. Sederholm, and A. J. Berlin, J . Amer. Chem.SOC., 1962, 84, 386.110 N. L. Allinger and L. A. Freiberg, J . Amer. Chem. SOC., 1960, 82, 2392; W. S.Johnson, V. J. Bauer, J. L. Margave, M. A. Frisch, L. H. Dreger, and W. N. Hubbard,ibid., 1961, 83, 606.ll1 N. L. Allinger and Shih-en Hu, J . Amer. Chem. Xoc., 1962,84, 370; W. L. Allinger,L. A. Freiberg, and Shih-en Hu, ibid., p. 2836.112 E. E. Eliel and L. A. Pilato, Tetrahedron Letters, 1962, 103.113 M. E. Pedinoff, J . Chem. Phys., 1962, 36, 777.114 Y. Takeoka, Bull. Chem. SOC. Japan, 1962, 35, 1371.115 A. C. Huitric and W.F. Trager, J . Org. Chem., 1962, 27, 1926.116 E. E. Eliel and M. H. Gianni, Tetrahedron Letters, 1962, 97.117 J. Laune, Ind. chim. belge, 1962, 27, 245.27, 602.1962, 27, 898MILLEN AND WHITE: PROPERTIES AND STRUCTURE 197resonance spectra of the pure compounds; cyclohexane-1,3-diol, m.p. 116",has the trans-conformation, as has 5,5-dimethylcyclohexane-1 ,3-dio17 m.p.108 '. 118 Nuclear magnetic resonance spectra of 4-alkylcyclohexanols havealso been obtained.llg The stereochemistry of isomeric cis- and truns-2-(chloropheny1)cyclohexanols (with o-, m-, and p-chlorine) and the corre-sponding acetoxy-derivatives has been investigated similarly. The resultsare consistent with a chair form having the aromatic ring in the equatorialorientation.120 The proton magnetic resonance spectra 121 of cis-, muco-,and allo-inositol hexa-acetate as a function of temperature have givenenthalpies of activation and Arrhenius factors for some of the skeletaloscillations of the six-membered ring.Optical rotatory dispersion curves for a few cyclohexanone-type ketones 122are of unusually large amplitude; it has been suggested that a twist con-formation provides a possible explanation of abnormal amplitudes in decalonederivatives.A small amount of a twist form is probably present in 2-methyl-cyclohexanone at equi1ibri~rn.l~~ To assist the understanding of the opticalproperties of &-unsaturated ketones, it is helpful to treat the compositecarbonyl-carbon n-system as an inherently dissymmetric chromophore ; thisoften enables one to determine absolute configuration or conformation.124Optical rotatory dispersion of @?-unsaturated ketones has also been dis-cussed.125 Combining the observed Cotton effect of (+)-3-methylcyclo-hexanone with the observed effect of a 3-keto-5%-steroid or its bicyclicanalogue leads to a calculated Cotton effect for 1- and 4-methyl-3-keto-steroids. The observed amplitudes differ from the calculated values, thedifference being ascribed to a conformational distortion of the cyclohexanonering owing to steric interaction between an equatorial methyl group anda suitably located hydrogen atom in another ring.lZ6 It has been shownthat in a series of phenylcholestanones those with an axial phenyl groupon the carbon next to the carbonyl group are distinguished by an abnormallyintense n --+ n* transition; this is attributed to mixing in of an allowedcharge-transfer transition, which also provides an explanation of the largeCotton effect.12' The n -+ n* component of the mixed transition has amagnetic dipole transition moment along the carbonyl axis, and the chargetransfer aspect leads to a component of electric dipole transition momentalong the same axis, thus satisfying the condition for the development ofoptical rotatory power. The attribution of both the optical rotatory strengthof the transition and its intensity enhancement to the mixing-in of the118 H.Finegold and H. Kwart, J. Org. Chem., 1962, 27, 2361.119 A. H. Lewin and S. Winstein, J . Amer. Chem.SOC., 1962, 84. 2464.120 A. C. Huitric, W. G. Clarke, jun., K. Leigh, and D. C. Staiff; J . Org. C12em.,121 S. Brownstein, Canad. J. Chem., 1962, 40. 870.1962, 27, 715.122 C. Djerassi and W. Klyne, Proc. Nut. Acid. Sci. U.S.A., 1962, 48, 1093.123 C. Beard, C. Djerassi, T. Elliott, and R. C. C. Tao, J . Amer. Chem. SOC., 1962,124 A. Moscowitz, K. Mislow, M. A. W. Glass, and C . Djerassi, J . Amer. Chern.125 C. Djerassi, R. Records, E. Bunnenberg, K. Mislow, and A. Moscowitz, J . Amer.126 C. Djerassi, E. Lund, and A. A. Akhrem, J . Amer. Chem. SOC., 1962, 84, 1249.12' R. C. Cookson and J. Hudec, J., 1962, 429.84, 874.SOC., 1962, 84, 1945; K. Mislow and J. G. Berger, ibid., p. 1956.Chenz. SOC., 1962, 84, 870198 ORGANIC CHEMISTRYcharge-transfer component requires that the rotatory strength be propor-tional to the square root of the intensity enhancement.l2* Rotatory powersof several asymmetric ketones have been found to approximate to thisrelationship.128 Optical activity of alicyclic ketones is considered in cal-culations based on the one-electron model of optical activity.129The dipole moment of 2-fluorocyclohexanone l 3 O suggests that this com-pound is a mixture of equatorial and axial conformers, the former predominat-ing, the amount depending on the solvent ; similar measurements 131 indicatethat 2-chloro- and 2-bromo-cyclohexanone are also mixtures of the con-formers. An extension of these arguments 132 leads to the view that theequatorial conformation is found a t position 4 in 4-fluoro-5#?-cholestan-3-one.It has been suggested from an infrared and Raman study 133 thatcyclohexane-l,4-dione oscillates between the two boat forms through anintermediate skew-form.The infrared spectra of cyclohexane-l,3-dione andits 5,5-dimethyl derivative 13* show that even in the solid state both mole-cules exist in the enolic form and internal hydrogen bonding is suggested.4-Benzoylcyclohexane-1,3-dione is found to enolise completely in chloro-form ;I35 nuclear magnetic resonance and infrared work indicate thatdehydroacetic acid enolises completely, only one enol, the a-pyrone, beingformed. 136 Characteristic carbon-halogen frequencies have been assignedfor cyclohexene derivatives ; deviation from planarity about the doublebond is indicated for 1,2-dibromocyclohexene.137Nuclear magnetic resonance spectra provide evidence forthe structures of substituted cycloheptadienes obtained by 1 &addition totroponoid systems.138 A study of the dipole moments of 5,6,8,9-tetrahydro-benzocyclohepten-7-one, bicyclo[5,4,0]undecan-4-one, and 6,7,8,9-tetra-hydro-5H-benzocycloheptene shows that the cyclohept-4-en-1 -one systemconsists of a mixture of boat and chair forms, the latter ~red0rninating.l~~The nuclear magnetic resonance spectra of annulenes and dehydroannuleneshave been obtained and have been interpreted in relation to the aromaticityof the compounds. [ 14]Annulene, [ 24]annulene, and tetradehydro[ 24lannu-lene are non-aromatic, while monodehydro[ 14]annulene, [ 18lannulene andtridehydro[18]annulene are aromatic 140 (see also section 7 of this Report).The presence of two strong O-H stretching vibrationsLarger rings.Aromatic rings.12* S.F. Mason, J., 1962, 3285; Mol. Phys., 1962, 5, 343.lZD M. Vc.Vol’kenshtein and I. 0. Levitan, Zhur. strukt. Khim., 1962, 3, 80.130 N. L. Allinger and H. M. Blatter, J . Org. Chem., 1962, 27, 1523.131 P. Mauret and J. Petrissans, Compt. rend., 1962, 254, 3662; T. N. Pliev, Zhur.132 N. L. Allinger, M. A. Darooge, and C. L. Neumann, J . Org. Chem., 1962, 27,133 N. L. Allinger and L. A. Freiberg, J . Amer. Chem. SOC., 1961, 83, 5028.134 C. Duval and J. Lecomte, Compt. rend., 1962, 254, 36.135 K. Kotera, J . Pharm. SOC. Japan, 1961, 81, 1525.136 S. Forsen and M.Nilsson, Arkiv Kemi, 1961, 17, 523.13’ G. Chiurdoglu, R. Ottinger, J. Reisse, and A. Toussaint, Spectrochim. Acta,1962, 18, 215.lSs 0. L. Chapman, D. J. Paslo, and A. A. Griswold, J . Amer. Chem. SOC., 1962,84, 1213.139 N. L. Allinger and W. Szkrybalo, J. Org. Chem., 1962, 27, 722.140 L. M. Jackman, F. Sondheimer, Y. Amiel, D. A. Ben-Efraim, Y. Gaoni, R.Wolovsky, and A. A. Bothner-By, J . Amer. Chem. SOC., 1962, 84, 4307.$2. Khim., 1961, 35, 2144.1082MILLEN AND WHITE: PROPERTIES AND STRUCTURE 199in the infrared spectrum of o-t-alkylphenols has been ascribed to the exist-ence of cis- and trans-isomers in which the hydroxyl group is co-planar withthe ring.141 cis-trans-Isomerism is also indicated for monodeuteratedprimary aromatic amines by the observation of two N-D stretching fre-quencies.142 The observation of only one N-D frequency for picramide isheld to indicate bilateral hydrogen bonding.143Studies of molecular polarisability show that measured molar Kerr con-stants can be reconciled with an s-truns-conformation for cinnamaldehyde,an s-cis-conformation for benzylideneacetophenone, mainly s-truns-s-cis forcinnamylideneacetophenone, s-cis-s-cis for dibenzylideneacetone, and s-truns-s-cis, s-cis-s-trans for dicinnamylideneacetone, provided that in certaincases the phenyl groups are twisted 20-30" out of the plane, around the1,4-axis. A twist of 41" is indicated for each phenyl group of benzo-phen0ne.1~4 Similar measurements with diphenyl ether suggest a conform-ation with a twist of 37" between the phenyl g r 0 ~ p s .l ~ ~ Two bands in theinfrared spectrum of dihydroxybenzaldehyde which were formerly taken toindicate the presence of a monomer and a dimer are now attributed toFermi resonance.146 The correlation between structure and mass-spectralfeatures of benzoate-type esters has been discussed. 147 The significantdifference between the ultraviolet spectra of benzylideneaniline and styrenehas been attributed to non-planarity of the former; protonation gives aspectrum resembling that of styrene. 14*A detailed microwave-spectroscopic study of nine isotopic species ofbenzonitrile has given a complete rs structure of a benzene derivative andhas revealed angular distortions of about 270,149 the ring angles, startingfrom the substituent, being 122.5" & 0.6", 118.4" &- 0.6", and 120.3" -J= 0.4".Carbon-halogen bond distances have been obtained for m-chlorofluoro-benzene, 150 and the possibility of structural determination by microwavespectroscopy of a molecule as laxge as 2-fluoronaphthalene has .beenexamined. 151The ultraviolet spectra and optical rotatory dis-persion of optically active biaryls have been investigated. This work 152provides the first instance of conformational and configurational correla-tions of atropisomers by means of optical rotatory dispersion. The mag-netically anisotropic double bond in bicyclic Diels-Alder adducts deshieldsprotons in an exo-configuration and shields protons in an endo-configura-Polycyclic compounds.141 K.U. Ingold, Canad. J . Chem., 1962, 40, 111.142 A. G. Moritz, Spectrochim. Acta, 1962, 18, 671.143 A. N. Hambly and B. V. O'Grady, Chem. and Ind., 1962, 459.144 R. Bramley and R. J. W. Le Fevre, J., 1962, 56.145 R. J. W. Le Fevre, A. Sundaram, and K. M. S. Sundaram, Bull. Chem. SOC.Japan, 1962, 35, 690.146 S. Pinchas, J., 1962, 2835.14' T. Aczel and H. E. Lumpkin, Analyt. Chem., 1962, 34, 33.14* P. Brocklehurst, Tetrahedron, 1962, 18, 299.149 B. Bak, D. Christensen, W. B. Dixon, L. Hansen-Nygaard, and J. Rastrup-150.A. Rachman, P. Kokeritz, and H. Selen, J . Mol. Spectroscopy, 1962, 8, 338.51 B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup-Anderson, Spectro-152 K. Mislow, M. A. W. Glass, R. E. O'Brien, P. Rutkin, D.H. Steinberg, J. Weiss,Andersen, J . Chem. Phys., 1962, 37, 2027.chim. Acta, 1962, 18, 229.and C. Djerassi, J. Amer. Chem. Soc., 1962, 84, 1455200 ORGANIC CHEMISTRYt i ~ n . l ~ ~ This enables the configuration of a proton or proton-bearingsubstituent to be ascertained by the change in chemical shift when thedouble bond is removed by hydrogenation, but if the double bond carriesa magnetically anisotropic substituent interpretation of the results is moredifficult. I n 5-nitrobornene the nitro-group is in the endo-configuration.The nuclear magnetic resonance spectra of substituted azulenes and thecorresponding conjugated acids show that monoprotonation occurs in thefive-membered ring. 154 Infrared, ultraviolet, and nuclear magnetic reson-ance spectra have been used to characterise the tetramethyl[2,2 Jparacyclo-phane obtained from a saturated aliphatic precursor.155 A theoreticaltreatment of conformations of the decalins has been presented.156Terpene systems investigated by nuclear magneticresonance include unsaturated systems of the type CH2*CMe:CH*CH,X,157triterpenes of the lupane series,158 and rotenone and related compounds (inwhich asymmetric shielding of the l-proton by the 12-carbonyl group canbe used to decide on the cis- or trans-fusion of the B/C rings 159). Opticalrotatory dispersion and infrared and nuclear magnetic resonance spectrahave been used in determining the structure of ivalin, a new sesquiterpenelactone.160 Mass spectra 161 of unsaturated pentacyclic triterpenoids havebeen reported.Mass spectra combined with other spectroscopic methods 162have been used to determine the structures of two minor products of thepyrolysis of thujone which, previously thought t o be Cg ketones, are in factC,, ketones. Calculations relating to optical activity and conformation ofsome alicyclic terpenes have been based on the one-electron model of opticalactivity. l 6 3Optical circular dichroism has been applied to the study of the stereo-chemistry of ~ t e r 0 i d s . l ~ ~ It is frequently convenient t o use the readilyprepared nitrite esters rather than xanthates for differentiating betweenepimeric pairs of steroidal alcoh01s.l~~ The nitrites show a multiple Cottoneffect in a convenient spectral region and the rotatory dispersion curvescan be used to differentiate epimeric alcohols even in the presence of theA*-3-keto-portion.Introduction of halogen atoms or y to a keto-groupleads t o unexpected rotatory dispersion results; 166 these have been inter-preted as due to conformational distortion from the chair form towardsa boat-like conformation as a result of electrostatic repulsion.Terpenes and steroids.153 R. R. Fraser, Canad. J. Chem., 1962, 40, 78.154 S. S. Danyluk and W. G. Schneider, Canad. J . Chem., 1962, 40, 1777.156 J. Levisalles and J. C. N. Ma, Bull. SOC. chim. France, 1962, 1597.1 5 7 R. B. Bates, R. H. Carnighan, R. 0. Rakutis, and J. H. Schauble, Chern. and158 J.-M. Lehn and G. Ourisson, Bull. SOC. chim. France, 1962, 1137.159 L. Crombie and J.W. Lown, J., 1962, 775.l 6 0 W. Herz and G. Hogenaner, J. Org. Chem., 1962, 27, 905.1 6 1 C. Djerassi, H. Budzikiewicz, and J. M. Wilson, Tetrahedron Letters, 1962, 263.1 6 2 W. von E. Doering, M. R. Willcott, 111, and M. Jones, jun., J. Amer. Chem.163 M. V. Vol’kenshtein and I. 0. Levitan, Zhur. strulct. Khim., 1962, 3, 87.1 6 4 M. Legrand and R. Viennet, Compt. rend., 1962, 254, 322; L. Velluz, ibid., p. 969.165 C. Djerassi, I. T. Harrison, 0. Zagneetko, and A. L. Nussbaum, J . Org. Chem.,166 C. S. Barnes and C. Djerassi, J . Amer. Chem. SOC., 1962, 84, 1962.D. T. Longone and C. L. Warren, J. Amer. Chem. SOC., 1962, 84, 1507.Ind., 1962, 1020.SOC., 1962, 84, 1224.1962, 27, 1173MILLEN AND WHITE: PROPERTIES AND STRUCTURE 201Molecular-polarisability studies of cholesterol, cholest-5-ene, cholest-5-en-3-one, cholesteryl chloride, bromide, iodide, and epicholesteryl chloride 16'indicate that the halogen atoms are attached equatorially in the cholesterylhalide and axially in epicholesteryl chloride.Mass spectrometry has been used for both analytical 168 and structural 169studies of steroids.Mass spectra of steroids with lreto-groups in all possiblenuclear positions have been reported. Characteristic features in the spectraare mainly due to cleavage of the C-C bond in the ring adjacent to thecarbonyl group and also to retention of the charge on the oxygen-containingfragment. It is suggested that this technique can locate, or at least reduce,the possible positions of attachment of a carbonyl g r 0 ~ p .l ~ ~Nuclear magnetic resonance studies of steroids show that spatial vicinityof hydroxyl and methyl groups can cause a chemical shift to low field forthe methyl signal, a feature which may be of use in the study of the stereo-chemistry of ster0ids.1~0 Spectra of steroids with hydrocarbon side chainshave been obtained and the methyl regions have been assigned.171Physical methods have been used in studies of the structure of digininand diginigenin,l72 otobain, 1 7 3 rearrangement products of 2a-hydroxytesto-sterone and its diacetate,l74 and the products of Claisen rearrangement ofcestrone ally1 ether.175The microwave spectrum of theparent compound of the recently discovered diazirines proves conclusivelythat diazirine has the cyclic structure (9) : dipole moment and bond distanceshave been e ~ a l u a t e d .1 ~ ~Four-membered cyclic sulphones have been investigated by means ofinfrared and nuclear magnetic resonance spectroscopy.Conformations of furanose derivatives in solution have been H,C ,I1 (9)oxetanes have been investigated by fluorine nuclear magnetic resonance.179Proton magnetic resonance spectra of pyrrolines and pyrroline oxidesaccord with the *N=CH* formulation of the bases.lS0 Nuclear magneticresonance studies of pyrrole include an investligation of the thiocyanationproducts of pyrrole lS1 and an examination of the coupling constants ofHeterocyclic Compounds.--SmaEZ rings.YNstudied by proton magnetic resonance. l 7 * Isomers of fluoro- N167 J.M. Eckert and R. J. W. Le F&vre, J., 1962, 1081.168 L. E. Peterson, Chem. and Ind., 1962, 264.169 H. Budzikiewicz and C. Djerassi, J. Amer. Chem. SOC., 1962, 84, 1430.170 Y. Kawazoe, Y. Xato, M. Natsume, H. Hasegawa, T. Okamoto, and K. Tsuda,171 G. Slomp and F. A. MacKellar, J. Amer. Chem. SOC., 1962, 84, 204.172 C. W. Shoppee, R. Lack, and. A. V. Robertson, Proc. Chenz. SOC., 1962,l i 3 T. Gilchrist, R. Hodges, and A. L. Portc, J., 1962, 1780.174 R. L. Clarke, J . Amer. Chenz. SOC., 1962, 84, 467.175 P. G. Holton, J. Org. Chem., 1962, 27, 357.176 L. Pierce and V. Dobyns, J . Amer. Chem. SOC., 1962, 84, 2651.17' G. Stork and I. J. Borowitz, J . Amer. Chem. SOC., 1962, 84, 313.l i 8 R. J. Abraham, K. A. McLauchlan, L. D.Hall, and L. Hough, Chem. and Ind.,179 J. F. Harris and D. D. Coffman, J. Amer. Chem. SOC., 1962, 84, 1553.180 R. Bennett and D. E. McGreer, Cunad. J. Chem., 1962, 40, 177.lS1 S. Gronowitz, A.-B. Hornfeldt, B. Gestblom, and R. A. Hoffman, Arlciv Kern;,Chem. and Pharm. Bull. (Japan), 1962, 10, 338.65.1962, 213.1962, 18, 151202 ORGANIC CHEMISTRYpyrroles. lB2 The proton resonance spectra of cis- and trans-hydroxy-I;-proline show that the ring in each compound is buckled in solution.ls3 Bothmolecules exist in C, or envelope conformations. I n the trans-compoundC-4 projects out of the plane of the other ring atoms, the angle of bucklebeing approximately 53", while in the cis-compound C-5 is out of plane,the angle of buckle being approximately 70".Nuclear magnetic resonancespectra have been used in proving the structures of 3,4-dehydro-proline and-prolinamide. 84A complete rs structure has been obtained for f~ran.18~ Infrared,ultraviolet, and nuclear magnetic resonance spectra show that the com-pound described in the literature as thiolan-3,4-dithione is probably&methyl- 172-dithiole-3- thione . Thiophen-3,4- dithiol exists in the dithiolform. l 8 6l7O Nuclear magnetic resonance spectra of benzofurazan oxide showtwo resonance lines, adding support to the N-oxide structure.187 Thespectra are temperature-dependent owing to an equilibrium (10). Theaverage lifetime of the tautomers is about sec. a t 45", the activationenergy is 17.2 & 1.5 kcal./mole, and the frequency3 x 1014 and 3 x 10l6 sec.-1.r 1factor lies between0Rotational constants and dipole moment have been reDorted forthiazole.88 Isomeric arninoisoxazolones have been identified & $amino-5- and 5-amino-3-isoxazolone. 189 Arylazopyrazolones have infrared spectraconsistent with an azo-keto-structure. 190 The nuclear magnetic resonancespectra of pyridine derivatives show that the coupling constants are littleaffected by substituents, except by strong electron-donors in the 3-position.The chemical shifts reflect the donor or acceptor properties of substituents,but anisotropy effects have to be borne in mind; 2- and 6-hydroxypyridinederivatives occupy a special position owing to their pyridone structure. lS1Dipole moments of phenyl derivatives of some N-heterocycles have beenreported: for phenyl-substituted 2-phenylpyridines internal rotation islS2 S.Gronowitz, A.-B. Hornfeldt, B. Gestblom, and R. A. Hoffman, Arkiv Kemi,lS3 R. J . Abraham and K. A. McLauch1an;MoZ. Phys., 1962,5, 195; R. J. AbrahamlE4 A. V. Robertson and B. Witkop, J . Amer. Chem. SOC., 1962, 84, 1697.lS5 B. Bak, D. Christensen, W. B. Dixon, L. Hansen-Nygaard, J. R. Andersen,lS6 S. Gronowitz and P. Moses, Acta Chem. Scand., 1962, 16, 105.P. Diehl, H. A. Christ, and F. B. Mallory, HeZv. Chim. Acta, 1962, 45, 504.B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup-Andersen, J . MoZ.lS9 C. L. Bell, C. N. V. Nambury, and L. Bauer, J. Org. Chem., 1961, 26, 4923.lgo F.. A. Snavelly, W. S. Trahanovsky, and F. H. Suydam, J .Org. Chesn., 1962,lgl W. Briigel, 2. Elektrochem., 1962, 66, 159.1962, 18, 133.and K. A. McLauchlan, ibid., p. 513.and M. Schottlander, J. Mol. Spectroscopy, 1962, 9, 124.Spectroscopy, 1962, 9, 222.27, 994MILLEN AND WHITE: PROPERTIES AND STRUCTURE 203restricted.192 The infrared and Raman spectra of piperazine lg3 have beenassigned on the basis of the chair form. The possibility of a boat-chairtransformation in the solid piperidinium halides 19* has been consideredbut is regarded as unlikely. Molecular-polarisability studies of tropinoneand 3-halogenotropanes in benzene solution show that piperidine rings ina chair conformation with equatorially disposed N-methyl groups are con-tained in the preferred conformations.195 The infrared and nuclear mag-netic resonance spectra l g 6 of quinolizidine and monomethylquinolizidinesindicate that in all except one of these compounds the ring system existspredominantly in the trans-fused conformation.The exception is 4-methyl-quinolizidine in which the 10- and the 4-hydrogen atoms are trans to oneanother; this compound appears to adopt a conformation in which therings are cis-fused and the methyl group is equatorial. The stereochemistryof the proton salts is similar to that of the free bases. Two possible meth-iodides of quinolizidine have been prepared and their structures determined.The spectra of methoxypyridine cations have features expected for pyridiniumions, 19' whereas with 4-mercaptopyridine and 4-mercaptoquinoline protona-tion occurs at the sulphur atoms.198 For hydrochlorides of aminopyridinesthe cations are represented well by amidinium str~ctures.1~9 The protonresonance spectra of indolizinium perchlorate and its methyl derivatives intrifluoroacetic acid show that protonation occurs preferentially at the3-position .200The proton magnetic resonance spectra of coumarins 201 confirm theethylenic nature of the 3,4-double bond, and provides a convenient meansof distinguishing between 3- and 4-substituted coumarins.The protonspectrum of pisatin 202 shows that the molecule contains a chromano-coumaran ring and is 3-hydroxypterocarpin. The proton spectrum ofdesosamine 203 (map. 86-87') shows that the 1-, 2-, 3-, and &hydrogenatoms are in the axial configuration.The configurations at positions 1,2, and 3 of methyl chalcoside and chalcose have been established by mutuallyconsistent chemical, nuclear magnetic resonance, and rotational data ; theconfiguration at position 5 has been deduced from nuclear magnetic reson-ance data. 204 Proton resonance spectra of six-membered heterocycles con-taining oxygen and sulphur have been used in studies of intramolecularlg2 C. W. N. Cumper, D. G. Redford, and A. I. VogeI, J., 1962, 1176, 1182; C. W. N.Cumper, R. F. A. Ginman, and A. I. Vogel, ibid., pp. 1188, 4518, 4525.lS3 P. J. Hendra and D. B. Powell, Spectrochim. Ada, 1962, 18, 299.lS4 A. Cabana, and C. Sandorfy, Canad. J. Chem., 1962, 40, 615.Ig5 J. M. Eckert and R. J. W. Le F$vre, J., 1962, 3991.lS6 T.M. Moynehan, K. Schofield, R. A. Y . Jones, and A. R. Katritzky, J., 1962,lS7 E. Spinner and J. C . B. White, J., 1962, 3115.lS8 E. Spinner, J., 1962, 3127.lgS E. Spinner, J., 1962, 3119.M. Fraser, A. Melera, B. B. Molloy, and D. H. Reid, J., 1962, 3288.201 S. S. Dharmatti, G. Govil, C . R. Kanekar, C. L. Khetrapal, and Y. P. Virmani,202 D. D. Perrin and D. R. Perrin, J . Amer. Chem. SOC., 1962, 84, 1922.203 P. W. K. Woo, J. W. Wion, L. Durham, and H. S. Mosher, Tetrahedron Letters,204 P. W. K. Woo, H. W. Dion, and L. F. Johnson, J . Amer. Chem. Soc., 1962,2637.Proc. Indian Acad. Sci., 1962, 54, A, 71.1962, 735.84, 1066204 ORGANIC CHEMISTRYmobility and conformation. *05 Proton resonance spectra of pyranosederivatives in solution have been reported.206The nuclear magnetic resonance spectra of 1 ,4-dioxans7 1 ,3-dioxolans7and 174-dioxano[2,3-b][ 1,4]dioxan have been interpreted by two methods ;characteristic shifts have been observed for the groups studied.207 Theproton magnetic resonance spectrum of 173,5-trithian 208 indicates a rapidlyoscillating chair structure in which axial and equatorial hydrogen are in-distinguishable.An ax : eq ratio of 2 : 1 in the spectrum of a-trithioacet-aldehyde shows that this is cis-truns-2,4,6-trimethyl-l ,3,5-frithian7 and theearlier assignment of y-trithioacetaldehyde as a eutectic mixture of the a-and the p-isomer has been confirmed. Similar nuclear magnetic resonancemeasurements show that a-trithiobenzaldehyde is cis-truns-2,4,6-triphenyl-1,3,5-trithian7 while the #?-compound is the all-cis-isomer.Characteristic frequencies are reported for sulphoxides 209, 210 and 88-dioxides, and cis-trans-isomers of 2,2-diphenyl-l,3-dithian 1,3-dioxide havebeen identified.210 Structures of cyclic sulphites have been discussed inrelation to their dipole moments; by using steric arguments to eliminatecertain configurations it is concluded that cyclic tetramethylene sulphitehas a chair configuration with an equatorial S=O bond.211The outstanding feature of recent work onalkaloids has been the application of mass spectrometry to structural andstereochemical problems.Work reported deals with polyneuridine andindole alkal0ids,21~ tabersonine, 213 refractine and aspidofractine,214 vindo-linine, 215 aspidoalbine, 216 echitamidine,217 nucleosides,21* eburnamenine,219purine derivatives,220 ananferine,221 pyrifoline and refractidine, 222 mos-205 H.Friebolin, s. Kabuss, W. Maier, and A. Luttringhaus, Tetrahedron Letters,1962, 683.2 0 6 L. D. Hall, L. Hough, K. A. McLauchlan, and K. Pachler, Chem. and Ind.,1962, 1465.207 E. Caspi, T. A. Wittstruck, and D. M. Piatak, J . Org. Chem., 1962, 27, 3183.208 E. Campaigne, N. F. Chamberlain, and B. E. Edwards, J . Org. Chem., 1962,2 0 9 S. Pinchas, D. Samuel, and M. Weiss-Broday, J., 1962, 3968.W. Otting and F. A. Neugebauer, Chem. Ber., 1962, 95, 540.211 R. Riemschneider and V. Wuscherpfennig, 2. Naturforsch., 1962, 17b, 516.212 L. D. Antonaccio, N. A. Pereira, B. Gilbert, H. Vorbrueggen, H.Budzikiewicz,J. M. Wilson, L. J. Durham, and C. Djerassi, J . Amer. Chem. SOC., 1962, 84, 2161.213 M. Plat, J. Le Men, M.-M. Janot, J. M. Wilson, H. Budzikiewicz, L. J. Durham,Y. Nakagawa, and C. Djerassi, Tetrahedron Letters, 1962, 271.214 C. Djerassi, T. George, N. Finch, H. F. Lodish, H. Budzikiewicz, and B. Gilbert,J . Arner. Chem. SOC., 1962, 84, 1499.215 C. Djerassi, S. E. Flores, H.. Budzikiewicz, J. M. Wilson, J. L. Durham, J. LeMen, M.-M. Janot, M. Plat, M. Gorman, and N. Neuss, Proc. Nat. Acad. Sci. U.S.A.,1962, 48, 113.216 C. Djerassi, L. D. Antonaccio, H. Budzikiewicz, J. M. Wilson, and B. Gilbert,Tetrahedron Letters, 1962, 1001.217 C. Djerassi, Y. Nakagawa, H. Budzikiewicz, J. M. Wilson, J. Le Men, H. Poisson,and M.-M.Janot, Tetrahedron Letters, 1962, 653.218 K. Biemann and J. A. McCloskey, J . Amer. Chem. SOC., 1962, 84, 2005.219 H. K. Schnoes, A. L. Burlingame, and K. Biemann, Tetrahedron Letters, 1962,220 G. Spiteller and M. Spiteller-Friedmann, Monatsh., 1962, 93, 632.221A. Rother, J. M. Bobbitt, and A. E. Schwarting, Chem. and Ind., 1962,222 B. Gilbert, J. M. Ferreira, R. J. Owellen, C. E. Swanholm, H. Budzikiewicz,Alkuloids and nucleosides.27, 135.993.654.L. J. Durham, and C. Djerassi, Tetrahedron Letters, 1962, 59MILLEN AND WHITE: PROPERTIES AND STRUCTURE 205sambine (diphlorrhyncine) ,223 and the periwinkle alkaloids vincamine and1 l-methoxy~incamine.~~~Chemical shifts of the 19-methyl group and infrared analysis can beused to classify heteroyohimbine alkaloids into six stereochemical groups.225The stereochemistry of rauniticine, raunitidine, isoraunitidine, mayumbine,and raunitorine has been completely described.225 Optical rotatory disper-sion studies have been reported for aporphine alkaloids.226 The protonmagnetic resonance spectra of nucleotides 227 lead to assignment of specificconformations for the sugar ring, but the analysis is valid only if the theoryrelating coupling constants and dihedral angles in these compounds isquantitatively correct.Free Radicals.-In this section results obtained from electron-spin reson-ance studies are summarised.A study of the spectra of ultraviolet-irradiated isotopically substitutedmethanol 228 as a function of isotopic substitution, time of irradiation, andtemperature permitted the identification with considerable certainty of theradicals: *CH,*OH, *CH2*OD, *CH3, CD,, *CHO, and *CDO, and evidencewas obtained for the radicals *CD,*OH, GOD, *COH, CH3*O*, CD,*O*. Thespectra of formyl 229 and deuteroformyl radicals support the conclusionthat the radical is not a n-electron radical.X-Irradiation of a single crystalof methylmalonic acid shows that the two main species produced by theradiation are the *CMe(CO,H), and the *CHMe*CO,H radicals ;230 analysisof the spectra of the radical *CMe(CO,H), at room temperature, 7 7 " ~ ~and 4.2" K, shows that the three methyl protons are equivalent, the methylgroup executing nearly free rotation about the C-C bond at 4.2" K. Theelectron-spin resonance of an irradiated single crystal of racemic tartaricacid grown from water wa.s found to be complex, whereas a deuteratedsingle crystal gave a spectrum which could be analysed.231 The radicalformed probably has struct,ure (1 1).7H,C -C - C -CH3I I H COZH('$1) ('2)y-Irradiation of ( + )-isovaline probably causes abstraction of NH, andformation of the radical ( 12).232 Similar irradiation of a single crystal ofacetyl-L-glutamic acid results in the initial production of the unstableradical (13), which is transformed into a more stable radical, and possible223 X.Monseur, R. Goutarel, J. Le Men, J. M. Wilson, H. Budzikiewicz, andC. Djerassi, Bull. SOC. chim. France, 1962, 1088.224 M. Plat, Due Dohkac Manh, J. Le Men, M.-M. Janot, H.Budzikiewicz, J. M.Wilson, L. J. Durham, and C. Djerassi, Bull SOC. c72irn. France, 1962, 1082.2 2 5 M. Shamma and J. B. Moss, J . Amer. Chem. SOC., 1962, 84, 1739.226 C. Djerassi, K. Mislow, and M. Shamma, Experientia, 1962, 18, 53; M. Shamma,ibid., p. 64.2 2 7 C. D. Jardetzky, J . Amer. Chena. SOC., 1962, 84, 62.2 2 8 P. J. Sullivan and W. S. Koski, J . Amer. Chem. SOC., 1962, 84, 1.229 F. J. Adrian, E. L. Cochran, and V. A. Bowers, J. Chem. Phys., 1962, 36, 1661.230 C. Heller, J. Chern. Phys., 1962, 36, 175.231 D. V. G. L. N. Rao, and W. Gordy, J . Chem. Phys., 1962, 36, 1143.230 T. S. Jaseja and R. S . Anderson, J. Chem. Phys., 1962, 36, 1098206 ORGANIC CHEMISTRYstructures of the latter have been h~ferred.~~sby y-irradiation of N-carbamoylglycine has the structure ( 14).234The free radical producedH02C.CHA study of the spectra 235 of irradiated single crystals of alanine showsthat the reorientation of the methyl group of the radical R*CHMe* is quencheda t low temperatures, and the lifetime of reorientation was estimated. Foralanine the potential barrier and frequency factor were found to be 3.6 & 0.2kcal./mole and (10 & 4) x 10l2 sec.-l. Free radicals produced by y-irradia-tion of single crystals of N-acetylmethionone probably have the chemicalforms (15) and (16).236C0,HI(15) CH,*CO-NH.CHICO,H1ICH,*CO*NH*C* (16)*S CH ,*CH, CH,WH ,*CH ,I n strong acid solution semiquinones exist as doubly protonated species,hyperhe splitting in the electron-spin resonance spectra being due to boththe added protons and to the aromatic ring protons.237 The line-widthalteration in the spectrum of the durosemiquinone cation is ascribed tocis-trans-isomerism, the lifetime of each isomer being comparable with theinverse frequency separation between proton hyperfine cornponent~.~38Organometallic and Organometalloid Compounds.-Infrared and nuclearmagnetic resonance studies indicate that ethyl-lithium exists as a singlespecies in hydrocarbon solvents, probably a h e ~ a r n e r .~ ~ ~ Molecular con-figurations of boric Z4O and boronic esters 240, 241 have been discussed andthe effect of bridging on the B-C1 stretching frequency 242 has been ex-amined. The infrared spectra of di( alky1amino)phenylborons 241 indicatethe presence of two rotational isomers arising from restricted rotation aboutthe B-N bond.Vibrational spectra for a number of organotin 243 and organoger-manium 244 compounds have been obtained.The infrared spectrum of233 Mikio Katayama, J. Chtm. Phys., 1962, 37, 2143.234 D. V. G. L. N. Rao and M. Katayama, J. Chem. Phys., 1962, 37, 382.235 I. Miyagawa and K. Itoh, J. Chem. Phys., 1962, 36, 2157.236 E. Cipollini and W. Gordy, J. Chem. Phys., 1962, 37, 13.237 J. R. Bolton, A. Carrington, and J. Dos Santos-Veiga, Mol. Phys., 1962, 5, 465.238 J. R. Bolton and A. Carrington, MoZ. Phys., 1962, 5, 161.239 T. L. Brown, D. W. Dickerhoof, and D. A. Bafus, J. Amer. Chem. Soc., 1962,84, 1371.240 H. Lumbroso and A. Grau, Bull. SOC. chim.France, 1961, 1866.241 J. E. Burch, W. Gerrard, M. Goldstein, E. F. Mooney, and H. A. Willis, Spectro-chim. Acta, 1962, 18, 1403.242 A. Finch, P. J. Hendra, and E. J. Pearn, Spectrochim. Acta, 1962, 18, 51.243 V. S. Griffiths and G. A. W. Derwish, J. Mol. Spectroscopy, 1962, 9, 83; W. F.Edge11 and C. H. Ward, ibid., 1962, 8, 343; T. V. Yakovleva, A. A. Petrou, and V. S.Zavgorodnii, Optics and Spectroscopy, 1962, 12, 106.244 N. A. Chumaerskii, Optics and Spectroscopy, 1962, 13, 37CAPON AND R E E S : REACTION MECHANISMS 207germyl cyanide has been analysed: there was no evidence of an isocyanideform. 245 A detailed structural determination of silyl isothiocyanate hasbeen made. 246 Temperature-dependence of the infrared spectrum indicatesa possible structural change when hexaethyldisiloxane is heated.247 Thestereochemistry of optically active organosilicon compounds has beendiscussed.24 *D. J. M.R. F. M. W.3. REACTION MECHANISMSSEVERAL books and the reports of two symposia 2 dealing wholly or largelywith organic reaction mechanisms were published in 1962.Nucleophilic Substitution at Saturated Carbon. Transient CarboniumIons. Aliphatic Reaxrangements.-Classiml and non-classical curboniumions. There is considerable interest as to whether non-classical ions arereaction intermediates or merely transition states for the interconversion ofclassical ions. H. C. Brown has pointed out 3 that suggestions for non-classical ions have multiplied fantastically in recent years 4 often withoutreasonable scientific basis and has examined the evidence for a number ofthe suggestions.The high rates of solvolyses of compounds (1)’ (2), and(3) have been attributed to the stabilisation of the transition states throughformation of incipient non-classical ions (4), ( 5 ) , and (6), but Brown suggeststhat they may be explained in other ways. He suggests that the high reac-tivity of compound (1) may result from a release of non-bonding compressionon going to the transition state (Le., is due to a raised initial-state free-energyrather than to a reduced transition-state free-energy). However, in theReporters’ view the arguments already presented by Ingold and by Win-stein and his co-workers 6 that-a large part of the high reactivity results from245 T.D. Goldfarb, J . Chern. Phys., 1962, 37, 642.246 D. R. Jenkins, R. Kewley, and T. M. Sugden, Trans. Faraday SOC., 1962, 58,247 G. G. Kirei and M. P. Lisitsa, Optics and Spectroscopy, 1962, 12, 206.248 L. H. Sommer, Angew. Chern., 1962, 74, 176.1284.( a ) J. Hine, “ Physical Organic Chemistry,’’ McGraw-Hill, New York, 2nd edn.,1962 ; ( b ) A. Streitwieser, “ Solvolytic Displacement Reactions,” McGraw-Hill, NewYork, 1962; (c) M. J. S. Dewar, “Hyper~onjugation,~~ The Ronald Press Co., NewYork, 1962; (d) t. L. Ingraham, “ Biochemical Mechanisms,” Wiley, New York, 1962;( e ) E. L. Eliel, Stereochemistry of Carbon Compounds,” McGraw-Hill, New York,1962; (f) W. A. Pryor, “ Mechanisms of Sulphur Reactions,’’ McGraw-Hill, New York,1962; (9) S.G. Waley, “Mechanisms of Organic and Enzymic Reactions,” Oxford,1962; ( h ) “ Comprehensive Biochemistry,” ed. M. Florkin and E. H. Stotz, Elsevier,New York, 1962; (i) “Progress in Stereochemistry,” ed. P. B. D. de la Mare andW. Klyne, Butterworths Scientific Publns., London. Vol. 111, 1962.( a ) “ The Transition State,” Chern. SOC. Special Publ., No. 16, 1962; ( b ) “ PeroxideReaction Mechanisms,” ed. J. 0. Edwards, Interscience, New York, 1962.H. C. Brown in ref. 2 ( a ) , p. 140.See Y. Pocker, Ann. Reports, 1959, 56, 172; 1960, 57, 166; M. D. Johnson,<bid., 1961, 58, 173.C. K. Ingold, “ Structure and Mechanism in Organic Chemistry,” Cornell Univ.Press, Ithaca, New York, 1953, p. 514.S. Winstein, B. K. Morse, E. Grunwald, K.C. Schreiber, and J. Corse, J . Amer.Chem. SOC., 1952, 74, 1113208 ORGANIC CHEMISTRYs ynartetic acceleration or anchimeric assistance are convincing. Brown'salleged linear relation between the logarithm of the rates of solvolysis ofcertain toluene-p-sulphonates and the rates of the reactions of the corre-sponding ketones with sodium borohydride is unconvincing since too fewother points are presented to define the normal line to test the divergence ofthe triphenylethyl system. Nevertheless, as Brown points out, the evidenceD- CH2 (2)for the stabilisation of transition states through incipient phenonium-ionformation in several other reactions is very slight.The high reactivity of cyclopropylmethyl and cyclobutyl derivatives isstill not fully understood. The small effect of a phenyl substituent in the3- and the 4-position on the reactivity of cyclopropylmethyl naphthalene-2-sulphonate indicates that there is.little positive charge dispersed to themethylene-carbon atoms whilst the moderately large effect of a methyl sub-stituent a t position 2 has been taken to indicate that some positive chargeis dispersed to this atom. These results support the view that the transitionstate involves incipient formation of an ion which is stabilised by resonancebetween structures (7) and (8) [Le., a non-classical ion, though different from(8)r-7(7) 9 - + 4->?< L+ P;-a(S)].However, a phenyl substituent a t position 2 has only a small effect onthe rate of acetolysis of cyclopropylmethyl arenesulphonates. 10 Further-more, the rate-accelerating effect of the cyclopropyl group is not alwaysassociated with rearrangement.Each successive replacement of an iso-propyl group by a cyclopropyl group in the series (9)-(12) results in a largeY v vX X X X(9) (10) ( ' 1 ) (12)23,500 23,500 x 1080 Relative rate : I 246[X = p-nitrobenzbate]See ref. 2(a), p. 153, Fig. 4.R. A. Sneen, K. M. Lewandowski, I. A. I. Taha, and B. R. Smith, J . Anter.E. F. Cox, M. C. Caserio, M. S . Silver, and J. D. Roberts, J . Amer. Chem. SOC.,Chena. SOC., 1961, 83, 4843.1961, 83, 2719.10 J. W. Wilt and D. D. Roberts, J . Org. Chem., 1962, 27, 3430CA4PON AND REES: XEACTION MECHANISMS 209increase in the rate of solvolysis in aqueous dioxan and the products are theunrearranged alcohols.11 Hence with these compounds there is either somefactor which strongly favours formation of only the cyclopropylmethanolsfrom the non-classical ion or a non-classical ion is not involved.An investi-gation of the corresponding cyclobutyl derivatives would be of considerableinterest. The rate of solvolysis of 1 -cyclobutyl- 1 -methylethyl p-nitro-benzoate in aqueous acetone is only 5-10 times faster than that of t-butylp-nitrobenzoate and the product is a complex mixture.12 The stabilisingeffect of the cyclopropyl group on carbonium ions is so great that the tri-cyclopropylmethyl cation is stable in concentrated sulphuric acid. l3 Thenuclear magnetic resonance spectrum of this ion somewhat surprisinglyconsists of only a single sharp band a t 6-85 z.The reported absence l4 ofa deuterium isotope effect in the solvolyses of compounds (13) and (14),which has been quoted as evidence against the formation of the cation (5)in the rate-determining step, is in~orrect.1~ There is in fact a small effectbut this, unfortunately, provides no clear evidence on the structure of thetransition state. Similarly the isotope effect in the acetolysis of 2,2-di-deutero-5,5-diphenylcyclopentyl toluene-p-sulphonate l 6 provides no con-clusive evidence on the occurrence of phenyl participation.Brown has also pointed out 3 that the exo-norbornyl acetate obtainedwith retention of configuration l7 on acetolysis of exo-norbornyl toluene-p-sulphonate (3) may not have been formed from the non-classical ion (6) butcould have come equally from a classical ion since attack on such an ionfrom the exo-side would be strongly favoured sterically.He attributes thelarge rate-difference between the exo- and the endo-norbornyl toluene-p-sulphonate to the inertness of the latter, caused by steric hindrance to ioni-sation, though this is not very convincing. It is interesting that Kleinfelterand Schleyer l8 have shown that the temperature-dependence of the nuclearmagnetic resonance spectrum of the carbonium ion obtained when 1 ,2-di-p-methoxyphenyl-2-norborneol is dissolved in sulphuric acid indicates thepresence of a rapidly equilibrating pair of ions (15) and (16) rather than ofa non-classical ion (17). did not challenge the view that the aceto- Brownl1 H.Hart and J. M. Sandri, J. Amer. Chem. SOC., 1959, 81, 320; H. Hart andl2 C. F. Wilcox and M. E. Mesirov, J. Amer. Chem. SOC., 1962, 84, 2757.l3 N. C. Deno, H. G. Richey, J. X. Lui, J. D. Hodge, J. J. Houser, and M. J.Wisotsky, J. Amer. Chem. SOC., 1962, 84, 2016; see Chem. Eng. News, Nov. 26th, 1962,p. 48.l4 S. BorEi6, M. Nikoleti6, and D. E. Sunko, Chern. and Ind., 1960, 527.l5 S. BorEi6, M. Nikoletid, and D. E. Sunko, J . Amer. Chem. SOC., 1962, 84, 1615.R. A. Sneen, R. W. Jenkins, and F. C. Riddle, J. Amer. Chem. SOC., 1962, 84,D. C. Kleinfelter and P. von R. Schleyer, Abs. Papers, Amer. Chem. Soc., 141stMeeting, March 1962, 28-0; 142nd Meeting, September 1962, 56-Q; quoted by H. C.Brown in ref. 2(a), p.158.P. A. Law, ibid., 1962, 84, 2462.1598.l7 S. M'instein and D. S. Trifan, J. Amer. Chem. SOC., 1952, '74, 1147210 ORGANIC CHEMISTRYlysis of 2-p-methoxyphenyl-l-methylpropyl p-bromobenzenesulphonate in-volves a p-methoxyphenonium nor that the solvolyses of cholesteryland norbornenyl derivatives l g b involve non-classical ions formed by partici-pation of the double bonds. A particularly striking example of such homo-allylic participation has been found by Rogan 2O in the acetolysis of 4-methylpent-3-enyl toluene-p-sulphonate (18), a compound with a less rigidstructure than the cholesteryl and norbornenyl derivatives. The rate ofsolvolysis is 1200 times greater than that of ethyl toluene-p-sulphonate,and the products are 2-cyclopropylpropene (21) and 4-methylpent-3-enylacetate (20) (see also p.221). The difference in the rates of ethanolysisof 2,3 -diphenylcyclopropenylmethyl and$H2Me- C-CH - CH2\ /CH2 (21)toluene-p-sulphonates is very slight,Z1 indicating the absence of participa-tion by the double bond as shown in formula (22). There is similar non-participation by the double bond in the solvolyses of cyclohex-3-enylmethylderivatives 22 and of 3-methylenecyclobuty1 bromides.23Homoallylic participation has also been investigatedin the steroid field 24 and in the solvolysis of cyclo-(22) oct -3-enyl p - bromobenzenesulphonate.A potentially very powerful method for the in-vestigation of carbonium ions has been discovered by Brown and Bell 26who showed that the carbonium ion formed when diphenylmethyl chlorideis dissolved in aqueous diethylene glycol dimethyl ether may be trappedby sodium borohydride to yield diphenylmethane:Deamination of endo-2-aminomethylnorbornane (23) by nitrous acidCH2----OTs j$ ph ._ .__ __ -l9 ( a ) S. Winstein, M. Brown, K. C. Schreiber, and A. H. Schlesinger, J . Amer.20 J. B. Rogan, J . Org. Chem., 1962, 27, 3910.21 R. Breslow, J. Lockhart, and A. Small, J . Amer. Chem. SOC., 1962, 84, 2793.22 C. F. Wilcox and S. S. Chibber, J . Org. Chem., 1962, 27, 2332.23 E. F. Kiefer and J. D. Roberts, J . Amer. Chem. SOC., 1962, 84, 784.2 4 W. J. A. Vandenheuvel, R. M. Moriarty, and E. S. Wallis, J . Org. Chem., 1962,27, 725; W. J. A. Vandenheuvel and E. S. Wallis, ibid., p. 1233; C.W. Ghoppee andG. A. R. Johnston, J., 1962, 2684; G. H. Whitham, Proc. Chem. SOC., 1962, 330.2 5 A. C. Cope, Sung Moon, and P. E. Peterson, J . Amer. Chem. Soc., 1962, 84,1935.26 H. C. Brown and H. M. Bell, J . Org. Chem., 1962, 27, 1928.Chem. SOC., 1952, 74, 1140; (b) see ref. l(b), pp. 153, 152, for summaryCAPON AND REES: REACTION MECHANISMS 21 1gives mainly bicyclo[3,2,l]octan-2(endo)-ol (28) and a little of the isomer(27).27 The alcohols obtained from the optically active amine are bothpartially racemised but the extent of racemisation differs, the endo (28)being more highly racemised than the exo isomer (27). These results arenot compatible with a mechanism involving only the non-classical ion (25)since then racemic products would be expected, nor is it; compatible withone involving only the enantiomeric cations (24) and (26) as sole intermedi-ates since then the extent of racemisation of the two alcohols should be thesame.There must be at least; two product-forming intermediates andBerson and Reynolds-Warnhoff 27 suggest. the annexed scheme (23) --+ (28).Classical ion (24) is apparently diverted to mesomeric cation and to products b-faster than it is transformed into its conformational isomer [the enantiomerof (29)] which is known to yield bicyclo[2,2,2]octan-2-01 (34).28The bicyclo[2,2,2]octan-2-01 (34) obtained from optically active exo-2-aminomethylnorbornane (28) is partially racemised and so cannot be derived(-> (28)HOmeso (32) (+I (33) (+I (34) (3 (34)exclusively from the non-classical ion (30), but racemisation would resultfrom the classical ion (31).Other products from this reaction are exo-bicyclo[3,2,l]octan-2(exo)-ol (33) of yet undetermined optical purity andmeso- bicyclo[ 3 , 2 , l loctan-3 - 01 (32). 28There is less aryl migration in the deamination of lJ2,2-tri-(methoxy-phenyl)[ l-14C]ethylamine (35) than in that of the corresponding phenyl27 J. A. Berson and P. Reynolds-Warnhoff, J. Amer. Chern. SOC., 1962, 84, 682.28 J. A. Berson and D. WiUner, J. Amer. Chern. SOC., 1962, 84, 675212 ORGANIC CHEMISTRYcompound (36).29a If this reaction involves formation of the classical ion(37) then the extent of migration will depend on the ease with which thearyl group undergoes electrophilic attack and the electrophilicity of thecarbonium ion-centre.A p-methoxy-group will enhance the ease of electro-philic attack but will decrease the electrophilicity of the carbonium-ioncentre because of resonance between structures (38) and (39), and this secondeffect must more than counterbalance the first.14 Ar2CH - CHAr Ar2CH J4CHAr(37)+INH2(35) Ar=p-Me0.CsH4 - E H e O M e - t--) - C H o & l e -(36) Ar = PhDeamination of optically active erythro- (40) and threo- 1 -amino-2-p-methoxyphenyl-1 -phenylpropan-2-01 gave ketonic products [ (42) and (43)from the erythro-isomer] where ratios of enantiomers 29b were nearly identical(38) (39)Me@:: Hk (42)InversionJIMe (41)JIH .AMe 'Ph(43)RetentionH R@:OH(40)OH (41)O& MePh H(43)RetentionR = p-Me-C,H, SimilarIy for the threo-seriesor p-MeO-C,H,SCHEME 1.with those obtained from erythro- and threo-1 -amino-1 -phenyl-Z-p-tolylpro-pan-2-01. Both reactions proceed with predominant retention of configura-tion a t the reaction centre.The results have been taken to indicate 29b that,the high-energy carbonium ion [ (41) for the erythro-isomer] generated a tC-1 reacts at once with the migrating p-aryl group before there is any2 9 ( a ) W. A. Bonner and T. A. Putkey, J. Org. Chew., 1962, 27, 2348; ( b ) C. J.Collins, M. M. Staum, and B. M. Benjamin, ibid., p. 3525CAPON AND R E E S : REACTION MECHANISMS 213rotation about the 1,2-bond so that the products reflect the conformation ofthe initial state (see Scheme 1 for the erythro-series). When the migratinggroup is o-tolyl which has different steric requirements, the product ratio isdifferent.The nitrous acid deaminations of 5,5-dimethylbicyclo[ 2,l ,l]hex-2p-ylamine 30 and 2-1’- and 2-2’-naphthyl[ 1 -W]ethylamine 31 have alsobeen investigated.Ion-pair return has been investi-gated by measuring the lSO equilibration 32 of diphenylmethyl p-nitro-[~nrbonyZ-~sO]benzoate and the isomerisation of the corresponding thionben-zoate to the thiobenzoate. 33 Solrolysis of thep-nitrobenzoate in 90:L aqueousacetone is accompanied by equilibration of the carbonyl-oxygen atoms inIon-pair return and related phenomena.the unsolvolysed e~ter.3~tion (Eeq) are both of the first order, and Ee,/lc, = 3.The rates of solvolysis (E,)I8OIIPhzCH-O-C-Ar(44)and oxygen equilibra-The kinetic behaviourk2 + Products(46)and the slow exchange between ester and p-nitrobenzoic acid indicate thatthe p-nitrobenzoate portion remains associated with the original diphenyl-methyl group.A mechanism is proposed, (44) -+ (46), involving ion-pairreturn from an ion-pair intermediate (45) in which theatoms are equivalent. Diphenylmethyl thionbenzoateisomerisation to the thiobenzoate concurrently with itsbeing 17% of ethanolysis and 837; of isomerisation.indicate that the ethanolysis involves ionisation sincecarbox ylat e - oxygenundergoes a similaret hanolysis , 33 thereSubstituent effectsPhzCH - S - 5 - Ph.0Productsp = -3.6. No di-phenylmethyl p-methoxythiobenzoate was formed when the thionbenzoatewas allowed to rearrange in the presence of potassium p-methoxythio-benzoate, indicating that return from free ions is unimportant.The oxygen-equilibration of triphenylmethyl [ carbonyl- lSO]benzoate indry acetone is suppressed by addition of lithium azide, the product then beingtriphenylmethyl azide.34 At low azide concentrations the rate constant forthe disappearance of azide is only slightly larger than the rate constant forequilibration. These results suggest that azide captures an intermediatewhich in its absence yields rearranged ester. This intermediate is probablya solvent-separated ion pair. It is suggested 34 for this and for other reac-tions that the dual (intimate and solvent-separated) ion-pair hypothesis is30 J. Meinwald, P.G. Gassman, and J. J. Hurst, J. Amer. Cliem. SOC., 1962, 84,31 A. G. Forman and C. C. Lee, Canad. J. Chem., 1962, 40, 1130.32 H. L. Goering and J. F. Levy, Tetrahedron Letters, 1961, 644; J . Amer. Chem.33 S. G. Smith, Tetrahedron Letters, 1962, 979.34 C. G. Swain and Gen-Ichi Tsuchihashi, J. Amer. Chem. SOC., 1962, 84, 2021.3722.Soc., 1962, 84, 3853214 ORGANIC CHEMISTRYunnecessary. In the presence of lithium and tetrabutylammonium bromidethe reactions of 2-p-methoxyphenyl-l-methylethyl toluene-p-sulphonateand 2pmethoxyphenyl- 1 -methylpropyl p - bromobuzenesulphonate inacetic acid are largely diverted from solvolysis to bromide formation.35 Thisis also thought to involve trapping of solvent-separated ion pairs.Optically active 1 -methylheptyl p-bromobenzenesulphonate yields in-verted alcohol of 77y0 optical purity on solvolysis in 75 vol.yo aqueous di-oxan.36 In the presence of sodium azide, however, 100% optically pureinverted alcohol is obtained. This suggests that the solvolysis proceedseither by SN2 displacement by water to yield inverted alcohol or by a path-way involving an intermediate which leads to either racemisation or reten-tion. Azide ion must then capture this intermediate, which may be acarbonium ion or an oxonium ion formed in an SN2 displacement by dioxan.Isobutyl p-bromobenzenesulphonate and 1 -methylheptyl toluene-p-sulphon-ate undergo ethanolysis with 100% inversion of configuration.3' The ratesof reaction of 4-phenoxybenzyl and 4-methoxybenzyl chlorides with a seriesof anions have been measured.3* With the weak nucleophiles, Ph*SO,- andNO,-, the rate ratios, ICp-MeO/kp-PhO, for the two substrates are similar to theratio for the XNl solvolyses but with strong nucleophiles, e.g., N3-, the ratiois considerably less. The results suggest that the transition state for ionisa-tion has already been reached before bond formation with benzenesulphonateand nitrate ions begins or that these weak nucleophiles react with fullydeveloped carbonium ions.In aqueous acetone cis- (47) and trans-5-methylcyclohex-2-enol (48)undergo racemisation and isomerisation.39 With each isomer the rate ofracemisation is several times faster than that of isomerisation.Experimentswith 180-labelled alcohols show that the racemisation of the cis-isomer isOHM e(+) (47) Mea 2 Me@ (+) (48)(4 9) .If Rac.(50) OHalmost exclusively intramolecular but that of the truns-isomer is inter-molecular. These results are interpreted to mean that the carbonium ion(49) from the trans-alcohol is solvated by two water molecules, but that fromthe cis-alcohol (50) by only one (derived from the original hydroxyl group)because of steric hindrance by the 5-methyl group.35 S. Winstein, P. E. Klinedist, aqd E. Clippinger, J . Amer. Chem. SOC., 1961, 83,4986.36 H. Weiner and R. A. Sneen, J.' Amer. Chem. SOC., 1962, 84, 3599.37 A. Streitwieser and A. C. Waiss, J . Org. Chem., 1962, 27, 290.38G. Kohnstam, A. Queen, and T. Ribar, Chem.and Ind., 1962, 1287.39 H. L. Goering and R. R. Josephson, J . Amer. Chem. SOC., 1962, 84, 2779CAPON AND REES: REACTION MECHANISMS 215Elimination-uddition mechanism. cc-Chlorodibenzyl ketone, but notor-chloroacetone, underwent ready methanolysis in the presence of 2,6-lutid-ine. The reaction was of the first order in chloro-ketone and also in 2,6-lutidine but independent of lutidiniurn ion concentration. An elimination-Slow o y IPh*fH*CO.CHzPh + C7H9N Ph.CH*C=CHPh + C7H9NH'c1 (51) CI , (52) J0/ \P h CH.CO. CH zP h(54) PhKH- C = CHPh (5.3) IOMeaddition mechanism [either two steps as shown (51) + (54) or concerted] ispr~posed.~O The intermediate (53) may be stabilised by resonance betweenstructures (55), (56), and (57). A similar intermediate (59) is thought tooccur in the Favorski rearrangement of 6-toluene-p-sulphonyloxyisophorone( 5 5 ) ( 5 6 ) (57)(58) which with an excess of methanolic sodium methoxide yields the re-arrangement products, the methylcyclopentanecarboxylates (62) and (63)as well as 2- and 6-methoxyisophorone (60) and (61).41 It is possible thatJCOzMeCO 2Me a-*O A.W. Fort, J . Arner. Chern. SOC., 1962, 84, 2620.41 A. W. Fort, J. Arner. Chem. SOC., 1962, 84, 2625216 ORGANIC CHEMISTRYall four products come from the same intermediate (59), the niethanecyclo-pentanecarboxylates by reaction with methoxide ions and the methoxy-phorones by reaction with methanol, a view which is supported by thevirtual absence of the former when the reaction is carried out in the presenceof a trace of sodium methoxide.The much greater ease of replacement of the dialkylsulphonyl groups byethoxide ions in cow’-dialkylsulphonyl-p-xylenes (64) than in alkyl arylsulphones has led to the suggestion of an elimination-addition mechanism(64) -+ (66).42 This is supported by the observation that in the presence ofEtOqpiperidine, a base without activity by itself, partial replacement of an alkyl-sulphonyl group by piperidine occurred.This could result from trapping ofthe intermediate (65). The absence of deuterated starting material in apartially completed reaction in O-deuterated ethanol suggests that theelimination is concerted.Base-promoted replacement reaction with 3-bromo-3-methylbut-1 -ynein 80% ethanol probably proceeds by the elimination-addition mech-anism (68) --+ (72),43 which is supported by the observation of deuteriumexchange by unchanged bromide when the reaction is carried out in 80%ethan[ 2H]ol-deuterium oxide and of a cornmon-ion “ mass-law ” effect (seealso the section on carbenes, p.242).Me Me Me1 I II IBr Br (68)Me-C-CZCH ye, Me-C-CnC- Me-C-C=C-+ (70)Me MeMe- C- C 3 CHI(72) OEtMe-C=C =C:(71)1,3-Hydride shifts. ‘‘ Deoxideation ” of propan-1-01 with bromoform andaqueous potassium hydroxide to give cyclopropane does not involve an inter-mediate carbene (74) since 1 , 1 -dideuteropropan- 1-01 yields deuterated cyclo-propane with loss of only a few per cent of deuterium.44 It is thought thatthe small deuterium loss results from a 173-hydride shift (75) +P (76).Asimilar hydride shift occurs in the deamination of n-[ 1 -14C]propylamine withCH,-CH,*CH: CH,*CH,*CD ,+ + +CH,CH,*CHD,(74) (75) (76)4 z A . T. Kader and C. J. M. Stirling, J., 1962, 3425.43 V. J. Shiner and J. W. Wilson, J. Amer. Chern. SOC., 1962, 84, 2402; V. J. Shiner,J. W. Wdson, G. Heinemann, and N. Solliday, ibid., p. 2408.44 P. S. Skell and I. Starer, J. Amer. Chem. SOC., 1962, 84, 3962CAPON AND REES: REACTION MECHANISMS 217nitrous acid.45, 46 It was shown by Roberts and Halman 47 that the pro-pan-1-01 obtained from this reaction was partially rearranged. They attri-buted this to methyl migration as (77), but Reutov and Shatkina 45 havenow shown that 14C is found only at positions 1 and 3(77)of the propan-1-01 and hence only hydrogen shifts haveoccurred.That this was mainly a 1,3-shift (78) + (79),and not two 1,2-shifts, (80) -+ (82), was shown byKarabatsos and Orzech 46 since [ 1,l ,2,2-2H,]propylamine yields propanolwith most of the protons at positions 1 and 3.,5.!3c < 2 c c ~ 2( 7 8) CH3-CD 2-CD 2+ + +CH 2-CD Z-CHD 2CH,-CD,-CDz+ + CH,-CD+-CD, -+ +CH2-CHD-CD,( 7 9)(80) (81) (82)Neighbouring-group participation by oxygen groups. Solvolysis of o-phen-oxycarbonyldiphenylmethyl bromide (83) in aqueous acetone is 60-80fPhOHtimes faster than that of the para-isomer, and the product is 3-phenyl-phthalide ( 85),48 i.e., the reaction involves neighbouring-group participa-tion by the ester group.Attempts to prepare theanalogous o-methoxy-carbonyl compound yielded only3-phenylphthalide. Participation, however, does notoccur in the solvolysis of the fluorene ester (86), presum-ably" because of the unfavourable geometry of this mole-c ~ l e . ~ 9 The solvolyses of 10-acetyl-la-halogeno-trans-decalin occur with participation of the ketone group asshown in cypher (87).50General reactions. There have been further measurements of rate con-stants with sufKcient accuracy to show the variation of activation energywith ternperat~re.~l-~S Although there does not appear to be universalMe\C = 0 32-44 5 0. A. Reutov and T. N. Shatkina, Tetrahedron, 1962, 18, 237.4 6 G. J. Karabatsos and C. F. Orzech, J. Amer. Chem. SOC., 1962, 84, 2838.4 7 J.D. Roberts and M. Halmann, J. Amer. Chem. SOC., 1953, 75, 5759.4 8 A. Singh, L. J. Andrews, and R. M. Keefer, J. Amer. Chem. SOC., 1962, 84,4 9 R. E. Lovins, L. J. Andrews, and R. M. Keefer, J. Amer. Chem. SOC., 1962,5 0 G. Baddeley, E. K. Baylis, B. G. Heaton, and J. W. Rasburn, Proc. Chem.51G. Kohnstam and D. Tidy, Chem. and Ind., 1962, 1193.5 2 J. Biordi and E. A. Moelwyn-Hughes, J., 1962, 4291; E. A. Moelwyn-Hughes,53 J. B. Hyne, R. Wills, and R. E. Wonkka, J. Amer. Chem. SOC., 1962, 84, 29141179.84, 3959.Soc., 1961, 451.ibid., p. 4301218 ORGANIC CHEMISTRYagreement as to whether the quantity d(ANi)/dT should be identified withACt,52, 54 there is no doubt that the quantity ACt/A8Z provides a t leasta useful empirical criterion of mechanism for solvolyses in aqueous organicsolvents. 55 This criterion indicates that solvolysis in 70% aqueous acetoneof PriOTs and p-X*C,H,*CH,*OTs where X = H, Me, or NO,, andTs = p-C,H&e*SO,, does not occur by an 8,l me~hanism.~~ In few investi-gations of this kind is the product composition determined to the samedegree of accuracy as the rate of formation of acid.A method has beendeveloped for measuring the rate of solvolysis of gaseous t-butyl chloride a tunit pressure in aqueous solution,56 and rates have been measured in alarge number of electrolyte solutions.57 The formation of the transi-tion state may be formulated, ButCl(g) + (aq) + ButCP,,,,, so thatk,= RT Fh Kt J$' 1 The activity coefficient of t-butyl chloride does not appearin this equation since its fugacity may be taken to be equal to its pressure.Hence kp/kpo = l/f t where the superscript O refers to the reference state ofpure water.It was thus possible to determine the variation of ft, the acti-vity coefficient of the transition state, with electrolyte concentration. Theactivity coefficients of t-butyl chloride, f(g), in the same electrolyte solutionswere also obtained from solubility measurements. Neither log f(g) norlog f t obeyed the expression obtained by Ingold and his co-workers 58 andbased on the ion-atmosphere model, but specific salt effects were found.However, the effects of the electrolytes on the conventional rate constant,for unit concentration, do obey the ion-atmosphere treatment owing to acancellation of the specific salt effects on log f(B) and log ft.The view that the solvent-isotope effect kD,O/kH,O on the solvolysisof methyl halides results mainly from an initial-state difference 59 is incor-rect. The solubility of each halide in light and heavy water is almost thesame, such that the standard free-energy differences between the initialstates are never greater than 60 cal.mole-1.60Full details of much of the work of Grob and his co-workers on fragmenta-tion reactions have now been published, 61 including the demonstration offragmentation of a carbonium ion (90) (shown here as classical) generatedby a Wagner-Meerwein rearrangement (88) + (90).The steric course of the ring expansion of (- )-2-methylcyclohexanonewith diazomethane to give ( +)-3-methylcycloheptanone has been investi-gated .62 Assigning configurations from the rotatory dispersion curves and54 See ref.2(a), pp. 196 et seq.6 5 G. Kohnstam in ref. 2(a), p. 179.6 6 G. A. Clarke, T. R. Williams, and R. W. Taft, J . Amer. Chem. SOC., 1962, 84,5 7 G. A. Clarke and R. W. Taft, J . Amer. Chem. SOC., 1962, 84, 2295.68 L. C. Bateman, M. G. Church, E. D. Hughes, C. K. Ingold, and N. A. Taher,6 9 See R. C. Heppolette and R . E. Robertson, J . Amer. Chem. SOC., 1961,83, 1834,6o C. G. Swain and E. R. Thornton, J . Amer. Chem. SOC., 1962, 84, 822.61 C. A. Grob and F. Ostermayer, Helw. Chim. Acta, 1962, 45, 1119; C. A. Grob,F. Ostermayer, and W. Raudenbusch, ibid., p. 1672; C. A. Grob, R. M. Hoegerle, andM. Ohta, ibid., p.1823.6 2 C. D. Gutsche and C. T. Chang, J. Amer. Chem. SOC., 1962, 84, 2263,2292.J., 1940, 979.and earlier papers.For early work see Ann. Reports, 1958, 55, 185CAPON AND REES: REACTION MECHANISMS 219the octant rule leads to the surprising conclusion that the ring expansionoccurs with inversion of configuration. The Beckmann rearrangement of(89)9-acetyl-cis-decalin oxime (92) in concentrated sulphuric acid or polyphos-phoric acid yields N - (trans-9-decaly1)acetamide (93), i.e., with inversion ofconfiguration of the migratingThe methoxy-group has no activating influence in the solvolyses of 1-bromomethyl-5-methoxy- and 2-bromomethyl-8-methoxy-naphthalene andonly a small effect in the solvolyses of l-bromomethyl-7-methoxy- and 2-bromomethyl-6-methoxy-naphthalene.6* A p-phenyl but not a p-methoxy-or p-methylthio-substituent in cumyl chloride is more activating whenconstrained to a planar configuration by a methylene bridge.e5 It has beensuggested that the faster reaction of benzyldimethylsulphonium toluene-p-sulphonate with phenoxide than with hydroxide ion may be explained byancillary molecular bonding of the n-complex or charge-transfer type.66The mechanisms of the following reactions have also received attention :acetolysis of neopentyl-type toluene-p-sulphonates of ~ p i r a n s , ~ ~ of 1 -phenyl-cycloalkylmethyl arenesulphonates, 68 of cyclononyl 69 and cyclodecyl tolu-ene-p-sulphonate, 70 and of 4-substituted cyclohexyl toluene-p-sulphonates ; 71solvolysis of y-branched alkyl toluene-p-sulphonates, 72 and of the conjugatebase of 4-p-hydroxyphenylbutyl p-bromobenzenesulphonate ; 73 addition andsolvolysis in the norbornane systems; 74 solvolysis, and reaction with iodideion, of chloromethylethylmercury ; nucleophilic replacement reactions ofbenzyl halides ; '6 amine-catalysed chloroacetolysis of triphenylmethyl63 R.K. Hill and U. T. Chortyk, J. Amer. Chem. SOC., 1962, 84, 1064.64 K. C. Schreiber and R. G. Byers, J. Amer. Chem. SOC., 1962, 84, 859.6 5 H. C. Brown and T. Inukai, J. Amer. Chem. SOC., 1961, 83, 4825.6 6 C. G. Swain and L. J. Taylor, J. Amer. Chem. SOC., 1962, 84, 2456.67 A. P. Krapcho and M. Benson, J . Amer. Chem. Xoc., 1962, 84, 1036.68 J. W. Wilt and D. D. Roberts, J. Org. Chem., 1962, 84, 3434.6s V.Prelog, W. Kiigi, and E. M. White, Helv. Chim. Acta, 1962, 45, 1658.70 V. Prelog, W. Kiing, and T. Tomljenovib, Helv. Chim. Acta, 1962, 45, 1352.71 D. S. Noyce, B. N. Bastian, and R. S. Monson, Tetrahedron Letters, 1962, 863.H. Fischer, C. A. Grob, and W. Schwarz, Tetrahedron Letters, 1962, 25.R. Baird and S. Winstein, J. Amer. Chem. Soc., 1962, 84, 788; see Ann. Reports,1957, 54, 161.7 4 S. J. Cristol, W. K. Seifert, D. W. Johnson, and J. B. Jurale, J..Arner. Chem.SOC., 1962, 84, 3918.75A. Ledwith and L. Phillips, J., 1962, 3796.76 R. F. Hudson and G. Klopman, J., 1962, 1062; J. F. Bunnett and J. A. Rein-heimer, J. Amer. Chem. SOC., 1962, 84, 3284; J. W. Hill and A. Fry, {bid., p. 2763;J. B. Stothers and A. N. Bourns, Canad.J . Chem., 1962, 40, 2007220 ORGANIC CHEMISTRYchloride in carbon tetrachloride ; reaction of benzyldimethylanilinium ionswith thiocyanate ions ; 78 ethanolysis of N-benzyl-NN-dimethyl-p-tolu-idinium bromide;79 and isomerisation of bicyclo[2,1,0]pentane 80 and its2 -methyl derivative. 81Ambidentate Nuc1eophiles.-Investigations of the influence of structureand environment on the position of covalent-bond formation in ambidentateanions (cf. ref. 82) continue. The proportions of 1- and 2-substitutedpyrroles formed in the alkylation of lithium, sodium, and potassium deriva-tives of pyrrole with allyl, but-2-eny1, and benzyl halides have been measuredfor a variety of solvents, under homogeneous and heterogeneous conditions. 83N-Alkylation increases with the solvating power of the medium and decreaseswith the co-ordinating ability of the metal ion, as expected if dissociation ofthe pyrryl-metal ion-pair favours N-alkylation and association of the ion-pair favours 2-alkylation.The transition states (94) and (95) are postulated,the latter providing for mutual stabilisation of charges on the departingcation and the halide anion which is important in poorly solvating media.Product ratios vary little from homogeneous to heterogeneous conditionsand appear to depend predominantly on the concentration and precise stateof the pyrrole derivative in solution.C H ~ - R(94) >is- (95)Another system in which heterogeneity per se has no significant effect onthe product ratio is the benzylation of sodium 2,6-dimethyl-4-t-bufylphen-oxide suspended in toluene or dissolved in toluene-tetrahydrofuran. Theratio of C-alkylation, giving the ketone (96), to O-alkylation in mixtures ofthese solvents and in the presence of varying amounts of the undissolvedsodium salt and a quaternary ammonium salt are discussed, and otherrecent work on factors influencing the position of alkylation of phenoxideions is reviewed;84 the importance of the state of ionic aggregation of thesubstrate is stressed.The mechanism of the oxidation of free sugars by periodate has beenexamined.The chief attack affects the pyranose ring form although earlyrelease of formaldehyde shows that the furanose or abdehydo-forms are alsoinvolved. The first product from D-glucose is 4-O-formyl-~-arabinose whichOxidations.25 G.0. Phillips and W. J. Criddle, J., 1962, 2733.26 G. 0. Phillips and W. J. Criddle, J., 1962, 2740.27 S. V. Starodubtsev, M. P. Tikhomolova, E. L. Aizenshtat, and K. Tashmuk-2 8 A. J. Bailey, S. A. Barker, I. R. L. Lloyd, and R. H. Moore, Radiatio)z Res.,29 G. 0. Phillips, W. J. Criddle, and G. J. Moody, J., 1962, 4216.30 H. Simon and J. Steffens, Chem. Ber., 1962,95, 358; J. D. Anderson, P. Andrews31 H. S. Isbell, L. T. Sniegoski, and H. L. Frush, Analyt. Chem., 1962, 34 982.32 H. S. Isbell, J . Res. Nut. Bur. Stand., 1962, 66, A , 233.33 R. J. Stoodley, Canad. J. Chern., 1961, 39, 2593.34 G. G. Post and L. Anderson, J. Amer. Chenb. SOC., 1963, 84, 471.35 D. B. Easty, J. Org. Chenz., 1962, 27, 2102.36 G.J. Moody, Nature, 1962, 195, 71.37 D. H. Rammler and C. A. Dekker, J. Org. Chenz., 1961, 26, 4615.38 6. Blom, Acta Chem. Scand., 1961, 15, 1667.hamedova, Zhur. obshchei Khim., 1961, 31, 3115.1961, 15, 532; A. J. Bailey, S. A. Barker, and M. Stacey, ibid., p. 538.and L. Hough, Biochem. J., 1962, 84, 140362 ORGANIC CHEMISTRYis then oxidized mainly in the open-chain modification. The same principleholds during the oxidation of D-mannose and ~-galactose.39 I n partialoxidations of methyl D-aldopyranosides with periodic acid any cis-a-glycolsystem present is attacked prefer en ti all^.^^ The ‘‘ polyaldehydes ” obtainedby periodate oxidation of a number of glycosides and oligosaccharides areshown to be hydrated; that from melibiose is exceptional in containing onefree aldehyde A colorimetric method for the determination ofsuch ‘‘ polyaldehydes ” has been described,42 as well as one for the detectionof malondialdehyde produced during oxidation^.^^ A spectroscopic methodfor following oxidations with lead tetra-acetate in dilute solutions enablesfast reactions to be studied; the data are consistent with the formation of afive-membered cyclic lead complex.44 Glycol fission has been used fordegrading hexose derivatives to pentose ones.45The course of formation of the methyl D-xylosides fromD-XylOSe involves the initial formation of furanosides followed by theirisomerization to the corresponding pyranosides.If the sugar is substitutedat C-2 or C-3 the equilibrium mixture contains more of the furanosides.46Some of the details of the mechanism proposed have, however, been con-tested.47 Treatment of 2,3,5- tri- 0- benzyl-~-ribosyl bromide with methanoland silver carbonate gives mainly the methyl a-D-ribofuranoside becausethe benzyl group does not have a neighbouring-group effe~t.~S Reaction ofmercuric acetate and methanol with D-glucal rapidly yields what is probablythe product of diaxial addition, methyl 2-acetoxymercuri-2-deoxy-a-~-mannopyranoside, which is reduced by borohydride to methyl %deoxy-a-~-glucopyranoside. The same sequence with D-glucal triacetate gives thesame product, together with a larger amount of the /I-an~rner.~Q The initialproduct from D-glUCal is, however, claimed to be methyl 2-acetoxymercuri-2-deoxy-~-~-mannoside, whereas from D-glucal triacetate the correspondingglucoside triacetate is formed.50 Phenyl D-glucosides are obtained by actionof the phenol on methyl or-D-glucoside-boron trichloride. Direct glucosyla-tion of benzene was achieved with the same reagent in the presence of asmall amount of aluminium chloride.51The optical rotations of o-nitrophenyl a- and p-D-glucopyranosides areunusually temperature-dependent, probably because of electronic inter-action between the nitro-group and the sugar.5239 S. J. Angyal and J. E. Klavins, Austral. J . Chem., 1961, 14, 577.4O M. Guernet, Bull. SOC. chim. France, 1961, 1752.41M. Guernet and A. Juardo-Soler, Compt. rend., 1962, 254, 2985.42 A. Juardo-Soh and M. Guernet, Compt.rend., 1962, 254, 2586.43 P. Mesnard and G. Devaux, Chim. analyt., 1962, 44, 287.44 A. S. Perlin and S. Suzuki, Canad. J . Chem., 1962, 40, 1226.45 K. Antonakis, A. Dowgiallo, and I,. Szabb, Bull. SOC. chim. France, 1962, 1355;4 6 C . T. Bishop and F. P. Cooper, Canad. J . Chem., 1962, 40, 224.47 B. Capon, G. W. Loveday, and W. G. Overend, Chem. and Ind., 1962,48 R. Barker and H. G. Fletcher, jun., J . Org. Chem., 1961, 26, 4605.49 G. R. Inglis, J. C. P. Schwarz, and (in part) L. McLaren, J., 1962, 1014.6 0 P. T. Menolopoulos, M. Mednick, and N. N. Lichtin, J . Amer. Chem. SOC.,51 T. G. Bonner, E. J. Bourne, and S. McNally, J . , 1962, 761.5zB. Capon, W. G. Overend, and M. Sobell, J., 1961, 5172.Glycosides.G. Rembarz, Chem. Ber., 1962, 95, 1565.1537.1962, 84, 2203HONEYMAN : CARBOHYDRATES 363Degradations. Starch, sucrose, and D-glucose have each been convertedinto 5-hydroxymethyl-2-furfuraldehyde (yields about 45%) by the combinedaction of a weak acid and a weak base.63 Unsaturated osones have beenshown to be formed during the conversion of D-fructose into 5-hydroxy-methyl-2-furfuraldehyde 64 and in the preparation of S-deoxy-~-erythro-hexosone from di-D-fructosylglycine.6 5 The presence of the ring-oxygenatom is essential for the alkaline hydrolysis of diethylsulphonylglyco-pyranosylmethanes to the lower aldose.56 Although the 1 -deoxy-l-nitro-heptitols undergo cyclizations and dehydrations similar to those of thediethylsulphonylglycopyranosylmethanes they are not similarly degradedby mildCyclic derivatives.Further evidence emphasizes the importance ofhydrogen bonding in the reactions of polyhydric alcohols with aldehydes.Use of nuclear magnetic resonance spectroscopy has enabled the conforma-tions to be determined for l ,3-0-benzylidene-erythritol diacetate (5), theHHI HPh (9) (9) Hanalogous L-threitol derivative which appears to be conformationally un-stable (6, 7), and 173:2,4-di-0-benzylidene-erythritol (8) and its L-threitolanalogue (9).58 The stability to acid of the benzylidene group in a series ofmethyl 4,6-0-benzylidene-aldohexosides is not much affected by structure. 59Treatment of inositols with 2,2-diethoxypropane in the presence of acidhas been found to be a good method for making O-isopropylidene derivatives.Even trans-pairs of hydroxyl groups may react.60 When attached to asix-membered ring in the chair conformation a single O-isopropylidene groupdeforms the chair only slightly, but if two such groups are attached to twopairs of cis-hydroxyl groups the cyclohexane ring assumes the skew con-formation, or possibly something between boat and skew forms.61 The53M.L. Mednick, J . Org. Chern., 1962, 27, 398.6 4 E. F. L. J. Anet, Chem. and Ind., 1962, 262.5 5 E. F. L. J. b e t , Austral. J. Chem., 1962, 15, 503.56 L. Hough and A. C. Richardson, J., 1962, 1019, 1032.5 7 L. Hough and S. H. Shute, J., 1962, 4633.5 8 A. B. Foster, A. H. Haines, J. Homer, J. Lehmann, and L. F. Thomas, J.,59 B. Capon, W. G. Overend, and M.Sobell, Tetrahedron, 1961, 16, 106.6o S. J. Angyal and R. M. Hoskinson, J., 1962, 2985.61 S. J. Angyal and R. M. Hoskinson, J., 1962, 2991.1961, 5005; A. B. Foster, A. H. Haines, and J. Lehmann, ibid., p. 5011364 ORGANIC CHEMISTRYfive-membered ring of some O-isopropylidene sugars in solution is shown bynuclear magnetic resonance evidence to be in a partially staggered non-planar form. 62Ethers. Reducing sugars may be completely methylated in one treat-ment with methyl iodide and silver oxide in dimethylformamide. FromL-arabinose, D-xylose, D-mannose, and D-glUCOSe the more stable of thepyranose forms is the main product, but with D-fructose, D-galactose, andD-gdaCtUrOniC acid furanose isomers predominate. 63 Partial methylationof sugar dithioacetals with methyl iodide and silver oxide in tetrahydrofuranhas shown that for D-galactose the 2-, 3-, and 6-positions are equally reac-t i ~ e , ~ ~ whereas for ~ - x y l o s e ~ ~ position 2 is twice as reactive as 3 which isten times as reactive as 6.Under these conditions the dithioacetals ofD-glucose and L-arabinose are methylated chiefly at position 2. Additionof sodium methoxide to the appropriate sugar a-nitro-olefin is a simplemethod for preparing 2-O-methyl-D-ribose and -D-mannose. 67Vinyl ethers may be prepared by treating the sugar with vinyl chlorideand sodium hydroxide in tetrahydrofuran,68 with a~etylene,~*-~O or withbutyl 7O or isobutyl 7l vinyl ether in the presence of a catalyst.The major products obtained by the direct trimethylsilylation of muta-rotated D-xylose are the fully substituted anomeric pyranose compounds.72Esters. Sugars have been completely acetylated by heating them withacetic anhydride and a small amount of an acidic ion-exchange resin.73Even a suspension of acetic anhydride in aqueous sodium hydroxide canbe used in suitable cases.74The racemization that occurs when 6-deoxy-6-iodo-aEdehydo-~-galactose2,3,4,5-tetra-acetate is converted by acetic anhydride and zinc chloride intoaldehydo-DL-galactose 1,1,2,3,4,5,6-hepta-acetate 75.has been shown to occuralso with the wglucose and D-mannose isomers.76 On use of [ l-14C]sugarsit became clear that the label remained a t C-1 on racemization. Hexosesacetylated a t position 6 do not undergo the conversion and the initial stepis probably ionization of iodine, leaving a carbonium ion at position 6 towhich the 5-acetyl group migrates, leaving in turn an ion a t position 5 whichmay racemize t o give the two possible isomers.This process may then recur6 2 R. J. Abraham, K. A. McLauchlan, L. D. Hall, and L. Hough, Chem. and Ind.,63 H. G. Walker, jun., M. Gee, and R. M. McCready, J. Org. Chem., 1962, 27, 2100.6 4 G. G. S. Dutton and Y . Tanaka, Canad. J. Chem., 1962, 40, 1146.6 5 G. G. S. Dutton and Y. Tanaka, Canad. J . Chem., 1962, 40, 1899.6 6 G. G. S. Dutton and K. Yates, Canad. J. Clzem., 1958, 36, 550; G. G. S. Dutton6 7 J. C. Sowden, M. L. Oftedahl, and A. Kirkland, J . Org. Chem., 1962, 27, 1791.68 A. J. Deutschman, jun., and H.W. Kircher, J . Amer. Chem. SOC., 1961, 83,69 R. L. Whistler, H. P. Panzer, and J. L. Goatley, J. Org. Chem., 1962, 27, 2961.70 S. A. Barker, J. S, Brimacornbe, M. R. Harnden, and M. Stacey, J., 1961, 5256.71 W. A. P. Black, E. T. Dewar, and D. Rutherford, Chem. and Ind., 1962,72R. J. Ferrier and M. F. Singleton, Tetrahedron, 1962, 18, 1149.73 G. M. Christensen, J. Org. Chem., 1962, 27, 1442.74A. Aszalos and V. Prey, Starke, 1962, 14, 50.75 F. Micheel, H. Ruhkopf, and F. Suckfull, Ber., 1935, 68, 1523.7 6 F. >lichee1 and R. Bohm, Tetrahedron Letters, 1962, 107.1962, 213.and Y. Tanaka, ibid., 1961, 39, 1797.4070.1624HONEYMAN : CARBOHYDRATES 365along the carbon chaim76 A rather similar type of transformation has beendescribed for cyclitols.7 7Treatment of D-glucal triacetate with silver benzoate and iodine in drybenzene gives the equimolecular mixture of 1 -0-benzoyl-2-deoxy-2-iodo-cc-D-glucopyranose triacetate and the D-mannose isomer expected on mechan-istic grounds.78Crystalline 5-deoxy-5- ethylthio-L- arabinose diet hyl dit hioace tal resultedfrom reaction of cc-L-arabinopyranose tetra-acetate with ethanethiol-borontrifluoride followed by deacetylstion. 79The 2- and 6-hydroxyl groups may be preferentially esterified in S-deoxy-D-mannose diethyl dithioacetal and in methyl cc-D-glucopyranoside. s1In 1,6-anhydro-~-~-glucopyranose the 2- and the 4-position are the mostreactive. 82For characterization of sugars, the p-p'-nitrophenylazobenzoates havebeen suggested.83The 6-chloroformate of a D-galactose derivative has been converted intothe 6-fluoroformate which has resisted attempts to decarboxylate it.84Sulphur trioxide in pyridine has been used for preparing the 2-sulphatefrom methyl 4,6-0- benzylidene- cc-~-glucoside 85 and also D-galactose 4-sul-phate which is probably present in algal polysaccharides.86 Under mildconditions sulphuryl chloride converts free sugars into chloro-sulphate estersalso containing chloro-deoxy-groups. In this way 4,6-dichloro-4,6-dideoxy-D-galactopyranosyl chloride 2,3-dichloro-sulphate has been obtained fromD-galactose, and the 4-chloro-4-deoxy-analogue from L-arabinose. 87Phosphate groups have been shown to be capable of migration.88Deoxy-sugars. D-Rhamnose and 6-deoxy-~-talose have been isolatedfroin a natural polysaccharide.89 Among deoxy-sugars that have beensynthesized are 6-deoxy-~-idose,gO l-deoxy-~-psicose,~~ 3,6-&deoxy-~-galac-t ~ s e , ~ ~ and 4-deoxy-~-g~ucose.~~ Chalcose and mycinose, obtained fromchalcomycin, are 4,6-dideoxy-3-0-methyl-~-glucose 94 and 6-deoxy-2,3-di-0-methyl-D-allose, 95 respectively. Mycarose, found in magnamycin and as7 7 S. J. Angyal, P. A. J. Gorin, and M. Pitman, Proc. Chem. Soc., 1962, 337.7 9 M. L. Wolfrom and T. E. Whiteley, J . Org. Chem., 1962, 27, 2109.81 A. K. Mitra, D. H. Ball, and L. Long, jun., J . Org. Chem., 1962, 27, 160.8 2 R. W. Jeanloz, A. M. C . Rapin, and S. Hakomori, J . Org. Chem., 1961,26,3939.83 El S. Amin, J., 1961, 5544.84V. A. Welch and P. W.Kent, J., 1962, 2266.asK. B. Guiseley and P. M. Ruoff, J . Org. Chem., 1962, 27, 1479.8 6 J. R. Turvey and T. P. Williams, J., 1962, 2119.8 7 H. J. Jennings and J. K. N. Jones, Canad. J . Chem., 1962, 40, 1408:8 8 P. Rivaille and L. Szab6, Compt. rend., 1962, 254, 3705; T. Ukita andK. Nagasawa, Chem. and Pharm. Bull. (Japan), 1961, 9, 544.R. U. Lemieux and S. Levine, Canad. J . Chent., 1962, 40, 1926.G. Rembarz, Chem. Ber., 1962, 95, 830.A. Markovitz, J . Biol. Chem., 1962, 237, 1767.31. L. Wolfrom and S. Hanessian, J . Org. Chent., 1962, 27, 1800, 2107.91 E. J. Reist, P. A. Hart, B. R. Baker, and L. Goodman, J . Org. Chem., 1962,9 2 H. Zinner, B. Ernst, and F. Kreienbring, Chent. Ber., 1962, 95, 821.93 M. Dahlgard, B. H. Chastain, and Ru-Jen Lee Han, J .Org. Chem., 1962, 27, 929.9 4 P. W. K. Woo, H. W. Dion, and L. F. Johnson, J . Amer. Chem. SOC., 1962,95 H. W. Dion, P. W. K. Woo, and Q. R. Bartz, J . Amer. Chern. SOC., 1962, 84, 880.27, 1722.84, 1066; P. W. I(. Woo, H. W. Dion, and Q. R. Bartz, ibid., p. 1512366 ORGANIC CHEMISTRYits 4-acetate in leucomycin B,96 is 2,6-dideoxy-3-C-methyl-~-xylohexose,97and cladinose, from erythromycin, is its 3-methyl ether.ss L-Lyxose,d-O-methyl-~-fucose, and an unidentified dideoxyaldohexose have beenisolated from curamy~in.~~ The carbohydrate portion of the cardiac glyco-side, gomphoside, is derived from a 4,6-dideoxyhexosone. loo An anhydro-derivative of a branched-chain trideoxyoctose has been isolated from anantibiotic. l01Amino-sugars .Acetamido- deoxy-ket oses having the nitrogen atomattached to the terminal position remote from the keto-group have beenmade by oxidizing 1 -acetamido-l-deoxy-pentitols or -hexitols with Aceto-bacter suboxydans. lo2The eight 3-amino-3-deoxy-~-aldohexoses have now been synthesized ;the method based on treatment of a suitable dialdehyde with nitromethanehas been particularly helpful.lo3 Sodium azide has been used to open thennhydro-ring of a 2,3-anhydro-~-alloside derivative, so giving mainly thediaxial 2-azido-2-deoxy-~-altroside with a small amount of the 3-azido-3-deoxy-D-glucoside. Similar treatment of a 2,3-anhydro-~-mannoside givesonly the 3-azido-3-deoxy-~-altroside. Conversion of the 2-azido-2-deoxy-~-altroside derivative into the 3-toluene-p-sulphonate, followed by treatmentwith sodium azide and then reduction, has given the 2,3-diamino-2,3-dideoxy-~-mannoside.l~* Another example of the synthesis of an amino-sugar in-volving replacement of a methanesulphonate group by azido has beenp~b1ished.l~~Magnesium methoxide in methanol has been found to be the best reagentfor de-O-acetylating acetylated amino-sugars.Magnesium-dried methanolmay cause deacetylation and should be purified by distillation from 2,4,6-trinitrobenzoic acid when necessary.106By use of nuclear magnetic resonance spectra and by synthetic methodsmycaminose has been shown to be 3,6-dideoxy-3-dimethylamino-~-glucose~~~~whereas similar spectra and degradation provide evidence that desosamineis 3,4,6- trideoxy- 3- dimet hylamino- D -xylohexose.log6 T. Watanabe, T. Fujii, and K. Satake, J. Biochem. (Japan), 1961, 50, 197.9 7 A. B. Foster, T. D. Inch, J. Lehmann, L. F. Thomas, J. M. Webber, and J. A.98 A. B. Foster, T. D. Inch, J. Lehmann, and J. M. Webber, Chenz. and Ind.,9 9 0. L. Galmarini and V. Deulofeu, Tetrahedron, 1961, 15, 76.Wyer, Proc. Chem. SOC., 1962, 254.1962, 1619.100 R. G. Coombe and T. R. Watson, Proc. Chem. SOC., 1962, 214.101 J. S. Webb, R. W. Broschard, D. B. Cosulich, J. H. Mowat, and J. E. Lancaster,102 J. K. N. Jones, M. B. Perry, and J. C. Turner, Canud. J. Chem., 1961, 39, 2400;103 H. H. Baer, J. Amer. Chem. SOC., 1962, 84, 83; A. C. Richardson, J., 1962, 373;104 R. D. Guthrie and D. Murphy, Chem. and Ind., 1962, 1473.105 E.J. Reist, R. R. Spencer, B. R. Baker, and L. Goodman, Chem. and Ind.,106 D. R. Whitaker, M. E. Tate, and C. T. Bishop, Canad. J . Chem., 1962,40, 1885.107 W. Hofheinz and H. Grisebach, 2. Naturforsch., 1962, 17b, 355; A. B. Foster,T. D. Inch, J. Lehmann, M. Stacey, and J. M. Webber, Chem. and Id., 1962, 142;J., 1962, 2116; A. C. Richardson, ibid., p. 2758.l 0 8 W. Hofheinz and H. Grisebrtch, Tetrahedron Letters, 1962, 377; P. W. K. WOO,H. W. Dion, L. Durham, and H. S. Mosher, ibid., p. 735; C. H. Bolton, A. B. Foster,M. Stacey, and J. M. Webber, J., 1961, 4831.J . Amer. Chem. SOC., 1962, 84, 3183.1962, 40, 503; J. C. Turner, ibid., p. 826.A. C. Richardson and (in part) K. A. McLauchlan, ibid., p. 2499.1962, 1794HONEYMAN CARBOHYDRATES 367Glucosamine has been converted into its l-thio- log and 6-thio-ana-logues.Di- and Oligo-saccharides.-Polymerization of 1,6-anhydro-~-~-gluco-pyranose by the action of concentrated hydrochloric acid gives isomaltose,gentiobiose, and a little cellobiose as well as tri- and higher oligo-sacchar-ides, 111 whereas thermal polymerization leads to a mixture containing the1,6-anhydro-derivatives of maltose, cellobiose, kojibiose, and sophorose.112By heating D-glucose with a cation-exchange resin a mixture was obtainedwhich differed from that obtained in aqueous solution by “reversion”mainly in the absence of maltose and the presence of larger amounts ofisomaltose and nigerose.113 Treatment of D-glucose with methyl a-D-glucoside-boron trichloride in nitrobenzene containing silver oxide gave a tleast eight of the D-glucopyranose disaccharides, the lxc,6-linkage beingformed most readily.51 The chief products from the action of a commercialemulsin on D -galactose were 3 - 0- and 6- 0-/3 -D -galact opyranosyl- D -galac-tose.114The low yields often obtained in the Konigs-Knorr synthesis of disac-charides have been shown to be in part caused by the decomposition of theglycosyl halide through reaction with silver oxide. The side reactions aregreatly affected by the type of silver oxide used and are retarded wheniodine is present ; all methods tried in order to remove water were ineffective.The by-products obtained from D-mannopyranosyl bromide tetra-acetateinclude D-mannose 2,3,4,6-tetra-acetate, a dimeric orthoacetate, and anorthoester of high molecular weight.115 The influences of conformation,solvent, and neighbouring groups largely decide which anomer is obtained. 116A marked increase in yield of the naturally occurring /?-D-ribofuranosyl/?-D-ribofuranoside resulted from the addition of silver perchlorate 117 t o theKonigs-Knorr reaction mixture.118Identification of the position of the link in disaccharides may be helpedby use of spray reagents on paper chromat~grams,l~~ or of sodium period-ate, 120 or by degradation with manganese dioxide. 121Exposure of sucrose to X-rays leads to reduction of hydroxyl content.122lo9 D. Horton and M. L. Wolfrom, J . Org. Chem., 1962, 27, 1794; W. M. Zu Recken-dorf and W. A.Bonner, ibid., 1961, 26, 4596.110 T. Ito, Agric. and Biol. Chem. (Japan), 1961, 25, 585; W. M. Zu Reckendorfand W. A. Bonner, J . Org. Chem., 1961, 26, 5241.l l 1 L. Reichel and H. Xchiweck, Naturwiss., 1961, 48, 696.112 M. L. Wolfrom, A. Thompson, R. B. Ward, D. Horton, and R. H. Moore,J . Org. Chem., 1961, 26, 4617.l13P. S. O’Colla, E. E. Lee, and D. McGrath, J . , 1962, 2730.l14A. M. Stephen, S. Kirkwood, and F. Smith, Canad. J . Chem., 1962, 40, 151.115 H. R. Goldschmid and A. S. Perlin, Canad. J . Chem., 1961, 39, 2025.116 P. A. J. Gorin and A. S. Perlin, Canad. J . Chem., 1961,39, 2474; P. A. J. Gorin,11’ H. Bredereck, A. Wagner, G. Faber, H. Ott, and J. Rauther, Chem. Ber., 1959,11* E. Rosenberg and S. Zamenhof, J . Riol. Chem., 1962, 237, 1040.119 R.W. Bailey, J . Chrmatog., 1962, 8, 57.lao I<. Takiura and K. Koizumi, Chem. and Pharm. Bull. (Japan), 1962, 10,ibid., 1962, 40, 275.92, 1135.134.121 J. L. Bose, A. B. Foster, N. Salim, M. Stacey, and J. M. Webber, Tetrahedron,lZ2 H. Shields and P. Hamrick, J . Chem. Phgs., 1962, 37, 202.1961, 14, 201368 ORGANIC CHEMISTRYIncompletely substituted O-alkyloxycarbonylsucroses were obtained ontreating the sugar with alkyl chloroformates in the presence of aqueousalkali, but octa-O-ethoxycarbonylsucrose resulted after further reaction inpyridine. The more highly substituted derivatives, although readilyhydrolysed by alkali, are unexpectedly stable to acid. Cross-linked polymersresult from heating the esters with alkaline catalysts.123 Reaction ofsucrose with vinyl ethers and with cyclic enol ethers such as 2,3-dihydropyranreadily yields a variety of a ~ e t a l s .1 ~ ~An unsaturated aldobiuronic acid, produced by an enzyme from Bacilluspolymyxn acting on pectic acid, is shown to be 4-0-(4,5-didehydro-a-~-galacturonosyl) -D -galacturonic acid. l2Branched trisaccharides have been synthesized 126 and panose, isomalto-triose, and 3-O-a-isomaltosyl-~-glucose have been isolated from “ hydrol,”produced by the incomplete acid hydrolysis of starch.f27 A homologousseries of sucrose D-galactosides has been isolated from carnation roots. 12*Acidic hydrolysis of a modified heparin gives D-glucose, D-glucosamine,and 4-0- a-~-g~ucopyranosy~-2-amino-2-deoxy-D-g~ucose. 129 Disaccharidederivatives containing D-glucosamine have been synthesized.l 3 O New sugarsisolated from human blood-group A substance include S-O-B-~-galacto-pyranosyl-2-acetamido-2-deoxy-~-galactose,~~~ 3-0-(2-acetamido-2-deoxy-a-D-galactosy1)-D-galactose, 3- and 4-0-~-~-ga~actosyl-2-acetamido-2-deoxy-D-glucose, and 2-acetamido-2-deoxy-a-~-galactosy~-( 1 +3)-~-D-galaCtOSyl-(1 +3)-2-acetamido-2-deoxy-~-glucose.~~~The increased reactivity and the change incrystal structure to cellulose I11 that results when cellulose I is treated withethylamine have been confirmed.133 The accessibility of cellulose has beenmeasured by observing the exchange that occurs between cellulose andtritiated water.134 However, there is some alteration in the proportion ofordered material during the interaction.135Because of greater molecular order cellulose is less reactive than starch.Hydroxyethylation of cellulose proceeds at a reasonable rate within a com-paratively limited range of sodium hydroxide concentration. Nevertheless,slight regular hydroxyethylation disrupts the crystal structure of cellulosePo~saccharides.-CeZluZose.123 R. S. Theobald, J . , 1961, 5359, 5366.124 S. A. Barker, J. S. Brimacombe, J. A. Jarvis, and J. &I. Williams, J., 1962,125 S. Hasegawa and C. W. Nagel, J . Biol. Chem., 1962, 237, 619.126 A. Klemer and K. Homberg, Chem. Ber., 1961, 94, 2747; I. J. Goldstein and127 A. Sato, Y. Ito, and H. Ono, Chem. and lnd., 1962, 301; A. Sato and H. Ono,128 J. E. Courtois and U. Ariyoshi, Bull.SOC. Chim. biol., 1962, 45, 23.M. L. Wolfrom, J. R. Vercellotti, and D. Horton, J . Org. Chem., 1962, 27, 705.130 K. Onodera, S. Kitaoka, and H. Ochiai, J . Org. Chem., 1962, 27, 156.131 T. J. Painter, I. A. F. L. Cheese, and W. T. J. Morgan, Chem. and Ind., 1962,132 G. Schiffman, E. A. Kabat, and S. Leskowitz, J . Amer. Chem. SOC., 1962, 84,T. P. Nevell and S. H. Zeronian, Polymer, 1962, 3, 187; H. Spedding, ibid.,3158.B. Lindberg, Acta Chem. Scand., 1962, 16, 383.ibid., p. 1536.1535.73.pp. 195, 211.134 0. Sepall and S. G. Mason, Canad. J . Chem., 1961, 39, 1934.lS5 0. Sepall and S. G. Mason, Canad. J . Chem., 1961, 39, 1944HONEYMAN: CARBOHYDRATES 369so that subsequent reaction is as rapid as in ~tarch.l3~ Chitin is less reactivethan cellul0se.~~7 Investigation of the distribution of substituents incellulose ethers has established the relative reactivities shown in the Tablej ReagentI Ethylene oxideDimethyl sulphateI Methyl chlorideEthyl chlorideDiazomethaneMonochloroacetic Acidc - 233.554.51.22C-3 I C-61 ~ 10q 21 21 1.5I 2.5for the different hydroxyl The relative acidities of the differenthydroxyl groups have been measured.139The grafting of other polymers on to cellulose has been achieved by usingdiazonium groups attached to the polysaccharide, lgo ceric ions, 141 or y-radiation,142 as initiators.Starch and gZycogen.Different amyloses have been separated into frac-tions ranging in degree of polymerization (DP) from 550 to 1840 by a methoddepending on the fact that the higher fractions form complexes with iodineat lower concentrations. Many carefully prepared starches have beenfractionated into amylose and amylopectin by the thymol method.Re-crystallization with butanol has given amyloses ranging in DP (determinedby viscosity) from 1000 (wrinkled pea) to 4400 (parsnip). The molecularweights (by light scattering) of the amylopectins were extremely high (e.g.,for broad-bean and banana, 10s).lg4 Electrodialysis gave pure amyloseand amylopectin fractions from potato starch. 145 In dilute aqueous solutionamylose molecules are probably highly associated deformed helices. 146Oligosaccharides as small as maltotetraose form I,- c0mplexes.14~ Byapplication of methods used with monosaccharides (‘ 3,6-anhydroamylose ”has been prepared and shown to have a, more stable glycosidic link thanamy10se.l~~ Reaction of ‘‘ monosodio-starch ” with methyl iodide gives amethyl ether having about half of the glucose units unsubstituted.The136 E. D. Klug, Starke, 1961, 13, 429.l37 S. N. Danilov, E. A. Plisko, and E. A. Pyaivinen, Izvest. Akad. Nauk S.S.S.R.,138 I. Croon, Svensk Papperstidn., 1960, 63, 247.139 V. A. Derevitskaya, G. S. Smirnova, and Z. A. Rogovin, Doklady Akad. Nauk140 G. N. Richards, J. Appl. Polymer Sci., 1961, 5, 553.1 4 1 G. N. Richards, J . Appl. Polymer Sci., 1961, 5, 539, 558.142 R. J. Demint, J. C. Arthur, jun., A. R. Markezich, and W. F. McSherry, TextileRes. J., 1962, 32, 918; U. Azizov, Tr.Tashkentsk, Konf PO Mirnomu .Ispol’z A t . EnergiiAkad. Nauk Uz.S.S.R., 1; Y. Hachihama and 8. Takamuru, Technol. Reports OsakaUniv., 1961, 11, No. 485, 431.Otdel. khim. Nauk, 1961, 1500.S.S.S.R., 1961, 141, 1090.143 J. Ho116 and J. Szejtli, Starke, 1962, 14, 75.144 C. T. Greenwood and J. Thomson, J., 1962, 222.145 M. Richter and M. Ulmann, Kolloid Z . , 1961, 176, 98.146 T. Kuge and S. Ono, Bull. Chem. SOC. Japan, 1961, 34, 1264.14’ J. A. Thoma and D. French, J . Phys. Chern., 1961, 65, 1825.148 R. L. Whistler and S. Hirase, J. Org. C’hem., 1961, 26, 4600370 ORGANIC CHEMISTRYrelative amounbs of substitution at positions 2, 3, and 6 are 2.6 : 1 : 1-2.149A method for finding the average chain-length of glycogen in 10-50 mg.samples is based on the use of salivary a-amylase.The results agree withthose obtained by periodate oxidation.150 Concanavalin A, a globulinfrom jack- bean meal, is a convenient reagent for distinguishing betweenglycogen, limit dextrins, and amylopectin on a milligram scale.151MisceZZaneous. In a sample of laminarin having about half of the mole-cules terminated by a mannitol residue it has been shown that the mannitolis attached only through C-1 .152 A water-soluble laminarin isolated fromthe seaweed Eisenia bicycZis has a molecule free from mannitol and consistingof about 20 D-glucose units linked 1,3 and 1,6 in the proportion of about 2 : 1.At least three of the 1,6-linked units are present in a block.153Confirmation that lichenin is a linear /?-D-glucopyranose polymer with.1,3- and 1,4-links has been obtained by enzymic hydrolyses.154An electrophoretically homogeneous mannan obtained in the medium-supporting growth of PeniciZZium chcrrlesii G.Smith has eight D-manno-pyranose units joined 1,2 except for a 1,6-bran~h.l~~ Another mannan,from the green coffee bean, is essentially linear and has about 45 pyranoseunits joined by lP,4-link~.I~~The glucomannan from Pinus silvestris L. has an acetyl content of about6% whereas the glucurono-arabinoxylan is almost free from acety1.157Glucomannans from Pinus densiJlora, Acer sacchurum, Larix decidw, andthe bark of Abies amabilis have been isolated and examined. The 1P,4-link predominates. 15*The presence of 1,4-linked L-guluronic acid in alginic acid has been con-fwmed.The reason for the high proportion of D-mannuronic acid residuesin the polymer that are not attacked by periodate is not yet kn0~n.1~9Although 2,3-di-O-methyl-~-lyxose has been isolated during structuralstudies of wood hemicelluloses it is an artifact produced by the readyepimerization by alkali of the D-xylose ether.l60Kinetic measurements of the rate of decarboxylation of uronic acidshas emphasized the care that is necessary to avoid decarboxylation duringthe isolation of pectic substances. Extractions should not be done with hotammonium oxalate and oxalic acid; even prolonged treatment with hot 70%ethanol causes some decarboxylation.149 B. J. Bines and W. J. Whelan, J., 1962, 4232.150 D. J. Manners and A. Wright, J., 1962, 1597.1 6 1 D.J. Manners and A. Wright, J., 1962, 4592; 0. Kjolberg and D. J. Manners,16aW. D. Annan, E. L. Hirst, and D. J. Manners, Chem. and Ind., 1962, 984.153 N. Handa and K. Nisizawe, Nature, 1961, 192, 1078.154 A. S. Perlin and S. Suzuki, Canad. J . Chern., 1962, 40, 50.155 L. Hough and M. B. Perry, J., 1962, 2801.156 M. L. Wolfrom, M. L. Laver, and D. L. Patin, J. Org. Chem., 1961, 26, 4533.157 H. Meier, Acta Chem. Scand., 1961, 15, 1381.158 T. Koshijima, Agric. and Biol. Chem. (Japan), 1961, 25, 706; G. A. Adams,Canad. J . Chem., 1961, 39, 2423; G. 0. Aspinall, R. Begbie, and J. E. McKay, J., 1962,214; T. E. Timell, Svensk Papperstidn., 1961, 64, 744.{bid., p. 4596.150 D. W. Drummond, E. L. Hirst, and E. Percival, J., 1962, 1208.160 G.G. S. Dutton and T. G. Murata, Canad. J. Chem., 1961, 39, 1995; G. G. S.1 6 1 D . M. W. Anderson, A. M. Bews, S. Garbutt, and N. J. King, J., 1961, 5230.Dutton and S. A. McKelvey, {bid., p. 2582ULBRICHT: NUCLEIC ACIDS 37 1In porphyran from the red seaweed, Porphyra umbiliuzlis, the sulphateester is attached mainly to C-6 of L-galactose units that are linked toother residues through positions 1,2 or 1,4. The other units are mainly1,3-linked. l6The chief repeating unit of the mucopolymccharide of bovine cornea 163is shown below (10).CHI*OH FH,.O*S03HIH n(10)“ O D 0 0.. .. . ..--* H OH H NHAcJ. H.11. NUCLEIC ACIDSIT has been noted that in the ten years after 1947 the nucleic acid entriesin Chemical Abstracts showed a logarithmic growth with a doubling of thenumber every 2.7 years.1 The Annuul Reviews of Biochemistry devoted onechapter to nucleic acids in 1948-57, two in 1958-60, three in 1961, and fourchapters, totalling 122 pages, in 1962,2an indication of the current importanceof this field.Since the last reviews in these ReportsY3 considerable progresshas been made in the organic chemistry of nucleic acids, but there is nodoubt that the most notable advances have been on the biochemical side.Bases.-There has been great interest in the effect of radiation (ultra-violet, unless otherwise stated) on the nucleic acid bases. Beukers andBerends * found that adenine, guanine, and thymine are not affected inaqueous solution, whereas uracil and cytosine are hydrated at the 4,5-doublebond.Irradiation of frozen solutions of thymine or uracil gives rise to theformation of dimers with a cyclobutane structure; the thymine dimer isregarded as having structure (1) or that with themethyl groups on the same side of the cyclobutanering. It is supposed that dimer formation occursin frozen solutions because of the longer life-timeof triplet-state radicals. The hydration can be re- H H Me 0 ( 1 )versed by a change in p€€ and heat. In dirnerisationthere is an equilibrium whose position depends on the concentration of para-magnetic substances, dimerisation being diminished by dissolved molecularHLB; 0162 D. A. Rees, J., 1961, 5168.163 S. Hirano, P. Hoffman, and K. Meyer, J. Org. Chem., 1961, 26, 5064.R.F. Steiner and R. F. Beers, “ Polynucleotides,” Elsevier, Amsterdam, 1961.L. F. Cavalieri and B. H. Rosenberg, “ Nucleic Acids: Molecular Biology ofDNA,” Ann. Rev. Biochem., 1962, 31, 247; E. S. Canellakis, “ Metabolism of NucleicAcids,” Ann. Rev. Biochem., 1962, 31, 271; M. Grunberg-Manago, “ Enzymatic Syn-thesis of Nucleic Acids,” Ann. Rev. Biochem., 1962, 31, 301; M. V. Simpson, “ ProteinBiosynthesis,” Ann. Rev. Biochem., 1962, 31, 333.A. 3%. Miehelson, Ann. Reports, 1960, 57, 294; J. N. Davidson, {bid., p. 352.R. Beukers and W. Berends, Biochtim. Biophys. Acta, 1960, 38, 573; 1960, 41,550; 1961, 49, 181372 ORGANIC CHEMISTRYoxygen and transition-metal ions. It is suggested that this dimerisation reac-tion is responsible for the biological effects of ultraviolet radiation on deoxy-ribonucleic acid (DNA).4 Wacker’s group have shown that the thyminedimer is formed in DNA when bacteria are irradiated and that the sameproduct is obtained by irradiating dilute aqueous solutions of thymine.5Similar dimers can be obtained from uridine and thymidine,6 dimethyl-uracil,7 and dimethylthymine,s and a mixture of uracil and thymine givesa mixed dimer.9 In the dinucleotide guanyloyl-5’,3’-uridine, the uracil washydrated but no dimer was formed.9 The action spectrum for the reversalof the dimerisation of thymine after thawing has a shape similar to that ofthe ultraviolet-absorption curve of the dimer itself; the intensity is very lowat 300 m p and increases as the wavelength decreases.1° The dimerisationof thymine and thymine nucleotides is an equilibrium depending on thewavelength; the equilibrium is on the side of the monomer at 235 mp, andon the side of the dimer at 285 mp.ll The rate of killing of Escherichia colion ultraviolet irradiation is proportional to the amount of thymine dimerformed;l2 also consistent with the view that thymine dimer formation isresponsible for the biological effects of ultraviolet radiation on DNA arethe fhdings that incubation of irradiated DNA with photoreactivatingenzyme from baker’s yeast in light destroys over 90% of the thymine dimerformedY13 and that incorporation of the thymine analogue azathymine intothe DNA of bacteria increases their resistance to ultraviolet irradiation.l4?-Irradiation of deaerated aqueous solutions of thymine gives quite differentproducts, namely, 5-hydroxymethyluracil, thymine cis- and trans-glycol, anddihydrothymine.l5Previous evidence 16 which had indicated that the site of protonation inthe nucleic acid bases and their nucleosides was N-1 in cytosine and adenineand N-7 in guanine has been confirmed by the X-ray diffraction of 9-methyl-adenine dihydrobromide (H on N-1 and N-7) and 3-methylcytosine hydro-bromide (H on N-1) 1 7 and by a study of the infrared spectra of protonatedand deprotonated nucleosides, in which the site of protonation was found tobe at N-1 in cytidine and adenosine, and at N-7 in guanosine.ls Resultsfrom the alkylation of bases and nucleosides are not always as clear-cut,since this may depend on the reaction conditions.Thus adenine givesA. Wacker, H. Dellweg, and D. Weinblum, Naturwiss., 1960, 47, 477.S. Y. Wang, Nature, 1961, 190, 690.A. Wacker, D. Weinblum, L. Triiger, and Z. H. Moustafa, J. Mol. Biol., 1961,10 R. Setlow, Biochim. Biophys. Acta, 1961, 49, 237.11 H. E. Johns, S. A. Rapoport, and M. Delbriick, J. Mol. Biol., 1962, 4, 104.12 A. Wacker, H. Dellweg, and D. Jackerts, J. Mol. Biol., 1962, 4, 410.l3 D. L. WuW and C. S. Rupert, Biochem. Biophys. Res. Comm., 1962, ‘7, 237.14A. Wacker and D. Jackerts, J. Mol. Biol., 1962, 4, 413; H. L. Giinther andl5 B. Ekert, Nature, 1962, 194, 278.l6 C. A. Dekker, Ann. Rev. Biochem., 1960, 29, 463.17R. F. Bryan and K. Tomita, Nature, 1961, 192, 812.ISM. Tsaboi, Y.Kyogoku, and T. Shhanouchi, Biochirn. Biophys. Acta 1968,8 A . Wacker, H. Dellweg, and E. Lodemann, Angew. Chem., 1961, 73, 64; A.8 n. L. Wulff and G. Fraenkel, Biochim. Biophys. Acta, 1961, 51, 333.Wacker, L. Trager, and D. Weinblum, ibid., p. 65.3, 790.W. H. Prusoff, Biochim. Biophys. Acta, 1962, 55, 778.55, 1ULBRICHT: NUCLEIC ACIDS 373adenine 1-oxide l9 but is alkylated a t N-3,203 21 whereas adenosine 22 anddeoxyadenosine 23 are alkylated a t N-1, cytosine and cytidine at N-1,24and guanine a t N-7 and bhen at N-9.20, 25The base analogue 2-aminopurine, which is highly mutagenic, was foundto be incorporated to a small extent (O-lyo of thymine) into DNA.26The occurrence of 5-hydroxymethylcytosine (HMC) in place of cytosinein the T-even bacteriophages of E.coli has led to many studies of thisinteresting system. Lehman showed that in T2, 25% of the 5-hydroxy-methylcytosine has no glucose attached t o the hydroxymethyl group, 70%has one molecule, and 5% has two molecules of glucose attached, the firstbeing bound by an a-linkage, and the second to the first by a @-linkage. InT4, every molecule of hydroxymethylcytosine has one molecule of glucose,of which 70% is in the a- and 30% in the b-linkage. In T6 the linkagesare as in T2 but the percentages of 0, 1, and 2 molecules of glucose are 25, 3,and 72, respectively.27 The DNA of T6 has been shown to contain gentio-biose ; hence the full structure of the hydroxymethylcytosine nucleoside isCH2 - 0 CH>*OHOHHOHO 'as shown (2) .2* The reaction leading to the glucosylation of hydroxymethyl-cytosine-DNA has been investigated and it has been shown that in T2 andT6 there is an enzyme transferring glucose from uridine diphosphate-glucoset o give a-glucosyl-HMC-DNA, but T4 contains two enzymes, the glucosyllinkage produced being a with one enzyme and @ with the other.29 Infec-tion of E .coli by T-even bacteriophage leads to the synthesis of new enzymes,such as those just discussed, and to an increase in the activity of various otherenzymes associated with DNA biosynthesis. It has been found that, atISM. A. Stevens and G. B. Brown, J . Amer. Chem. SOC., 1960, 82, 2759.2o J. W. Jones and R. K. Robins, J. Amer. Chem. SOC., 1962, 84, 1914.21 B. C. Pal, Biochemistry, 1962, 1, 558; N.J. Leonard and R. A. Laursen, J. Org.Chem., 1962, 27, 1778; N. J. Leonard and J. A, Deymp, J . Amer. Chem. SOC., 1962,84, 2148.Z2P. Brookes and D. Lawley, J., 1960, 539.23 A. Codington, Biochim. Biophys. Acta, 1962, 59, 472.Brookes and D. LawIey, J., 1962, 1348.25 P. Brookes and D. Lawley, J., 1961, 3923.26 A. Wacker, S. Kirschfeld, D. Hartmann, and D. Weinblum, J. Mol. Biol., 1960.2, 69; A. Wacker, S. Kirschfeld, and L. Trager, ibid., p. 241; H. Gottschling and E.Freese, 2. Naturforsch., 1961, 16b, 515.27 I. R. Lehman and E. A. Pratt, J. Biol. Chent., 1960, 235, 3254.28 S. Kuno and I. R. Lehman, J. Biol. Chem., 1962, 237, 1266.2 9 S. R. Kornberg, S. B. Zimmerman, and A. Kornberg, J. Biol. Chem., 1961,236, 1487; S. B. Zimmerman, S. R.Kornberg, and A. Kornberg, ibid., 1962, 237, 512;J. Josse and A. Kornberg, ibid., p. 1968374 ORGANIC CHEMISTRYleast in the cases of thymidylate kinase 30 and DNA polymera~e,~~ theseare new enzymes, different from those present in the uninfected host.5-Hydroxymethylcytosine has not been found in any other DNA, anduntil recently it was the only case of a normal base completely replaced byan analogue, but it has now been found that the DNA of bacteriophage SP8of Bacillus subtiEis contains 5-hydroxymethyluracil in place of thymine. 32The synthesis of this compound has been previously reported,33 and itsstructure confirmed by a study of its infrared spectrum.34 The antibioticbacimethrin has been identified as the 2-methyl ether of 5-hydroxymethyl-cytosine 35 and is an analogue of the pyrimidine portion of thiamine and ofthe biologically active corresponding 2-methylthio-compound, methi~prim.~~There has been further work on the minor bases in ribonucleic acid(RNA).6-Methylaminopurine is produced by the alkaline rearrangement ofl-methyladenine; acid hydrolysis of RNA shows that only E. coli actuallycontains this base, whereas yeast and liver RNA contain 1 -meth~ladenine.~The methyl groups of the methylated purines and of RNA-thymine arederived from methionine 38 (the methyl group of DNA-thymine is derivedfrom formate or serine via folic acid) and it appears that an enzyme existsin E. coli which can methylate the base components of soluble (transfer)RNA (s-RNA) when the latter are already in polynucleotide form.39 Thereaction of reduced vitamin B,, with s-adenosylmethionine gives “ methyl-cobalamin,” conceivably the actual biological methylating agent .40In a study of the proton mobility of substituted uracils it was reported 41that “ the lability of the N(3,-proton of thymine does not differ significantlyfrom that of uracil, and the lability of N(3)-proton of 6-azauracil falls in thesame range, though slightly more so, as do the N(3,-protons of thymine anduracil.’ ’Nuc1eosides.-The synthesis of nucleosides has been reviewed 42 and ithas been pointed out that the direct synthesis of 2’-deoxynucleosides, e.g.,2’-deoxycytidine, 43 from pyrimidine mercury salts, probably involves anO+N-glycosyl rearrangement ; 42 O+N-alkyl rearrangements are readilybrought about in pyrimidine~.~4 Reaction of the silver salt of N-acetyl-30 L.J. Bello, M. J. V. Bibber, and M. J. Bessman, Biochim. Biophys. Acta, 1961,53, 194.31H. V. Aposhian and A. Kornberg, J. Biol. Chem., 1962, 237, 519.3 2 R. G. Kallen, M. Simon, and J. Marmur, J. Mol. Biol., 1962, 5, 248.33 R. E. Cline, R. M. Fink, and K. Fink, J. Amer. Chem. SOC., 1959, 81, 2521.3 4 T. L. V. Ulbricht, Naturwiss., 1958, 45, 416.35 H. C. Koppel, R. H. Springer, R. K. Robins, and C. C. Cheng, J . Org. Chem.,313 T. L. V. Ulbricht and J. S. Gots, Nature, 1956, 178, 913; R. Guthrie, M. E.37 D. B. Dunn, Biochim. Biophys. Acta, 1961, 46, 198.38 L. R. Mandel and E. Borek, Biochem. Biophys. Res. Comm., 1961, 4, 14; 1961,39 E.Fleissner and E. Borek, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1199.4 0 W. Friedrich and E. Konigk, Biochenz. Z., 1962, 336, 444.41 J. P. Kokko, L. Mandell, and J. H. Goldstein, J. Amer. Chem. SOC., 1962, 84,4 2 T. L. V. Ulbricht, Angew. Chem., Internat. Ed., 1962, 1, 476.43 J. J. Fox, N. C. Yung, I. Wempen, and M. Hoffer, J. Amer. Chem. SOC., 1961,4 4 T. L. V. Ulbricht, J., 1961, 3345.1962, 27, 1492.Loebeck, and M. J. Hillman, Proc. SOC. Exp. Biol. Med., 1957, 94, 792.6, 146; B. B. Biswas, M. Edmonds, and R. Abrams, ibid., p. 146.1042.83, 4066ULBRICHT: NUCLEIC ACIDS 375cytosine with a glycosyl halide gives an O-glycoside, which rearranges tothe N-glycoside with mercuric br0mide.~5 The finding that a similar re-arrangement can occur in an O-glycoside of 2-hydroxypyridine but not of4-hydroxypyridine 46 supports a suggested mechanism in which the key stepis the formation of a mercuric complex on the nitrogen atom ortho to theO-glycoside group :45 it is hardly consistent with a mechanism involvingionisation to give a glycosyl cati~n,~e particularly as these reactions arecarried out in non-polar solvents.The yield in the synthesis of 4(6)-aza-uridine can be raised from 14% 47 to 25% 48 by using an azauracil with aprotecting group on N-1 (the most acidic position-in uracil it is N-3), butsix steps are required in place of two. A general synthesis of pyrimidinylB-D-arabinosides has been rep~rted.~g 3‘-Deoxyadenosine can be syn-thesised by the reaction of the corresponding p-nitrobenzenesulphonic esterwith iodide ion and subsequent reduction since a cyclonucleoside cannotbe involved as an intermediate, this synthesis shows that by using a morereactive secondary sulphonyl ester nucleophilic displacement can be achieved.An alternative synthesis of 3’-deoxyadenosine has also been reported.51The reaction of 0,2’-cyclouridine with iodide ion in the presence of acid 52has been extended to the synthesis of 2’-fluoro-, 2’-chloro-, and 2’-bromo-deoxyuridine ;53 the mechanism of these reactions is strictly analogous tothat of the dealkylation of alkoxypyrimidines by iodide ion in the presenceof acid.44Uridine and cytidine on treatment with polyphosphoric acid give, notonly the expected diphosphates of the above nucleosides, but also those ofspongouridine and of 3 - B- D - ara bofuranosylcyt osine.54 0,2’-Cyclonucleo-sides are intermediates and can be isolated. The ultraviolet spectra of theuric acid riboside from beef blood suggest that it is the 3-rib0side.~~ Thestructure of the vitamin B,, co-enzyme has been reported;56 in it, the 5-methylene group of the ribose is directly linked to cobalt. A partial syn-thesis, analogous to cyclonucleoside formation, is achieved by reactionof fully reduced hydroxocobalamin and 2’,3’-isopropylidene-5’-tosyladeno-sine.The structure of pseudouridine has been confirmed by syntheses 42, 5 8by using a pyrimidine-lithium intermediate, as previously suggested for4 5 T. L. V. Ulbricht, Proc. Chem. SOC., 1962, 298.46 G. Wagner and H.Pischel, Arch. Pharm., 1962, 295, 373.4 7 R. E. Handschumacher, J . Biol. Chem., 1960, 235, 764.4 8 M. Prystas, J. Gut, and F. Sorm, Chem. and Ind., 1961, 467.40 E. J. Reist, J. H. Osiecki, L. Goodman, and B. R. Baker, J . Amer. Chem. Soc.,5 0 Sir Alexander Todd and T. L. V. Ulbricht, J., 1960, 3275.51 W. W. Lee, A. Benitez, C. D. Anderson, L. Goodman, and B. R. Baker, J . Amer.s2 D. M. Brown, D. B. Parihar, and Sir Alexander Todd, J., 1958, 4242.53 J. F. Codington, I. Doerr, D. Van Praag, A. Bendich, and J. J. Fox, J . Amer.54 E. R. Walwick, W. K. Roberts, and C. A. Dekker, Proc. Chem. Soc., 1959, 84.5 5 D. Hatfield and H. S. Forrest, Biochim. Biophys. Ada, 1962, 62, 185.66 P. G. Lenkert and D. C. Hodgkin, Nature, 1961, 192, 937.5 7 K.Bernhauer, 0. Miiller, and G. Muller, Biochem. Z., 1962, 336, 102; E. L.5 8 R. Shapiro and W. Chambers, J . Amer. Chem. SOC., 1961, 83, 3921.1961, 83, 2208.Chem. Soc., 1961, 83, 1906.Chem. SOC., 1961, 83, 5030.Smith, L. Mervyn, A. W. Johnson, and N. Shaw, Nature, 1962, 194, 1175376 ORGANIC CHEMISTRYmaking pyrimidinyl C-glycosides,59 and by its conversion into the 06,5’-cyClo-nucleoside.60 The biosynthetic pathway is not yet clear, but probablyinvolves uridine and possibly 3,5-diribo~yluracil.~l A curious finding is thata PeniciZZium species contains enzymes which catalyse the conversion ofpseudouridine into pseudoisocytidine.62The mutagenic activity of hydroxylamine 63 has led to investigations ofits chemical reaction with pyrimidine nucleosides.The reaction with urid-ine or uridylic acid causes ring fission with formation of 5-isoxazolone andribose oxime 64 and is fastest at pH 10, whereas the optimum pH for reac-tion with cytidine is 6. At this pH or in anhydrous hydroxylamine, cytosinederivatives react by addition of one molecule of hydroxylamine to the 45-double bond followed by exchange a t N-6, the final product being an N(6)hydroxycytosine derivative. 65 The compound responsible for the bluecolour in the Dische reaction used for estimating deoxyribose has been shownto be p-acetylacraldehyde.66Nucleotides and Polynuc1eotides.-Details have been published of thesynthesis of nucleotides by use of 2-cyanoethyl phosphate 67 and pyrophos-phoryl chloride 68 as phosphorylating agent.A new synthesis of nucleotidesinvolves 2,3 -di- 0- benzoyl- 5 - diphenox yphosphinyl-D -ribofuranosyl bromideas the key intermediate.69 Two syntheses of coenzyme A have appeared. 709 71That by Moffatt and Khorana 70 yields a mixture with isocoenzyme A re-quiring a difficult separation as the last step; Michelson’s synthesis 71 is anexample of a general method for nucleotide anhydrides, by anionic displace-ment of diphenyl phosphate from an intermediate triesterified pyrophos-phate. 72 PI-Adenosine 5’- (2’,3’-cyclic phosphate) P2P2-diphenyl pyrophos-phate with pantethine 4’,4’-bisphosphate gave the 2’,3’-cyclic phosphate ofoxidised coenzyme A, which was cleaved by takadiastase ribonuclease T, tothe 3’-phosphate exclusively. Conversion into the thiol form and chromato-graphic purification gave the lithium salt of coenzyme A in an overall yieldof 63% from adenosine diph0sphate.7~ In another synthesis of nucleotideanhydrides, 73 nucleotide-imidazole compounds are used : adenosine mono-5 9 T.L. V. Ulbricht, Tetrahedron, 1959, 6, 225.6o W. E. Cohn and A. M. Michelson, Biochemistry, 1962, 1, 490.J. B. Hall and F. W. Allen, Biochim. Biophys. Actu, 1960, 39, 557; 1960, 45,163; A. W. Lis and F. W. Allen, ibid., 1960,44,224; P. W. Robbins and J. B. Hammond,J . Biol. Chem., 1962, 237, PC 1379; J. K. Pollak and H. R. V. Arnstein, Biochim.Biophys. Acta, 1962, 55, 798.62 A. W. Lis and F. W. Allen, Biochim. Biophys. Acta, 1962, 61, 250.63 E. Freese, E. Bautz, and E. B. Freese, Proc.Nut. Acad.Sci. U.S.A., 1961,47,845.6 4 H. Schuster, J. Mol. Biol., 1961, 3, 447; D. W. Verwoerd, H. Kohlhage, andG 5 D. M. Brown and P. Schell, J. Mol. Biol., 1961, 3, 709.G 6 L. Birkofer and R. Dutz, Annulen, 1962, 657, 94.6 7 G. M. Tener, J. Arner. Chem. SOC., 1961, 83, 159.68 W. Koransky, H. Grunze, and G. Miinch, 2. Natzcrforsch., 1962, Ub, 291.7 0 J. G. Moffatt and H. G. Khorana, J. Amer. Chem. SOC., 1961, 83, 663.71 A. M. Michelson, Biochim. Biophys. Acta, 1961, 50, 607.7 2 A. M. Michelson, Colloquium on Nucleic Acids and Polyphosphates, Strasbourg,July 1961 (Editions C.N.R.S., Paris, 1962, p. 39).73 F. Cramer and G. Weimann, Chem. Ber., 1961,94,996; F. Cramer, H. Neunhoffer,K. H. Scheit, G. Schneider, and J. Tennigkeit, Angew. Chem,, Internat.Ed., 1962, 1,331.W. Zillig, Nature, 1961, 192, 1038.T. Ukita and H. Hayatsu, J. Amer. Chem. SOC., 1962, 84, 1879ULBRICHT: NUCLEIC ACIDS 377phosphate (AMP) reacts with imidazole and trichloroacetonitrile to give anAMP-imidazole which gives adenosine diphosphate (95%) with orthophos-phate, and flavin adenine nucleotide (62%) with riboflavin 5’-phosphate,Similarly, uridine monophosphate-imidazole reacts with glucose 1 -phosphateto give uridine diphosphate-glucose (67%). New syntheses of adenyloyl~ulphate,7~ of thymidine diphosphate glu~ose,‘~ and uridine diphosphate-glucuronic acid 74 have been accomplished. A large number of new nucleo-tide anhydrides of the nucleoside diphosphate-sugar type have been isolated.Chemical synthesis of specifically 3’,5’-linked ribonucleotides and ofpolynucleotides has made little progress since a recent review.76 A numberof 3’,5’-linked dinucleotides have been synthesised in 25--40y0 yield,77 butthe methods lack the simplicity essential if polynucleotides are to be pre-pared by them.Cohn and his colleagues 78 have continued work on thecleavage of the phosphate of periodate-oxidised 5’-nucleotides, which pro-ceeds at pH < 8 after formation of an amine addition product at pH > 10;the method is very useful for determining sequences of short oligonucleotides.The catalytic oxidation of the hydroxymethyl group in nucleosides 79 hasbeen developed into a method 80 which may be applicable to the stepwisedegradation of deoxyribopolynucleotides.Thymidinyl-5’, 3’-thymidine masoxidised to the carboxylic acid and converted into the amide (3) which under-goes base-catalysed elimination to thymidine-5’ phosphate (97%), thymine(69%), and what may be anhydrothpmidine uronic acid (23%).PrHN*CO /O, ThymineI n - ~(R= 5’-Thymidinyl)unThe key intermediate in the metabolic conversion of nucleotides intodeoxynucleotides remains to be determined. Reichard has shown thatwith cytidine-5’ phosphate, conversion into the pyrophosphate is necessary,followed by a reduction requiring adenosine triphosphate, Mg2 f, and lipoicacid. The incorporation of [ 2-14C]cytidine-[H3]ribosyl into the deoxycytidineof DNA without significant loss of tritium from the sugar S 2 indicates thatthe reduction does not involve loss of hydrogen from the 2’-position.7 4 A.M. Michelson and F. Wold, Biochemistry, 1962, 1, 1171.75 R. Okazaki, T. Okazaki, J. L. Strominger, and A. M. Michelson, J . BioZ. Chem.,‘13 A. M. Michelson, Ann. Rev. Biochem., 1961, 30, 130.7 7 J. Smart and F. so-, CoZE. Czech. Chem. Comm., 1962, 27, 86; D. H. Rammler7 8 W. E. Cohn and J. X. Khym, Colloquium on Ribonucleic Acids and Poly-7 9 C. B. Reese, K. Schofield, R. Shapiro, and Sir A. Todd, Proc. Chern. SOC., 1960,*l P. Reichard, J . Biol. Chem., 1962, 237, 3513.8 2 R. Y . Thompson, G. T. Scotto, and G. B. Brown, J . Biol. Chem., 1962, 237,1962, 237, 3014.and H. G. Khorana, J . Amer. Chem. SOC., 1962, 84, 3112.phosphates, Strasbourg, July 1961 (Editions C.N.R.S., Paris, 1962, p.217).261.J. P. Vizsolyi and G. M. Tener, Chem. and Ind., 1962, 263.3510378 ORGANIC CHEMISTRYA natural copolymer of deoxyadenylic and thymidylic acid has beenisolated from the DNA of a marine crab, Cancer borealis, by chromatographyon kieselguhr impregnated with methylated albumin. It constitutes 30%of the total DNA 83 and has alternating adenine and thymine residues, witha guanine and cytosine content of 3%.84 Synthesis of a polymer of deoxy-guanylate and deoxycytidylate has now been achieved from the triphos-phates by using the DNA polperase from E. coli, in the absence of addedprimer, and after an extended lag period.s5 A synthetic trinucleotide ofdeoxyguanosine appears to be highly aggregated in 0.25~1-phosphate buffera t pH 6.8, having Tm = 58" and = 10-12.s6 The synthesis of polyribo-guanylic acid by means of polynucleotide phosphorylase has now beenaccomplished with low concentrations of guanosine diphosphate and Mg2fand a high concentration of enzyme ;87 previous failures to synthesise poly-guanylic acid may have been due to an inhibition of the enzyme by a multi-stranded helical form of guanosine oligonucleotides.There is an excellentrecent survey of nucleic acid biosynthesis by Grunberg-Manago.2A very important paper is that of Spencer, Fuller,Wilkins, and G. L. Brown 88 on the X-ray diffraction of crystalline s-RNAwhich indicates that it has a helical structure similar to that of DNA type A.It consists of a single strand folded back on itself, the two halves of thechain being anti-parallel.The region where the strand folds back forms itloop in which the bases (perhaps three in number) are unpaired. Otherphysical properties of s-RNA also indicate that it has a highly asymmetric,relatively rigid secondary structure, more like DNA than like high-mole-cular-weight RNA. 89 There is also evidence suggesting that pseudouridineand the methylated bases are concentrated in the central region of S-RNA,~Oand on this basis a model of s-RNA has been proposed 91 which is very likethe structure proposed by Spencer et al. except that the loop is thought tocontain about 20 residues. Doty 92 has reviewed the physical chemistry ofpolynucleotides and nucleic acids. The base composition of DNA can bedetermined by a number of purely physical measurements : the &260/&280 ratioa t pH 3,93 the buoyant density in czesium chloride,g4 and, perhaps mostaccurately, the denaturation temperature.95 Electron micrographs ofdeoxyribonucleoprotein from M . lysodeikticus show a tangled skein withoutfree ends,96 and autoradiography of labelled DNA obtained from E. coli83 N. Sueoka and T. Cheng, J. Mol. Bwl., 1962,4, 161 ; Proc. Nut. Acad. Sci. U.S.A.,1962, 48, 1851.84 M. N. Swartz, T. A. Trautner, and A. Kornberg, J . Biol. Chem., 1962, 237, 1961.85 C. M. Radding, J. Josse, and A. Kornberg, J . BioE. Chern., 1962, 237, 2869.86 R. K. Ralph, W. J. Connors, and H. G. Khorana, J . Amer. Chem. SOC., 1962,87 J. R. Fresco and D. Su, J . BioZ. Chem., 1962, 237, PC 3305.88 M.Spencer, W. Fuller, M. H. F. Wilkins, and G. L. Brown, Nature, 1962, 194,89 S . W. Luborsky and G. ,L. Cantoni, Bwchim. Biophys. Acta, 1962, 61, 481.90 T. Nihei and G. L. Cantoni, Biochim. Biophys. Acta, 1962, 61, 463.01 K. S. McCully and G. L. Cantoni, J . MoZ. Biol., 1962, 5, 497.9zP. Doty, J . Polymer Sci., 1961, 55, 1.93 A. Fredericq, A. Oth, and F. Fontaine, J . Mol. BioZ., 1961, 3, 11.94 C. L. Shildkraut, J. Marmur, and P. Doty, J. MoZ. Biol., 1962, 4, 430.95 J. Marmur and P. Doty, J . Mol. Biol., 1962, 5, 109.OeA. Kleinschmidt, D. Lang, and R. K. Kahn, 2. Nuturforsch., 1961, 16b, 730.Physical chemistry.84, 2265.1014ULBRICHT: NUCLEIC ACIDS 379by gentle lysis is consistent with a length of at least 400 p and a molecularweight of I09 or more,97 suggesting that bacterial DNA may exist as a singlemolecule. The usual methods of extraction probably break molecules byshearing.Effective and mild methods of denaturing DNA in solution(breaking hydrogen bonds) are the addition of high proportions of glycol andof glycerol, which increase the relative absorbance a t 260 mp at roomtemperature,98 and of formamide ; measurements of the infrared spectra 99of sodium salts of nucleic acids treated with formamide and of the opticalrotatory dispersion 100 indicate that nucleic acids have no secondary structurein this solvent.Further studies of the DNA of bacteriophage $X 174, which appears tobe single-stranded, show that the replicative form has several propertiessimilar to those of double-stranded DNA, and that the normal, single-stranded form, when undegraded, probably has a covalently linked ringstructure.lo1The Genetic Code and Protein Synthesis.-Only a few of the resultsrecently obtained in this, by far the most active, area of currenti nucleic acidresearch can be mentioned here, and attention is directed to other reviewsfor further detailsa2* lo2 Jacob and Monod,lo3 in their theory of proteinsynthesis, postulated the existence of a special form of RNA, short-lived,and with a base-composition complementary to that of DNA, which carriesthe necessary information from the nucleus to the ribosomes, where proteinsynthesis takes place. High turnover in a minor RNA fraction after phageinfection of E. coli, this fraction having a nucleotide composition correspond-ing to that of phage DNA, had already been dem0n~trated.l~~ Furtherexperiments with E .coli showed that, after infection with T2-bacteriophage,no new ribosomes can be detected, and a fraction corresponding in propertiesto messenger RNA is found to be added to pre-existing ribosomes.lo5 Thetechnique of ‘‘ pulse-labelling ” has been of great value in connexion withthese experiments; that is, after addition of the DNA primer to the system(which may be a living cell, or an in vitro system containing RNA polymer-ase), labelled RNA precursors are made available for a very short time only.It is then found that a fraction with the postulated properties of messengerRNA is labelled first ; only subsequently is ribosomal RNA labelled. In thismanner it has been possible to synthesise an RNA with a base compositioncomplementary to that of the priming DNA used with an RNA polymerasefrom E.coli in vitro,lo6 and similarly to show the formation of an RNAO 7 J. Cairns, J . MoZ. Biol., 1962, 4, 407.98 E. L. Duggan, Biochem. Biophys. Res. Comm., 1961, 6, 93.OD Y. Kyogoku, M. Tsuboi, T. Shknanouchi, and I. Watanabe, J . MoZ. BWZ., 1961,loo P. 0. P. Ts’O, G. K. Helmkamp, and C . Sander, Biochim. Biophys. Ach, 1962,lol R. L. Sinsheimer, B. Starman, C. Naylor, and S . Guthrie, J . Mol. BioZ., 1962,4, 142; W. Fiers and R. L. Sinsheimer, ibid., 1962, 5, 424.lo2 P. C. Zamecnik, Biochem. J., 1962, 85, 257.lo3 F. Jacob and J. Monod, J . MoZ. BioZ., 1961, 3, 318.lo* E.Volkin and L. Astrachan, Virology, 1956, 2, 149.lo5 S. Brenner, F. Jacob, and M. Meselson, Nature, 1961,190, 576; F. Gros, H. Hiatt,log M. Chamberlain and P. Berg, Proc. Nut. Acud. Sci. U.S.A., 1962, 48, 81.3, 741.55, 584.W. Gilbert, C. G. Kurland, R. W. Risebrough, and J. D. Watson, ibid., p. 581380 ORGANIC CHEMISTRYcomplementary to DNA in ~ i ~ 0 . 1 0 7 Many authors have reported similarresults-DNA-dependent synthesis of an RNA of the messenger type-inmammalian systems, lo8 and messenger RNA has also been demonstratedin pea seedlings.loD Specific hybrid formation has been shown to occurbetween T2-DNA and the RNA synthesised in E. coli infected withT2,110and T4-specific RNA has been separated from E. coli RNA by chromato-graphy on columns of cellulose linked to T4-DNA.l11 Hybrid formationhas also been shown to occur between ribosomal RNA and homologous DNAfrom E.C O Z ~ , ~ ~ ~ indicating that there is a sequence in DNA complementaryto its ribosomal RNA although, as a whole, they are not complementary.All these results are consistent with the theory that DNA is the fundamentalsource of information in living systems which is passed on by a templatemechanism in the formation of RNA.Ribo-somal RNA appears to be first; formed on DNA and finally built into acomplete ribosomal particle by sequential intermediate steps, including aDNA-RNA complex in which the RNA is not complementary to DNA buthas the composition of ribosomal RNA.l13 Development of a method forthe isolation of undegraded messenger RNA from E. coli 114 has made itpossible to show that it is heterogeneous, consisting of four main componentsof differing sedimentation coefficients.There is not, however, a precursor-product relationship among them. Chloramphenicol specifically inhibitsthe synthesis of the highest-molecular-weight messenger RNA (23 to 305)which is the only one found to associate with 708 ribosomes (active inprotein synthesis) in vitro.The discovery, reported in a classic paper by Nirenberg and Matthaei,l15that, in a protein-synthesising system, addition of polyuridylic acid led tothe synthesis of polyphenylalanine from phenylalanine, initiated a periodof frenzied activity devoted to " cracking the genetic code," the latestresults being reported in the New York Times.By assuming a non-over-lapping triplet code 116 (three adjacent nucleotide residues coding for oneamino-acid) it was soon possible to propose a complete code on the basisJapanese workers have made important contributions. 113, 1141 0 7 M. Takai, N. Kondo, and S. Osawa, Biochim. Biophys. Acta, 1962, 55, 416.l o s P. Cheng, Biochim. Biophys. Actu, 1961, 53, 232; A. Sibatani, S. R. de Kloet,V. G. Allfrey, and A. E. Mirsky, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 471; H. H.Hiatt, J. MoZ. BioZ., 1962, 5, 217; P. A. Marks, C. Willson, J. Kruh, and F. Gros,Biochem. Biophys. Res. Comm., 1962, 8, 9.log U. E. Lohning, Nature, 1962, 195, 467.110 B. D. Hall and S. Spiegelmann, Proc. Nat. Acad. Sci. U.S.A., 1961, 4'7,E.K. F. Bautz and B. D. Hall, Proc. Nut. Acad. Sci. U.S.A., 1962, 48,112 S. A. Yankovsky and S. Spiegelmann, Proc. Nat. Acad. Sci. U.S.A., 1962, 48,113 E. Otaks, S. Osawa, Y. Oota, A. Ishima, and H. Mitsui, Biochim. Biophys.114 A. Ishima, N. Mizuno, M. Takai, E. Otaka, and S. Osawa, J. Mol. BioZ., 1962,115 M. W. Nirenberg and J. H. Matthaei, Proc. Nut. Acad. Sci. U.S.A., 1961, 47,116 F. H. C. Crick, L. Barnett, S. Brenner, and R. J. Watts-Tobin, Nature, 1961,137.400.1069.Acta, 1962, 55, 310.5, 251.1588.192, 1227ULBRICHT: NUCLEIC ACIDS 381of these results.11' All the triplets contained uracil and Chargaff 118 calcu-lated that messenger RNA for bovine ribonuclease would have to have thefollowing composition : adenine, 16-9 ; guanine, 15.9 ; cytosine, 20-7 ; anduracil, 46.5% ; which appeared very unlikely, to say the least.An investiga-tion of satellite tobacco necrosis virus indicated that 60% of its RNA chainwould be required to code for its protein and that the uracil content wassuch that all of it would have to be in this portion of the chain if the codewere correct; also the maximum number of nucleotide residues betweentwo uracils cannot exceed four in the coding part. Analysis of the oligo-nucleotides obtained by the action of pancreatic ribonuclease showed thatthese requirements were not fulfilled.119 It seems that 6he requirementifor uracil is an accident of the experimental system, uracil conferring somedesirable property on the polynucleotide chain; it has been noted above thateven a trinucleotide of deoxyguanosine has a complex secondary structureand this may well explain the failure to achieve incorporation of amino-acidswith polymers containing high proportions of guanylic acid.Some of thecoding assignments made have depended on the assumption that the com-position of the polynucleotide is the same as that of the mixture of monomersfrom which it was prepared; this has been strongly criticised by Bretscherand Grunberg-Manago 120 who determined the exact ratios in the polymersthey used and found them to be often very different from the original ratioof diphosphates. The same authors consistently found incorporation ofsmall amounts of leucine with polyuridylic acid in addition to phenylalanine ;since triplets are assigned on the basis of the ratio of incorporation of theamino-acid to that of phenylalanine as standard, they point out that assign-ments on the basis of small amounts of incorporation may be incorrect.They also obtained some incorporation of amino-acids with polycytidylic-adenylic acid. The general conclusion now appears to be that the code isdegenerate.Similar incorporations of amino-acids stimulated by added polynucleo-tides have been obtained in other systems.121 In other tests of the univer-sality of the genetic code, it has been found that tobacco-mosaic virus-RNAdirects the synthesis of a protein similar to this virus-protein in an E. colisystem,122 and that addition of ribosomal RNA from E . coli cells inducedto form /?-galactosidase led to the synthesis of this enzyme when added toa homologous (E. coli) cell-free system; when this RNA was added to aheterologous system (Pseudomonus pyocyuneus) protein synthesis occurredbut enzyme was not produced.12311' P. Lengyel, J. F. Speyer, and S. Ochoa, Proc. Nut. Acad. Sci. U.S.A., 1961,47, 1936; J. F. Speyer, P. Lengyel, C. Basilio, and S. Ochoa, ibid., 1962, 48, 63, 282,441; C. Basilio, A. J. Wahba, P. Lengyel, J. F. Speyer, and S. Ochoa, ibid., p. 613;J. H. Matthaei, 0. W. Jones, R. G. Martin, and M. W. Nirenberg, ibid., p. 666.118 E. Chargaff, Nature, 1962, 194, 86.119 M. E. Reichmann, M. W. Rees, R. H. Symons, and R. Markham, Nature, 1962,195, 999.lZo M. S. Bretscher and M. Grunberg-Manago, Nature, 1962, 195, 283.lZ1 E. S. Maxwell, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1639; H. R. V. Arnstein,R. A. Cox, and J. A. Hunt, Nature, 1962, 194, 1042.lZ2 A. Tsugita, H. Fraenkel-Conrat, M. W. Nirenberg, and J. H. MatLhaei, Proc.Vat. Acad. Xci. U.S.A., 1962, 48, 846.123 B. R. Chatterjee and R. P. Williams, Biochem. Biophys. Res. Comm., 1962 $9, 72382 ORGANIC CHEMISTRYOf the theoretical and speculative papers on the nature of the geneticcode, that by Woese is worthy of note.124 He suggests a degenerate tripletcode, in which one member of the triplet codes according to its 2 positiononly, a second codes according to its 6 position only, while the third codesaccording to positions 2 and 6. This gives a code of 24 sets of triplets andis in good agreement with experimental results;l17 perhaps even more inter-esting is that it accounts for the wide variation in guanine-cytosine contentwhich is found in bacterial DNA. Many authors have " tested " the code byapplying it to amino-acid replacement data, but Hendler,125 with goodreason, has questioned the conclusions reached. Statistical analysis of theprobabilities involved (e.g., that code designations of two amino-acids willbe related by only a single nucleotide difference) shows that a considerablylarger number of correlations is required. The findings that DNA-primedRNA synthesis in mouse fibroblasts can be inhibited by actinornycin Dwithout significant interference with the production of an infectious RNAvirus,126 and that RNA-primed RNA nucleotidyl-transferase activity isincreased in Krebs I1 ascites tumour cells on infection with EMC virus,127suggest that replication of some RNA viruses may be dependent on RNA-and not on DNA-primed synthesis of RNA.Work on the fractionation and purification of s-RNA, which transfersthe amino-acids to the ribosomes, has involved a variety of methods, in-cluding counter-current distribution.12* It has been found that E. coEicontains two leucine-acceptor s-RNA's, which are separable by this tech-nique. Ribosomal incorporation of leucine attached to one of these isstimulated by polyuridylic-cytidylic acid, the other by polyuridylic-guanylicacid,129 explaining the degeneracy observed in coding experiments withleucine 117 and incidentally confirming the view that coding specificity iscarried by s-RNA. This had already been shown by an ingenious experi-ment in which cysteine attached to its s-RNA was treated with Raney nickelto give alanine-s-RNA(cysteine). This was found to be active in an in-corporating system in which cysteine-s-RNA( cysteine) is active but alanine-s-RNA- (alanine) is inactive. l 3 0 The nucleotide sequence in s-RNA, nextto the common terminal sequence cytidylic-cytidylic-adenylic, varies and isdifferent in isoleucine- and leucine-specific s-RNA.131Studies of the actual transfer process indicate 132 that in the course of1 2 4 C. R. Woese, Nature, 1962, 194, 1114.1 2 5 R. W. Hendler, Proc. Nut. Acad. Sci. U.X.A., 1962, 48, 1402.. E. Reich, R. M. Franklin, A. J. Shatkin, and E. L. Tatum, Proc. Nut. Acad.Sci. U.S.A., 1962, 48, 1.238.1 2 7 R. Eason, M. J. Cline, and R. M. S. Smellie, Biochim. Biophys. Acta, in thepress.128 J. Agar, R. W, Holley, and S. H. Memill,, J. Biol. Chem., 1962, B7, 796; 3%. L.Stephenson and P. C. Zamecnik, Biochern. Biophys. Res. Comm., 1962, 7, 91; M. Tsda,M. Schweiger, and H. G. Zachau, 2. physiol. Chem., 1962, 328, 85; G. Zubay, J. Mol.Biol., 1962, 4, 347.1 2 9 B. Weisblum, 5. Benzer, and R. W. Holley, Proc. Nut. Acad. Sci. U.S.A., 1962,48, 1449.130 F. Chapeville, F. Lipmann, G. Van Ehrenstein, B. Weisblum, W. J. Ray, jun.,and S. Benzer, Proc. Nut. Acad. Sci. U.X.A., 1962, 48, 1086.131 U. Lagerkvist and P. Berg, J. Mol. Biol., 1962, 5,-139; P. Berg, U. Lagerkvist,and M. Dieckmann, ibid., p. 159.132 M. Takanami, Biochim. Biophys. Acta, 1962, 55, 132ULBRICHT: NTJCLEIC ACIDS 383amino-acid transfer to ribosome, the s-RNA itself is also transferred, a processrequiring guanosine triphosphate and occurring whether an amino-acid isattached at the acceptor end or not, provided the terminal sequence cytidylic-cytidylic-adenoylic-apparently necessary for the binding of s-RNA toribosome-is intact. This has been confkmed ; stimulation by adenosinetriphosphate is due to restoration of the terminal sequence. 133 It appearsthat one molecule of guanosine triphosphate is degraded for each moleculeof amino-acid transferred from s-RNA to protein. 134Finally, attention is drawn to Lord Todd’s addresses to the ChemicalSociety, in which some problems in the field of Nucleic Acid Chemistry areconsidered in a wider context. 135T. L. V. U.R. &I. ACHESON.G. C. BARKER.K. W. BENTLEY.C. J. W. BROOKES.B. CAPON.L. CROMBIE.G. EGLINGTON.J. ELKS.V. GOLD.G. W. GRAY.J. HONEYMAN.D. J. IMILLEN.K. H. OVERTON.C. W. REES.D. H. REID.T. L. V. ULBRICHT.R. F. M. WHITE.w. KJLYNE.133 H. Bloemendal, F. Huizinga, M. de Vries, and L. Bosch, Biochim. Biophys.13* G. Webster and S. L. Whitman, Biochim. Biophys. Acta, 1962, 61, 316.135 (Sir) A. Todd, Proc. Chen?,. SOC., 1961, 187; Lord Todd, Proc. Chent. SOC., 1962,Acta, 1962, 61, 209; L. Bosch, F. Huizinga, and H. Bloemendal, ibid., p. 220.190

ISSN:0365-6217    

DOI:10.1039/AR9625900187

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

BIOLOGICAL CHEMISTRY1. INTRODUCTIONIT has now been established that d-aminolaevulic acid contributes all thecarbon and nitrogen atoms of the haem of haemoglobin, myoglobin, cyto-chromes, peroxidase, and catalase as well as those of the dihydroporphyrinof chlorophyll and of the tetrahydroporphyrin of bacteriochlorophyll.Recent work also shows that d-aminolaevulic acid is incorporated intact intothe corrin ring of vitamin BIZ, but a number of additional carbon atoms, inthe form of methyl groups, are provided by methionine. The paramountposition of 6-aminolaevulic acid was already recognised when the last Reportwas presented,l and in the intervening years much has been learned of theenzymes involved in its formation and in its conversion into porphyrins.These studies have also brought to light certain inhibitory processes, whichcould exert control over porphyrin biosynthesis.Of particular interest isthe finding that protohaemin I X is a powerful inhibitor of 6-aminolaevulicacid synthetase, thus indicating the possibility of control by the negativefeed-back effect of the final product on the first enzymic step.Studies of vitamin B,, have been concerned less with its biosynthesisthan with its metabolic r61e and this remains somewhat enigmatic. Itseems unlikely that the vitamin or its coenzyme derivatives play a veryimportant part in one-carbon metabolism-a possibility which has beenextensively investigated. In spite of many observations which point to afunction in the biosynthesis of deoxyribonucleosides , clear-cut evidence ofthe importance of such a r61e is lacking and thymidine is ineffective in thetreatment of pernicious anzmia.An important break-through may havebeen made by the finding that vitamin B,, coenzymes function in isomerasesystems involving the migration of carboxyl groups, in particular thatcausing conversion of methylmalonate into succinate. In man, in vita-min B,, deficiency, the level of methylmalonate in the urine is always higherthan normal and is reduced when the vitamin is administered. This raisesthe question whether the neurological symptoms of pernicious anaemiacould be due to an accumulation of methylmalonate.Investigations of the biological and chemical properties of nicotinamide-adenine dinucleotide analogues have shed light on the structural require-ments for coenzymic activity.They have revealed the expediency of thecarbamoyl group attached to the pyridine ring and that of the ribose portionas against one of deoxyribose. I n certain of the dehydrogenase enzymesconsiderable variation in the structure of the purine portion seems to bepermissible. The apoenzymes have aroused considerable interest as a resultof the recognition of the existence of isozyrnes-enzymes of the same activityand from a single species which differ from one another in the structures oftheir sub-units. This is reminiscent of the behaviour of the haemoglobinsand it may transpire that the structures of the sub-units are under geneticAnn. Reports, 1954. 51, 311MARKS: THE BIOSYNTHESIS O F PORPHYRINS 385control.The year has been marked by an outstanding contribution tothe stereochemistry of nicotinamide-adenine dinucleotide in its function asa coenzyme. The absolute alignment, relative to the pyridine ring, of thehydrogen atom transferred between coenzyme and substrate has beenestablished for each of two classes of enzymes in which it was known thathydrogen transfer occurred on one side only of the pyridine ring.Cholesterol, itself formed from acetate, is now known to be the source ofmany steroid compounds and for the adrenal cortex, at least, it has beenestablished that pathways not involving it are of minor importance. Thecomplexity of the situation is shown, however, by the number of differentroutes which can lead to any one substance, such as cortisol and the variousestrogens; the relative importance of these pathways is not, in general,known.Much has been learned of the processes involved in the aromatisa-tion of ring A. Steroid conjugates, rather than being mere excretoryproducts, may, in some instances, be of considerable importance-a sugges-tion which has been made on account of the high metabolic activity of someof them.D. F. E.2. THE BIOSYNTHESIS OF PORPHYRINSWHEN this subject was last reviewed in these Reports eight years agoY1the key r61e played by 6-aminolzvulic acid and porphobilinogen in thebiosynthesis of porphyrins was reported. At that time, it was consideredlikely that uroporphyrin and coproporphyrin were intermediates in the bio-synthesis of hzm and chlorophyll although there was no experimental sup-port for this idea.The recent recognition that uroporphyrinogen andcoproporphyrinogen, the colourless reduced forms of uroporphyrin andcoproporphyrin, respectively, containing six extra hydrogen atoms, are thetrue intermediates has been an important advance. Succinyl-CoA has beenconfirmed as an intermediate in porphyrin biosynthesis and an enzyme,6-aminolaevulic acid synthetase, has been isolated from various sources whichcan form 6-aminolzvulic acid from succinyl-Cod and glycine ; pyridoxalphosphate is the only co-factor required. The first two steps in the conver-sion of protoporphyrin into bacteriochlorophyll have been shown to beprotoporphyrin --+ magnesium protoporphyrin -+ magnesium protopor-phyrin monomethyl ester.There has been considerable progress in theisolation and purification of the enzymes responsible for porphyrin bio-synthesis and studies on the mechanism of control of porphyrin biosynthesishave appeared.Several interesting reviews on porphyrin biosynthesis have been pub-lished in recent years, vix., on the metabolism of ham and chlorophyll,2the biosynthesis of protochlorophyll,3 the biosynthesis of porphyrins andC. Rimington, Ann. Reports, 1954, 51, 311.S. Granick and D. Mauzerall, in “ Metabolic Pathways,” ed. D. M. Green-L. Bogorad, in “ Comparative Biochemistry of Photoreactive Systems,” ed.berg, Academic Press Inc., New York, 1961, Vol. 11, p. 525.M. B. Allen, Academic Press Inc., New York, 1960, p.237.386 BIOLOGICAL CHEMISTRYchlorophyll^,^ haem pigments and porphyrin~,~ and porphyrins and hzemo-proteins. 6Formation of 6-Aminolaevulic Acid.-In 1953 it was shown ' 9 8 that6-aminolmulic acid could replace succinate and glycine for porphyrin bio:synthesis. This finding led to the proposal that d-aminolaevulic acid wasformed from glycine and an asymmetrical succinyl derivative, probablysuccinyl-CoA, by condensation of these two substances to form a-amino-p-oxoadipic acid, which is subsequently decarboxylated to d-arninolaevulicacid. That pyridoxal phosphate and coenzyme A were required for thiscondensation was indicated by the studies of Lascelles 9 on porphyrinsynthesis in Tetrahymena vorax and by the studies of Schulman and Richert l oon vitamin B, and pantothenic acid-deficient ducklings.Recently the enzyme which catalyses this reaction, 6-aminolaevulic acidsynthetase, has been found in a variety of cells. Gibson et aZ.ll found thata preparation of freeze-dried particles obtained from erythrocytes of anemicchickens synthesised 6-aminolaevulic acid from succinyl-CoA and glycine ;pyridoxal phosphate was the only co-factor required. This reaction has alsobeen demonstrated with particle-free extracts of Rhodopseudmonas spher-oides and Rhodospirillium rubrurn, and the enzyme catalysing the reactionhas been purified 60--80-fold from extracts of the former organism.l2 Thework of Lascelles 13 indicated that biotin might be involved in the productionof 8-aminolevulic acid and recently it has been shown that the activity of6-aminolaevulic acid synthetase is reduced in biotin-deficient organisms 14, l5whereas a number of other enzymes are not affe~ted.1~ This is not, however,a specific effect of biotin, since other growth conditions which are unfavour-able to bacteriochlorophyll synthesis also cause a fall in the activity of6-a,minolaevulic acid synthetase.14On the basis of their experimental evidence Kikuchi et aZ.I2 have sug-gested that a stabilised carbanion (1) is formed from glycine and pyridoxalphosphate by loss of a proton and that this reacts with the electrophiliccarbonyl-carbon atom of succinyl-CoA (2).The latter reaction may thenproceed in one of two ways: decarboxylation occurs by a concerted attack(pathway b) or the product of condensation is a-amino-p-oxoadipic acid (3)which loses carbon dioxide (pathway a) to yield 8-aminolaevulic acid (4).Because decarboxylation of a-amino-8-oxoadipic acid is virtually instantane-ous at room temperature 16 its isolation from a biological system is pre-4 K.D. Gibson, M. Matthew, A. Neuberger, and G. H. Tait, Nature, 1961, 192,204.C. Rimington, Ann. Rev. Biochem., 1957, 30, 561.E. Margoliash, Ann. Rev. Biochem., 1961, 30, 549.D. Shemin and C. S. Russell, J . Amer. Chem. Soc., 1953, 7'5, 4873.* A . Neuberger and J. J. Scott, Nature, 1953, 172, 1093.9 J. Lascelles, Biochem. J., 1957, 66, 65.lo M. P. Schulman and D. A. Richert, J. BioZ. Chem., 1957, 226, 181.11 K. D. Gibson, W.G. Laver, and A. Neuberger, Biochem. J., 1958, 70, 71.l 2 G. Kikuchi, A. Kumar, P. Talmage, and D. She&, J . Biol. Chem.., 1958, 233,13 J. Lascelles, Biochem. J., 1956, 62, 78.14 K. D. Gibson, A. Neuberger, and G. H. Tait, Biochem. J., 1962, 83, 539.16 J. Lascelles, J. Qen. MicrobioZ., 1960, 23, 499.l6 W. G. Laver, A. Neuberger, m d J. J. Scott, J., 1959, 1474, 1483.1214MARKS: THE BIOSYNTHESIS O F PORPHYRINS 387cluded and there is no information as to whether it is a free intermediate.A similar overall scheme has been put forward by Neuberger.17The enzyme preparations obtained by Gibson et aE.ll and by Kikuchiet ~ 1 . 1 2 are not specific for succinyl-CoA. Propionyl-CoA, glutaryl-CoA, andacetyl-CoA also serve as substrates but the reactions are slower.Amino-acetone has been identified as the product with the latter substrate, andproducts reacting as amino-ketones have been obtained with the other twosubstrates. From recent experiments by Granick and Urata l8 it seemslikely that these reactions, utilising different acyl-CoA substrates, are notcatalysed by a single enzyme but that several specific synthetases are presentin these preparations. These authors have shown that normal animal livermitochondria form aminoacetone readily from glycine and pyruvate butonly traces of 6-aminolzevulic acid from glycine and a-keto-glutarate. Afterinduction of a chemical porphyria with diethyl 1,4-dihydrocollidine-3,5-dicarboxylate the isolated liver mitochondria had the capacity to form largeamounts of d-aminolaevulic acid from glycine and citrate.Furthermore,frozen and thawed preparations of these mitochondria have acquired theability to synthesise 6-aminolzevulic acid from succinyl-CoA and glycine.The synthetase for 6-aminolaevulic acid differs from that for aminoacetonein distribution, in greater sensitivity to penicillamine, and in looser bindingof pyridoxal phosphate. No other major change in protoporphyrin bio-synthesis is observed in the liver of these porphyric animals.The synthesis of 6-aminolzevulic acid is markedly inhibited by amino-malonate and kinetic investigation has shown this inhibition to be of thecompetitive type with respect to glycine. Several specific inhibitors ofd-aminolaevulic acid synthetase occur naturally.As yet unidentified com-ponents of egg-white and of Rps. spheroides l2 have a specific inhibitoryeffect on this enzyme and Kikuchi et a2.l2 have suggested that the inhibitorfrom Rps. spheroides may play an important r61e in the control of porphyrinbiosynthesis. They point out that the energy requirement for d-amino-lzevulic acid formation would make this step a likely place for the cellularcontrol of porphyrin synthesis.Protohzemin IX has been shown 4 9 l9 to be a relatively potent inhibitorof d-aminolamlic acid synthetase, causing about 50% inhibition at a con-centration of 1 0 - 5 ~ . This inhibition, which is reversible,l9 is quite specificfor protohaemin IX, since other metal-porphyrin complexes and the corre-sponding free porphyrins have little inhibitory action.This is an exampleS . Granick and G. Urata, Fed. Proc., 1968, 21, 150.l7 A. Neuberger, Biochem. J., 1961, 78, 1.ID B. F. Burnham, Biochem. J., 1962, 84, 15P388 BIOLOGICAL CHEMISTRYof inhibition through a negative feed-back mechanism in which the finalproduct in a metabolic sequence inhibits the first enzymic step leading ex-clusively to the end product. It is thought that this mechanism may operatein the control of porphyrin biosynthesis. I n earlier investigations Las-celles 13, 2o showed that Bps. spheroides, when cultured in the light underiron-deficient conditions, accumulated large quantities of porphyrin in themedium. The addition of iron resulted in a decreased production of por-phyrin, an effect which seemed to be due to the catalytic action of iron andnot to the formation of stoicheiometric amounts of haemin.From the aboveinhibition experiments it appears that iron added to deficient culturesexerted its catalytic influence on porphyrin formation after incorporationinto protohaemin IX, which directly inhibits the activity of Q-aminolaevulicacid synthetase.Succinate-Glycine Cycle.-In an attempt to unify the reactions of glycineShemin 21 postulated a series of reactions, called the succinate-glycine cycle.According to this postulate, 6-aminolaevulic acid, in addition to its utilisationfor porphyrin synthesis, can be further metabolised in such a manner thatits &carbon atom (originally the a-carbon atom of glycine) is utilised forthe synthesis of the ureido-group of purines, the #&carbon atom of serine,and methyl groups ; the remaining 4-carbon residue is reconverted intosuccinate.Although certain experimental results support the existence ofthis cycle,21, 22 its general metabolic significance remains to be evaluated.Enzyme studies have been restricted to the first reaction in this cycle, wix.,the conversion of 6-aminolaevulic into y 6-dioxovaleric acid. An enzymecatalysing this reaction has been demonstrated in mammalian tissues, 23Bacterium diphtheriae ,z4 and Rhodopseudomonas spheroides. l4 It has beensuggested that this reaction might provide a control mechanism for thesynthesis of hzm and chlorophyll. I n recent work with Rhodopseudomonusspheroides it has been found more convenient to study the reverse reaction,vix., the conversion of yd-dioxovaleric acid into 6-aminolaevulic acid, becausethe equilibrium appears to be in favour of the production of 6-aminolaevulicacid and a sensitive method is available for estimating the amino-ketone.The enzyme catalysing this reaction has been purified thirty-fold 25 andL-alanine found to be the specific amino-group donor.Formation of Porphobilin0gen.-The enzyme catalysing the condensationof two molecules of 6-aminolaevulic acid to porphobilinogen ( 5 ) has beenfound to be widely distributed in animal tissues, plants, and bacteria, andhas been considerably purified. Bogorad has summarised the propertiesof several purified 6-aminolaevulic acid dehydrase preparations.Since thisis a rare case of an enzyme catalysing a reaction between two identical sub-strate molecules, Granick and Mauzerall 26 have made a detailed kinetic2o J. Lascelles, J . Gen. Microbiol., 1960, 23, 487.2 l D. Shemin, in Ciba Foundation Symposium on Porphyrin Biosynthesis andMetabolism, ed. G. W. Wolstenholme, J. and A. Churchill, London, 1955, Vol. IV.22A. M. Nerneth, C. S. Russell, and D. Shemin, J . Biol. Chern., 1957, 229, 415.23 E. Kowalski, A. M. Dancewicz, and Z. Szot, Bull. Acad. Polon. Sci., 1957, 11,24 M. Bagdasarian, Natzwe, 1958, 181, 1399.z 5 A. Neuberger and J. M. Turner, personal communication.26 S. Granick and D. Mauzerall, J . Biol. Chem., 1958, 232, 1119.5, 223MARKS: THE BIOSYNTHESIS OF PORPHYRINS 389investigation of the reaction.On the basis of their data they suggest thatboth molecules of 6-aminolzevulic acid form complexes with Q-aminolzevulicacid dehydrase, one molecule being held more tightly than the other.Formation of Uroyorphyrinogen III.-The next step in porphyrin bio-synthesis is the enzymic conversion of porphobilinogen (5) into uroporphyr-inogen I11 (6). It is clear from the work of Tarlton et aL2' that great careA@cH*p N H HN( 6 )is needed in establishing the purity of uroporphyrin isomers. UroporphyrinI11 methyl ester cannot be distinguished from a mixture of isomers contain-ing it by m.p.s, infrared spectra, or X-ray powder photographs so that it isprobable that various workers have handled mixtures of uroporphyrinisomers which they have assumed to be uroporphyrin I11 (7).It has been known for some time that porphobilinogen 28-30 may beconverted into a porphyrin by heating it in acid solution and, in view of thedifficulty in establishing the purity of uroporphyrin isomers, reports haveappeared in the literature that this porphyrin is uroporphyrin III.31 Forthis reason it has been assumed that the enzyme merely accomplished whatacid did and that the mechanisms of the enzymic and the acidic conversionsof porphobilinogen into uroporphyrin are closely related.That this assump-tion is not necessarily correct is clear from the following considerations.(i) Whereas isoporphobilinogen (8) is converted into a mixture of uropor-phyrinogen isomers by heating it in acid, the enzyme preparation is withoutaction upon it.32 (ii) WH20 is incorporated into the porphyrinogen2 i E.J. Tarlton, S. F. MacDonald, and E. Baltazzi, J. Arner. Chem. SOC., 1960,2 8 J. Waldenstrom and B. Vahlquist, 2. physiol. Chem., 1939, 260, 189.29 R. G. Westall, Nature, 1952, 170, 614.30 G. H. Cookson and C. Rimington, Biochem. J., 1954, 57, 476.31 E. Bullock, A. W. Johnson, E. Markham, and K. B. Shaw, J., 1958, 1430.32 A. T. Carpenter and J. J. Scott, Biochim. Biophys. Acta, 1961, 52, 195.82, 4389390 BIOLOGICAL CHEMISTRYformed from porphobilinogen by heating it in acid solution in the presenceof labelled f~rmaldehyde,~~~ 34 but not into the porphyrinogen formedenzymically from porphobilinogen in the presence of labelled formalde-h ~ d e .* ~ ~ (iii) Condensation of porphobilinogen in acid solution is arandom process as regards the isomers formed, since the product porphyrino-gen isomerises rapidly in hot acid solution.36 This isomerisation has beenused to demonstrate the thermodynamic stability of the cyclised macrocycleover the linear polypyrrylmethanes. The ratio of isomers formed is therandom mixture: 1/8 I, 1/8 11, 1/2 111, l/4 IV. The enzyme, on the otherhand, produces uroporphyrinogen I11 - Isomer I PA-PA-PA-PAI1 PA-AP-P A - ~ kI11 +A-PA-PA-~bIV +A-PA-AP-A~When porphobilinogen is heated in acid solution 33 in the presence offormaldehyde the relative amounts of uroporphyrinogen isomers remain thesame as in the absence of formaldehyde and considerable incorporation offormaldehyde takes place.Furthermore, when any uroporphyrinogenisomer is heated 36 in acid solution in the presence of formaldehyde the samerandom ratio of isomers is obtained and considerable incorporation offormaldehyde takes place. Consequently neither the isomer ratios nor theformaldehyde incorporation can be used to explain the mechanism of con-densation of porphobilinogen in acid solution as has been attempted pre-I n neutral and alkaline solution, however, uroporphyrinogen neitherisomerises nor incorporates formaldehyde, and the results of condensingporphobilinogen under these conditions can be interpreted more readily.When porphobilinogen is heated under neutral conditions the isomer ratiofound is: 1/2 I, 1/2 (I11 + IV) and under alkaline conditions 3/4 I, l/4(I11 + IV).In the presence of formaldehyde incorporation of formaldehydeinto the uroporphyrinogen occurred and an approximately random mixtureof isomers was obtained. These observations in neutral and alkaline solu-tion have been explained by Mauzerall using a general mechanism firstsuggested by Cookson and Rimingt0n.3~Considerable experimental evidence has accumulated regarding the detailsof the enzymic conversion of porphobilinogen to uroporphyrinogen 111.Bogorad and Granick showed that a preparation from ChZoreZZa formeduroporphyrinogen I11 from porphobilinogen but, after it had been heated to60°, only uroporphyrinogen I was formed. This observation indicated thatviously.ss D. Mauzerall, J . Amer. Chem.SOC., 1960, 82, 2605.34 W. H. Lockwood and A. Benson, Biochem. J., 1960, 75, 372.35 L. Bogorad and G. S. Marks, J . Biol. Chem., 1960, 235, 2127.36 D. Mauzerall, J . Amer. Chem. Soc., 1960, 82, 2601.37L. Bogorad, J . Bwl. Chem., 1968, 233, 610.38 L. Bogorad and S. Granick, Proc. Nut. Acad. Sci. U.X.A., 1953, 89, 1176MABKS: THE BIOSYNTHESIS O F PORPHYRINS 391a t least two enzymes participate in the synthesis of uroporphyrinogen 111from porphobilinogen and that the two enzymes differ in their susceptibilityto heat. Thus fromaqueous extracts of acetone powders of spinach leaf tissue an enzyme,uroporphyrinogen I-synthetase, was isolated 39 and purified, which convertedporphobilinogen into uroporphyrinogen I. The yields approach 100 yo whenthe reaction proceeds anaerobically. The second enzyme, uroporphyrinogenIII-cosynthetase, was isolated from aqueous extracts of wheat germ 40 andshown to have no capacity for catalysing porphobilinogen consumptionwhen incubated alone with this substrate. However, when incubatedtogether with uroporphyrinogen I-synthetase and porphobilinogen it broughtabout the production of uroporphyrinogen I11 instead of the I isomer.Uroporphyrinogen I is not a substrate for the cosynthetase.26, 409 4 1 Similarresults have been obtained with extracts from Rhodopseudomoms spheroid@.42The key to the clarification of the mechanism of uroporphyrinogen I11formation is the identification of the substrate or substrates of uroporphyr-inogen III-cosynthetase. It appears likely either (i) that the substrate is aproduct (9, 10, or 11) of the linear condensation of porphobilinogen byuroporphyrinogen I-synthetase; or (ii) that the substrates are one of theseThis has been confirmed by subsequent experiment.( 9 ) \ .- 1A A P( J 1 )H2N.CHl c l C H 2 <l CH2 N CH2 kj NH H H Hsubstances and porphobilinogen. Recently Bogorad 43 has been able toaccumulate an intermediate in the conversion of porphobilinogen intouroporphyrinogen I whose properties are consistent with those of a dipyrryl-methane. It is possible that this intermediate may be a substrate for thecosynthetase. Synthesis of the possible substrates (9-1 1) would be helpfulin clarifying the mechanism of this reaction, and an approach in this direc-tion has been made.44 The more readily synthesised dippylmethanes(12-14) have been prepared,44, 45 but none of these compounds is concepnedin the biosynthesis of uroporphyrinogen I or III.39 32, 46Mathewson and Corwin 47 recently suggested that the substrate of thecosynthetase is a linear tetramer (15) formed by the action of uroporphyrino-gen I-synthetase on porphobilinogen.This tetramer differs from the tetra-39 L. Bogorad, J. Biol. Chem., 1958, 233, 501.40 L. Bogorad, J. Biol. Chem., 1958, 233, 510.41L. Bogorad and G. S. Marks, Biochim. Biophys. Acta, 1960, 41, 356.&2H. Heath and D. S. Hoare, Biochem. J., 1959, 72, 13.45 L. Bogorad, Fed. Proc., 1962, 21, 400.44 G. P. Arsenault and S. F. MacDonald, Canad. J. Chem., 1961, 39, 2043.4 5 G.P. Arsenault, E. Bullock, and S . F. MacDonald, J. Arner. Chem. Soc., 1960,46H. Heath and D. S. Hoare, Biochim. Biophys. Acta, 1960, 39, 167.4' J. H. Mathewson and A. H. Corwin, J . Amer. Chem. SOC., 1961, 83, 135.82, 4384392 BIOLOGICAL CHEMISTRYpyrrylmethane (1 1) by retention of a-hydrogen atoms after successive self-condensations of porphobilinogen, allowing sufficient flexibility for cyclisa-tion to uroporphyrinogen 111. It is thought that the cosynthetase catalysesan attack by the CH,*NH,+ group, on the " occupied " position of pyrrole a,followed by rearrangement of this cyclic structure to uroporphyrinogen 111.In the absence of the cosynthetase the linear tetramer (15) is assumed tocyclise to uroporphyrinogen I. This hypothesis accounts for all the observa-tions with enzyme systems, and experiments designed to test it are awaitedwith interest.According to an earlier hypothesi~,~~, 49 the cosynthetase is assumed tocatalyse the condensation of opsopyrroledicarboxylic acid (16) with thetetrapyrrylmethane (1 1) which is presumably produced by the action ofuroporphyrinogen I-synthetase on porphobilinogen.The resulting pentamer(17) is thought to be ruptured at the bond indicated by the dotted line, withUroporphyrinogen I11 + Opsopyrroled i c a r b o x y I i c acidregeneration of opsopyrroledicarboxylic acid and cyclisation of the tetramert o an isomer of series 111. The opsopyrroledicarboxylic acid, which wouldneed to be present in catalytic quantities only, would act as a coenzyme ofuroporphyrinogen III-cosynthetase.In experiments designed to test thishypothesis opsopyrroledicarboxylic acid (synthesised by MacDonald et al. 5O)was found not to be incorporated 3 during the enzymic synthesis of uropor-phyrinogen I11 from porphobilinogen, nor was 14C-labelled opsopyrroledi-carboxylic acid incorporated 48 during the enzymic formation of haem from4sA. T. Carpenter and J. J. Scott, Biochem. J . , 1959, 71, 325.4 9 A. H. Jackson and S. F. MacDonald, Cunad. J . Chem., 1957, 35, 715.5'3D. M. MacDonald and S. F. MttcDonald, Cunad. J. Chem., 1955, 33, 573MARKS: THE BIOSYNTHESIS O F PORPHYRINS 393glycine and succinic acid in lysates of fowl red cells. Further experimentshave shown 32 that isoporphobilinogen (synthesised recently by Arsenaultet aZ.44), considered as a possible coenzyme of uroporphyrinogen I11 cosynthe-tase, is also not concerned with the enzymic formation of uroporphyrinogenI or 111.The availability of purified enzyme preparations has permitted a quanti-tative investigation of the possible participation of formaldehyde in theenzymic synthesis of uroporphyrinogen I and I11 from porphobilinogen.Itwas found that formaldehyde was neither a product 34 nor a reactant 3 4 9 35in the enzymic synthesis, thus excluding several hypotheses on the mechanismof enzymic formation of uroporphyrinogen I11 from porph~bilinogen.~~, 519 52Several other mechanisms for the biosynthesis of uroporphyrinogen I11from porphobilinogen have been suggested 3, 31, 35, and these are sum-marised by Bogorad.Prodigiosin, the red pigment of Serratia mrcescens, was wrongly as-signed 54 the tripyrrylmethene structure (18) in 1934 and on this basis atripyrrylmethene was suggested as an intermediate in porphyrin bio-synthesis.55 Prodigiosin has recently been synthesised 56 and its structureshown to be that of a pyrryldipyrrylmethene (19).8-Aminolaevulic acid isnot a precursor of this compound.57Formation of Coproporphyrinogen IU.-The finding that uroporphyrino-gen I11 rather than uroporphyrin I11 is the true precursor 26, 58, 59 of copro-porphyrinogen I11 [ hexahydro-derivative of (26)l has resolved the somewhatcontradictory evidence concerning the intermediates in hzm synthesis fromporphobilinogen. Recently, an enzyme, uroporphyrinogen decarboxylase,which catalyses the conversion of uroporphyrinogen I11 into copropor-phyrinogen I11 has been isolated 26 from rabbit reticulocytes by zone electro-phoresis on starch.All the hexahydro-derivatives (porphyrinogens) of theuroporphyrin isomers (I-IV) recently synthesised by MacDonald and hisco-workers 2 7 9 60, 61 are decarboxylated by this enzyme and the yield ofcoproporphyrinogen from the various isomers is I11 > IV > I1 > I.62 The51D. Shemin, C. S. Russell, and T. Abramsky, J . Biol. Chem., 1955, 215, 613.5 2 A. Treibs and W. Ott, Annalen, 1958, 615, 137.53 J. Wittenberg, Nature, 1959, 184, 876.54 F. Wrede and A. Rothhaas, 2. physiol. Chem., 1934, 226, 95.55 W. J. Turner, J. Lab. Clin. Med., 1940, 26, 323.5 6 H.Rapoport and K. G. Holden, J. Amer. Chem. SOC., 1960, 82, 5510.57 G. S. Marks and L. Bogorad, Proc. Nat. Acad. Sci. U.S.A., 1960, 46, 25.5 8 R. A. Neve, R. F. Labbe, and R. A. Aldrich, J. Arner. Chem. SOC., 1956,78,691.59 L. Bogorad, J . Biol. Chem., 1958, 233, 516.6 o S. F. MacDonald and R. J. Stedman, Canad. J . Chem., 1954, 32, 896.61 S. F. MacDonald and J. Michl, Canad. J . Chern., 1956, 34, 1768.6 a D. Mauzerall and S. Grrrtnick, J . Biol. Ch.em., 1958, 232, 1141394 BIOLOGICAL CHEMISTRYenzyme contains essential thiol groups, has a pH optimum of 6.8 and K ,of < 5 x An enzyme preparation with similar properties has re-cently been isolated from Rps. spheroid@ by Hoare and Heath,63 who haveevidence for the requirement of a heat-stable co-factor in this conversion.When 6-aminolzevulic acid or porphobilinogen was incubated with wholeblood or supernatant liquid from normal rabbits and humans, an intermediateheptacarboxylic acid designated phyriaporphyrin I11 was isolated.64Evidence has'been presented 65 that this heptacarboxylic acid is a' normalintermediate, following uroporphyrinogen I11 in the metabolic pathway ofprotoporphyrin IX biosynthesis. This heptacarboxylic acid is identicalwith pseudouroporphyrin 136 and with " porphyrin 208 " which is presentin significant quantities in the urine of patients with porphyria hepatica.Recent preparations of natural coproporphyrin I11 67 have higher melt-ing points than Fischer's synthetic specimens. This brought the purity ofboth into question, and to resolve these differences the syntheses of copro-porphyrin I11 and IV have been repeated.68 By this means it has beenshown that the natural and synthetic material are identical and datarelevant to the identification of coproporphyrin have been corrected andextended.Biosynthesis of Protoporphyrin IX and Haem.-The enzyme copropor-phyrinogen oxidase removes two hydrogen atoms and a carboxyl groupfrom each of the two propionic acid side chains in rings A and B of copro-porphyrinogen, and at the same time six hydrogen atoms are removed fromthe ring system to giveP H Pprotoporphyrin IX (25).The enzyme was first(20 ; R = R' = CHMe*OH\(21; R = R ' = COMe) Me(22; R = R ' = CH:CH.C02H) PN H N <( 2 3 ; R = R ' = HI HC( 2 4 ; (25; R = R ' = CHZCH2) E t )R"& d C : e( 2 6 ; R = R ' = CH2-CH2.C02H) p p(27)demonstrated in a frozen-thawed Euglena preparation 69 and in hEmolysedchicken erythrocyte^.^^ Subsequently this enzyme has been found 71 in avariety of tissues and in particularly high concentration in liver, bonemarrow, and small intestine.The enzyme present in beef-liver mitochondriawas purified twenty-fold by solubilising it with thioglycollate at pH 9 andisolating it in the 40-70% -saturated ammonium sulphate fraction. Oxygenc3 D. S. Hoare and H. Heath, Biochem. J., 1959, 73, 679.64 A. M. del C. Battle and M. Grinstein, Biochim. Biophys. Acta, 1962, 57, 191.G6 A. M. del C. Battle and M. Grinstein, Biochim. Biophys. Acta, 1962, 62, 197.6 6 J.E. Falk, E. I. B. Dresel, A. Benson, and C. Knight, Bioch.em. J., 1956, 63, 87.6 7 C. H. Gray and L. B. Holt, Biochem. J., 1948, 43, 191.6a F. Morsingh and S. F. MacDonald, J . Amer. Chem. SOC., 1960, 82, 4377.e9 S. Granick and D. Mauzerall, Fed. Proc., 1958, 17, 233.7 0 S. Granick and D. Mauzerall, Ann. N . Y . A d . Sci., 1958, 75, 115.7l S. Sano and S. Granick, J . Biol. Chem., 1961, 236, 1173MARKS: THE BIOSYNTHESIS OF PORPHYRINS 395was the only oxidant found to be used by this enzyme. In contrast to thedecarboxylation of all four isomers of uroporphyrinogen by uroporphyrinogendecarboxylase this enzyme is specific for coproporphyrinogen 111. Duringthe enzymic reaction, an intermediate porphyrin that has one vinyl andthree propionic acid groups appears and then disappears.The finding in 1953 that haematoporphyrin IX (20) and monohydroxy-ethylmonovinyldeuteroporphyrin IX accumulate in cultures of ChZoreZZamutant W,B-17 729 73 suggested that these two compounds might be inter-mediates in the conversion of coproporphyrinogen I11 into protoporphyrinIX, and that a series of steps similar to that found in fatty acid oxidationmight be necessary in this conversion.3 However, the following two observa-tions show that this idea is incorrect.(i) Frozen and thawed Chlorellapreparations which can catalyse the formation of protoporphyrin IX fromporphobilinogen fail to utilise haematoporphyrin IX, haematoporphyrinogenIX, diacetyldeuteroporphyrin IX (21), or diacetyldeuteroporphyrinogenIX.74 (ii) Hydroxylamine and semicarbazide do not inhibit the reaction,indicating that the oxidation does not involve an intermediate containinga carbonyl gro~p.~g, 7 1 Another possible course for this reaction would bethrough deuteroporphyrin IX 2,4-diacrylic acid (22) or its hexahydro-75 This compound (22), first synthesised by Fischer andBeer,76 has recently been prepared by Sparatore and Mauzerall 75 by a moresatisfactory procedure.However, neither this nor its hexahydro-derivativeserved as substrates for coproporphyrinogen oxidase. 7 1 This suggests thatthe reaction is concerted, oxidation and decarboxylation occurring simul-taneously;2, 71 evidence for this has been obtained from a study of theenzyme reaction in tritiated water.2Sano and Graniclr 71 have pointed out that, whereas coproporphyrinogenoxidase and the enzymes connected with the synthesis of 6-aminolaevulicacid are localised in cellular particulates, the enzymes catalysing the con-version of 6-aminolaevulic acid into coproporphyrinogen are present in thecytoplasm.It appears that this acid, synthesised in mitochondria, leaksinto the cytoplasm, to be converted into coproporphyrinogen, which migratesback into the mitochondria, to be transformed into protoporphyrin. It issuggested 71 that this localisation might permit permeability to play a partin control of porphyrin synthesis by the cell.An enzyme catalysing the chelatiun of iron by protoporphyrin to formprotohaemin IX has been found in several tiss~es.~7-83 With a partially73 L.Bogorad and S. Granick, J. Biol. Chem., 1953, 202, 793.73 S. Granick and L. Bogorad, J. Amer. Chem. SOC., 1953, 75, 3610.7 4 G. S. Marks and L. Bogorad, 1958, unpublished work.7 5 F. Sparatore and D. Mauzerall, J. Org. Chem., 1960, 25, 1073.7 6 H. Fischer and L. Beer, 2. physiol. Chem., 1936, 244, 54.7 7 R. F. Labbe and N. Hubbard, Biochem. Biophys. Acta, 1960, 41, 185.78R. F. Labbe and N. Hubbard, Biochim. Biophys. Acta, 1961, 52, 130.79 H. Oyarnrt, Y. Sugita, Y. Yoneyama, and H. Yoshikaya, Biochim. Biophys.so R. C. Krueger, I. Melnick, and J. R. Klein, Arch. Biochem. Biophys., 1956,s l A . Goldberg, Brit. J. Haematol., 1959, 150, 5.s2 H. C. Schwartz, G. E. Cartwright, E. L. Smith, and M. M. Wintrobe, Blood,Acta, 1961, 4'7, 413.64, 302.1959, 14, 486396 BIOLOGICAL CHEMISTRYpurified preparation from duck erythrocytes 79 the stoicheiometry of thisreaction has been demonstrated.The solubilised enzyme from rat liver isactivated by reducing agents and exhibits numerous properties of an enzymerequiring a thiol group for activity. With the liver enzyme, no evidencefor more than one component has been obtained,77 while the chicken erythro-cyte preparation has been divided into two heat-labile, non-dialysablefractions.83 The enzyme obtained from rat liver 78 and from duck erythro-cytes 79 is relatively unspecific with respect to the porphyrin requirement,and with the latter preparation haems are formed from deuteroporphyrin (23),mesoporphyrin (24), and haematoporphyrin.The enzyme preparationswere, however, more selective with respect to their metal requirement.Labbe and Hubbard 78 attribute this to the fact that the enzyme is presentedin vivo with only one porphyrin, namely, protoporphyrin, while it has toselect the Fe2+ ion from a variety of metal ions in order to form hsm.Cfiochromes and Haem Enmes.-It is now generally accepted that thehaems of catalase, peroxidase, and the various cytochromes are derived inthe same manner as the haem of haemoglobin. Cytohaemin (haem a), theprosthetic group of cytochrome-a, and of cytochrome-a, has been degradedto ~ytodeuteroporphyrin~84 and the latter has been shown85 to be 8-de-methyldeuteroporphyrin IX (27; R = R’ = R” = H). In recent work onhaem a it has been shown S6 that R” = CHO and evidence has been presentedregarding the nature of the substituents a t R and R’.87, 88 An improvedmethod of isolation of haem a has recently been reported which will bevaluable in further structural studies.89 It is clear that the structure ofhaem a differs markedly from that of protohzmin IX, and a study of itsbiosynthesis will be of considerable interest.It has been claimed that astreptomycin-resistant variant of Micrococcus pyogenes can use protohaeminas a source for the production of haem a, but no experiments with labelledprotohaemin have yet been carriedSano and Granick 71 have recently shown that protoporphyrinogen IXreacts readily with cysteine to form a porphyrin C-type compound.g1 Thisinteresting finding has led these authors to suggest that cytochrome-c maybe formed by the interaction of the thiol groups of the apocytochrome-cpeptide with protoporphyrinogen during its oxidation.The coupling ofprotohaemin to the catalase apoprotein, synthesised by the cell, is a CoA-linked enzymic process. A 1 : 1 ratio between CoA and haemin is neededin the coupling reaction.02 It has been suggested 93 that the haem apoen-83 H. C. Schwartz, R. L. Hill, G. E. Cartwright, and M. M. Wintrobe, Fed. Proc.,1959, 18, 545.84 0. Warburg and H. S. Gewitz, 2. physiol. Chem., 1953, 292, 174.85 G;. S. Marks, D. K. Dougall, E. Bullock, and S. F. MacDonald, J. Amer. Chem.Soc., 1960, 82, 3183.8 6 M. Piatelh, Tetrahedron, 1960, 8, 266.87 M. Morrison, J.Connelly, J. Petix, and E. Stotz, J . Biol. Chem., 1960, 235, 1202.D. B. Morrel, J. Barrett, and P. S. Clezy, Biochem. J., 1961, 78, 793.89 W. S. Caughey and J. L. Yorlr, J. Biol. Chem., 1962, 237, PC 2414.M. Kiese, H.rcKurz, and E. Thofern, Biochem. Z., 1958, 330, 541.9lK. G. Paul,Press Inc., New York, 1951, Vol. 11, p. 357.O 2 J. Jensen, J. Bacteriol., 1957, 73, 324.9 3 J. Jensen, Biochem. Biophys. Res. Comm., 1962, 8, 271.The Enzymes, ed. J. B. Sumner and K. Myrback, AcademiMARKS: THE BIOSYNTHESIS O F PORPHYRINS 397zymes synthesised by Staphlococcus aureug JT/52 (a mutant strain) in theabsence of hem act as inhibitors of the enzymes catalysing the conversionof porphobilinogen into uroporp hyrinogen.Hzmophilus species comprise a group of organisms with absolute require-ments for hemin and/or pyridine nucleotide.It has been shown that theenzymes required for hem synthesis are present in four hem-independentspecies but are absent from three distinct haem-requiring species.94Chlorophyll Biosynthesk-The discovery by Granick in 1948 of aChlorella mutant which produced no chlorophyll but accumulated proto-porphyrin IX instead 95 established the biosynthetic relation betweenseveralsteps - fH2I-I02C*CH2*CH2 1 I. .,c - c=oMg Protoporphyrin IX monomethyl e s t e r(28)H- C02MeMg Vinylphaeoporphyrin a,PhytoIJ \Light + 2HProtochlorophyll ChlorophyllideLight + 2H \ JPhytoIChlorophyll ABacteriochlorophyllprotoporphyrin IX and bacteriochlorophyll. In subsequent work magnesiumprotoporphyrin IX and magnesium vinylpheoporphyrin a5 (29) were isolatedfrom ChZoreZZa mutants.96, 9 7 Recently protoporphyrin monomethyl esterand magnesium protoporphyrin monomethyl ester (28) have been isolatedfrom a Chlorella mutant No.60-A and from barley seedlings treated with9 4 D. C. White, New York Branch American SOC. for Microbicl., 97th Meeting,95 S. Granick, J . Biol. Chem., 1948, 172, 717.96 S. Granick, J . Biol. Chem., 1948, 175, 333.9 i S. Granick, J . Biol. Chem., 1950, 183, 713.January, 1962398 BIOLOGICAL CHEMISTRYb-aminolaevulic acid.98 On the basis of these findings the annexed bio-synthetic pathway was postulated.Further clarification of the biosynthetic pathway has come from thestudies of Gibson et aLg9 who found that 10-4M-ethionine and 10-3~-threonine almost completely inhibited bacteriochlorophyll synthesis byRhodopseudomoms spheroides and at the same time markedly increased ex-cretion of copro- and uro-porphyrin into the medium in which the organismwas illuminated. At these concentrations there was little inhibition ofprotein synthesis or growth.The effects of both ethionine and threoninewere reversed by addition of methionine or homocysteine thiolactone, andhomoserine reversed the effect only of threonine. These results suggestedthat methionine might be the direct precursor of the methyl ester group ofbacteriochlorophyll. To test this, organisms were illuminated in the pres-ence of [Me- 14C]methionine, and highly radioactive bacteriochlorophyll wasisolated and degraded.Radioactivity was found to be almost exclusivelyin the methyl group, showing that the methyl group of methionine was thespecific precursor of the porphyrin ester-carbon atom. Less specific utilisa-tion of formate for the methyl group of chlorophyll had been shown inearlier work of Green et aZ.lWRecently threonine has been shown lol to inhibit synthesis de novo ofmethionine in this organism by competitively inhibiting homoserine dehydro-genase, which explains why threonine and ethionine exert similar effectson the biosynthesis of bacteriochlorophyll and on the accumulation ofporphyrins.The mechanism by which methionine provides the methyl ester groupof bacteriochlorophyll has recently been elucidated. Chromatophores fromRhodopseudomoms spheroides, when incubated with magnesium protopor-phyrin and X-adenosylmethionine, form magnesium protoporphyrin mono-methyl ester.102 The enzyme catalysing this synthesis (S-adenosylmethion-ine-Mg-protoporphyrin methyl transferase) has been extensively studied.1°3It has optimal activity at pH 8-4 and is stable to freeze-drying of thechromatophores. Acetone-dried chromatophores contained 33% of theoriginal activity but attempts to solubilise the enzyme from such prepara-tions have been unsuccessful. S- Adenosyl-ethionine and -homocysteinewere found to be competitive inhibitors with respect to S-adenosylmethion-ine, so that in methyl-group deficiency the rate of synthesis of Mg proto-porphyrin monomethyl ester may be low, both because of a low concentrationof X-adenosylmethionine and a relatively high concentration of X- adenosyl-homocysteine.The specificity of the enzyme for other porphyrins and metalloporphyrinswas examined.Magnesium deuteroporphyrin and magnesium mesopor-phyrin exhibited about a fifth of the activity, and zinc protoporphyrin aboutS . Granick, J . Biol. Chem., 1961, 236, 1168.O 0 K. D. Gibson, A. Neuberger, and G. H. Tait, Biochem. J . , 1962, 83, 550.loo M. Green, K. T. Altman, J. E. Richmond,.and K. Salomon, Nature, 1957, 179,lol K. D. Gibson, A. Neuberger, and G. H. Tait, Biochem. J., 1962, 84, 483.loa G. H. Tait and K. D. Gibson, Biochim. Biophys. Acta, 1961, 52, 614.lo3 K. D. Gibson, A. Neuberger, and G. H. Tait, personal communication.375MARKS: THE BIOSYNTHESIS OF PORPHYRINS 399half the activity, of magnesium protoporphyrin; ferrous and ferric proto-porphyrin were inactive.Of the metal-free porphyrins tested, protopor-phyrin was the best substrate, exhibiting -10% of theactivity of magnesiumprotoporphyrin, and other dicarboxylic porphyrins, meso-, deutero-, andhzmato-porphyrin were much less active. The tetracarboxylic acid por-phyrin, coproporphyrin, was inactive, as was protoporphyrinogen. Of theporphyrins tested as inhibitors of the methylation, hzmatoporphyrin wasthe most potent and of the metalloporphjTins ferrous, ferric, and man-ganese protoporphyrin were active inhibitors. It has been suggested thatunder some conditions of growth the inhibition caused by hzem may be ofphysiological importance.Since protoporphyrin is only one-tenth as active as magnesium proto-porphyrin as a substrate for enzymic methylation it was concluded that thefirst two steps in the conversion of protoporphyrin into bacteriochlorophyllare protoporphyrin -+ Mg protoporphyrin -+ Mg protoporphyrin mono-methyl ester.The further conversion of magnesium protoporphyrin monomethyl esterinto magnesium vinylphzoporphyrin a5 must involve several intermediatesteps and further understanding of this conversion awaits detailed enzymicstudies.Me.:H.OH_, , MeMe wHfiEtMe.CH . OHE t/ HMe. CHOn the basis of recent evidence lo4 chlorophyll d is thought to be2-devinyl-2-formylchlorophyll a. A chlorophyll isolated from Chbrobiumthiosulphatophilum possesses several novel features ; it does not give a positiveMolisch phase test and the alcohol component of the ester linkage to thepropionic acid group is trans,trans-farnesol.lo5 The proposed structure forthis compound log is that of a derivative of 2-devinyl-2-l’-hydroxyethyl-6-methylpyrophzophorbide (30), and a study of the biosynthesis of thiscompound will be of considerable interest.G. S. M.104 A. S. Holt and H. V. Morley, in “ Comparative Biochemistry of Photoreactivelo5 If. Rapoport and H. P. Hamlow, Biochem. Biophys. Res. Comm., 1961, 6, 134.lo6 A. S. Holt, D. W. Hughes, H. J. Kende, and J. W. Purdie, J . Amer. Chem.Systems,” ed. M. B. Allen, Academic Press Inc., New York, 1960, p. 169.SOC., 1962, 84, 2835400 BIOLOGICAL CHEMISTRY3.VITAMIN B I ZIN this Report consideration is given primarily to the structure, function,and mechanism of action of the recently discovered cobamide coenzymesand to the impact which this new knowledge has had on the question of themetabolic role of vitamin B12. The biosynthesis of cobamides will also bediscussed.The Isolation and Structure of the Cobamide Coenzmes.-The investiga-tions by which H. A. Barker and his co-workers have recently revolutionisedthe field of vitamin B,, chemistry and biochemistry began during a study ofcell-free extracts from Clostridium tetanomorphum which were able toconvert L-glutarnate (1) into mesaconate (3) via an isomerisation to L-threo-p-methylasparate (2).1 21 C0,H 1 C0,H H O 2C-CHI5I2 CH-NH,4 CHCH,6 COOH12 CH*NH,I3 CH,I4 CH,16 C0,H(1) (2) (3)2 7 1 3 =$ 4 C.CO,H3 CH,IThe isomerisation required a factor which could be removed from thecell-free extract by absorption on charcoal.2 Partial purification of thefactor, after extraction from whole cells with boiling 80% ethanol, showed i tto be orange-red, with absorption maxima a t 263, 303, 374, and 475 mp.Light inactivated it and produced spectral changes to give maxima a t 261,( fR' ( d ) \ ,o-PO& ' 0 OHI I2 Y-(1) Cobyrinic acid: R1 = OH,(2) Cobinamide:(3) Cobamide :R2 = OHR1 = NH,, R2 = NH.CH,-CHMe*OX, X = HR1 = NH,, R2 = NH.CH,*CHMe*OX'H.A. Barker, R. D. Smyth, E. J. Wawszkiewicz, M. N. Lee, and R. M.Wilson,Arch. Biochem. Biophys., 1958, 78, 468; A. Munch-Petersen and H. A. Barker, J. Biol.Chem., 1958, 230, 649.H. A. Barker, H. Weissbach, and R. D. Smyth, Proc. Nat. A d . Sci. U.S.A.,1958, 44, 1093WHITE: VITAMIN B12 401351, 407, and 495 mp. The last set of maxima was reminiscent of that ofthe cobalamins. Alkaline potassium cyanide inactivated the factor, changedits colour to reddish-purple, and produced a change to a spectrum char-acteristic of cobinamide dicyanide (2; Y = CN). Hydrolysis of the factorwith acid yielded adenine and on this and other evidence it was concludedthat the compound under investigation was the coenzyme form of pseudo-vitamin B12. After more extensive purification in which the solubility ofthe coenzyme in ethanol (80%), its solubility in phenol, and its retention oncation-exchangers at pH < 5.5 were utilised, the structural hypothesis wasconfirmed.3 However, it now became apparent that there were two mole-cules of adenine to each atom of cobalt and it was suggested that the" extra " adenine occupied the site usually taken by cyanide in pseudo-vitamin Bz2.The ribonucleotide adenine, present also in pseudovitaminB1,, was readily removed by mild acid hydrolysis with consequent loss ofcoenzymic activity but without gross alteration of spectral properties. The" extra " adenine was more resistant to removal by acid but could be readilydisplaced by alkaline cyanide with resultant loss, by the coenzyme, of itsbiological activity and a change in its spectrum to conform with that ofpseudovitamin B,,.4At the same time as the structure of pseudovitamin B,, coenzyme wasbeing established, the synthetic ability of C.tetanomorphum was utilised toincorporate 5,6-dimethylbenzimidazole into the coenzyme form of vitaminB,, i t ~ e l f . ~ Also the coenzyme of vitamin B,, was successfully isolated 6from Propioniibacterium shermanii without addition of dimethylbenzimid-azole to the growth medium. Further chromatographic and electrophoreticevidence for the existence of an extra adenine molecule in the vitamin B,,CH-0 -P-,oJH C-P I / ALHO*H,; ' 0\I- CH r - - - N 'Me I \(4) Cyanocobalamin (vitamin B , 2)(5,6-dimethylbenzimidazolyl cobamide cyanide)(5) I n pseudovitamin B,, (adenylcobamide cyanide)adenine replaces 5,6-dimethylbenzimidazo3e)(6) In cobamide coenzymes, cyanide is replaced by adenosine.H. A.Barker, R. D. Smyth, H. Weissbach, A. Munch-Petemen, J. I. Toohey,J. N. Ladd, B. E. Volcani, and R. M. Wilson, J. Biol. Chem., 1960, 235, 181.H. Weissbach, J. N. Ladd, B. E. Volcani, R. D. Smyth, and H. A. Barker,J. Bid. Chem., 1960, 235, 1462.ti H. Weissbach, J. Toohey, and H. A. Barker, Proc. Nut. Acad. Sci. U.S.A.,1959, 45, 521.H. A. Barker, R. D. Smyth, H. Weissbach, J. I. Toohey, J. ItT. Ladd, andB. E. Volcani, J. Biol. Chem., 1960, 235, 480402 BIOLOGICAL CHEMISTRYcoenzyme was obtained, thus giving a, clear structural distinction betweenvitamin B,, [a- (5,6-dimethylbenzimidazolylcobamide) cyanide] (5) andvitamin B,, coenzyme [a'( 5,6-dimethylbenzimidazolyl)cobamide coenzyme](7).Adenine picrate was later isolated from the products of the cyanide-induced decomposition of the coenzyme.' The nature of the productsresulting from photolysis of adenylcobamide coenzyme and acid hydro-lysis (O-h-HCl, loo", 90 minutes) of dimethylbenzimidazolylcobamidecoenzyme indicated that the " extra )' adenine is linked to a sugar. Theresults could not be rationalised, however, until X-ray crystallographicanalysis showed that adenine is present as. its riboside and that the ribosideis, surprisingly, linked directly to cobalt at C-5'. Presumably erythro-2,3-dihydroxypent-4-enal lo which can be obtained by mild acid hydrolysis andby cyanide treatment of the coenzyme is a degradation product of riboseafter rupture of the Co-C bond; and the identification,ll under similardegradative conditions, of adenosine-5'-carboxylic acid, a cyclic riboside,and adenosine-5'-aldehyde is in agreement with the X-ray crystallographicwork.Magnetic-susceptibility measurements indicate that vitamin B,, co-enzyme is paramagnetic in solution,12 and the magnetic moment l3 of asolution of the coenzyme form of cobinamide indicated the presence of anoctahedral bivalent cobalt complex. Johnson and Shaw also consider thesolid coenzyme to be paramagnetic, but Bernhauer et aZ.12 consider it to bediamagnetic, like cyanocobalamin. A compound which has close spectralaffinity with the bivalent cobalt-containing vitamin B12r is produced onphotolysis of the coenzyme under anaerobic conditions, and aquocobalaminis formed quantitatively, immediately after the admission of oxygen.l4However, measurement of the oxygen uptake l 5 with the oxygen electrodeduring this process indicated the consumption of 0-75 mol. of oxygen permol. of coenzyme instead of 0.25 mol. necessary for the conversion ofcobalt(rr) into cobalt(m). Also, during anaerobic photolysis in the presenceof 2,6-dichlorphenol-indophenol one equivalent of dye per mol. of coenzymeis reduced without causing the oxidation of the B,, state to that whichexists in aquocobalamin.16 Thus, the photolytic conversion of coenzyme intovitamin may involve an oxidative process in the peripheral part of thecoenzyme molecule.15 Thus the true valency state of cobalt in the co-enzyme is not clear, neither is the state of conjugation in the chromophore.Apart from the microbial sources mentioned above, the cobamide co-enzymes have also been isolated from Clostridium sticklandii,16 C.per-* 5. N. Ladd, H. P. C. Hogenkamp, and H. A. Barker, Biochem. Biophys. Res.A. W. Johnson and N. Shaw, Proc. Chem. Soc., 1960, 420.P. G. Lenhert and D. C. Hodgkin, Nature, 1961, 192, 937.Cornm., 1960, 2, 143.loH. P. C. Hogenkamp and H. A. Barker, J . Biol. Chem., 1961, 236, 3097.l1 H. P. C. Hogenkamp, J. N. Ladd, and H. A. Barker, J. Biol. Chem., 1962,l2 K. Bernhauer, P. Gaiser, 0. Miiller, and F. Gunter, Biochem. Z . , 1961, 333, 560.l3 L. Nowicki and J. Pawelkiewicz, Bull. Acad. polon. Sci., Ser. Sci. Chim. et Biol.,l4 R.0. Brady and H. A. Barker, Biochem. Biophys. Res. Comm., 1961, 4, 373.l5 H. A. Barker, 2nd European Symposium on Vitamin B12, Ferdinand Enkel6 T. C. Stadtman, J . Bact., 1960, 79, 904.237, 1950; A. W. Johnson and N. Shaw, J., 1962, 4608.1960, C1. 11, 8, 433.Verlag, Stuttgart, 1962, p. 99WHITE: VITAMIN B l a 403fringens,lT Bacillus rnqaterium,lg Escherichia coli 113-3, Xtreptomyces fradiae,and Aerobacter aerogenes.17 The coenzymes probably occur also in theacraldehyde-forming lactobacillus 2O8-A.l9The isolation of the coenzyme from the nodules of a number of legumes,from alder, and from Rhixobium melitoti has gone some way towards explain-ing the essential nature of cobalt in nitfogen fixation.,OMammalian sources of vitamin B,, coenzyme include rabbit, chicken,sheep, and human liver.21@-Methylasparate Isomerisation.-The isomerase has been isolated onlyfrom Clostridium tetanomorphum 2 and no metabolic significance for thisreaction in mammals has yet been found.Attempts to do so have beenstimulated mainly by the possibility of a biosynthetic route to thymineribose phosphate involving the carbamoylation of p-methylaspartic acid.,,However, DL-threo-p-methylaspartic acid is a competitive inhibitor ofL-aspartic acid for the growth of E. .coZi strain B 23 and, moreover, in thesame organism, no radioactivity is incorporated into thymine from triti-ated /I-methylaspartic acid 24 or ~~-threo-[Me- 14C]-#?-methylaspartic acid.25L-threo-#?-Methylaspartic acid is not a growth factor for the vitaminB,,-requiring protozoon Ochromoms malhamensis, 26 but it has been reportedto stimulate the growth of Poteriochromonas stipitata in the absence ofcyanocobalamin.However, even here, the growth stimulation is nevefequivalent to that of vitamin B1,, and it falls off as the level of /I-methyl-aspartic acid in the medium rises from 0.1% to 0.6%.[Me- 14C]Methylaspartic acid is not incorporated into the thymine ofregenerating rat liver.28While these results on the metabolism of p-methylaspartic acid do notpresent a completely unified picture it seems unlikely that this compound isin fact a component of thymine biosynthesis.MethyImalonyl-coenzyme A Isomerisation.-H. R. Marston g9 suggestedin 1959 that inability to utilise propionic acid was the main metabolic lesionin vitamin B,,-deficient sheep, and subsequently it was shown that indeficient rats the activity of the liver enzyme catalysing the isomerisation ofmethylmalonyl-CoA to succinyl-CoA was much less than in controls.30l7 R. H. Abeles and H. A. Lee, J. Biol. Chem., 1961, 236, 2347.Is K. L. Smiley and M. Sobolov, Arch. Biochem. Biophys., 1962, 97, 538.2o M. Kliever and H. J. Evans, Nature, 1962, 194, 108.z1 J. I. Toohey and H. A. Barker, J. Biol. Chem., 1961, 236, 560; H. R. Marston,22E. Seifter and E. Manson, Amer. Chem. SOC. Meeting, Abs., 1959, NO. 41.24 I. H. Koehelik and D. W, Woolley, Biochem. Biophya. Res. Comm., 1961, 6,26 T. Abramsky, L. P. Rowland, and D. Shemin, J. BioZ. Chem., 1962, 237, PC265.26 H.A. Nathan and H. B. Funk, Proc. SOC. Ezp. Biol. Med., 1962, 109, 213.27 H. D. Isenberg, E. Seifter, and J. I. Berkman, Biochim. Biophys. Acta, 1960,naR. E. Webb, S. Kirschfeld, and B. C. Johnson, 2nd European Symposium on2s H. R. Marston, Med. J. Australia, 1959, 2, 105.soR. M. Smith and K. J. Monty, Biochem. Biophys. Res. Comm., 1959, 1, 105.B. E. Volcani, J. I. Toohey, and H. A. Barker, Arch. Biochem. Biophys., 1961,92, 381.S. H. Allen, and R. M. Smith, Nature, 1961, 190, 1085.D. W. Woolley, J. Biol. Chem., 1960, 235, 3238.279.39, 187.Vitamin BIZ, Ferdinand Enke Verlag, Stuttgart, 1962, p. 198404 BIOLOGICAL CHEMISTRYPropionyl-CoA was already known to be directly carboxylated t o methyl-malonyl-CoA 31 and thus Marston's results could be explained.Smith andMonty 30 also pointed out the similarity between the isomerisations ofp-methylaspartic acid and methylmalonic acid, indicating that the vitaminB,, coenzymes might be coenzymes for methylmalonyl-CoA isomerase. Thisprediction was correct. Methylmalonyl-CoA isomerase activity in an extractof acetone-dried rat-liver mitochondria from vitamin B,,-deficient animalsis restored by dimethylbenzimidazolylcobamide coenzyme, 32 and similarlythe activity of a partially purified isomerase from ox liver was enhanced bythe coenzyme.33 The separation of apoenzyme and coenzyme provedcWEcult when the holoenzyme, which could not be inactivated by light orcharcoal, was derived from sheep kidney. The apoenzyme had to be pre-cipitated from an ammonium sulphate solution with acid,34 and methyl-malonyl-CoA isomerase activity was restored by dimethylbenzimidazolyl-cobamide coenzyme or benzimidazolylcobamide coenzyme but not byadeninylcobamide coenzyme.34Isomerase activity in cell-free extracts of Propioniibacterium shermaniiis eliminated by treatment with charcoal and restored with pure vitaminB,, coenzyme.s5The enantiomorph of methylmalonyl-CoA which is the immediate pro-duct of the action of HC0,- and biotin on propionyl-CoA is subjected to theaction of a racemase before its isomerisation to succinyl-CoA. The racemasehas been partially purified from Propioniibacteria 36 and from an extractof sheep liver.37 The racemisation appears t o occur by movement of thehydrogen atom attached to the tertiary carbon.This has been shown byexchange studies in T20 37 and by proton magnetic resonance studies.36Present evidence supports the migration of the intact thioacylated car-boxyl group during the isomerisation of methylmalonyl-CoA (4) to succinyl-CoA ( 5 ) , as originally suggested by Stern and Friedman:33WH ,CO*S*CoA B,* /lCo*S*CoA _____, HC0,-CH,*CH,CO*S*CoA - CH3*2CH f--- fBiotin \3C0,H Coenzyme 3CH,*C0,H(4) ( 5 )Thus, [2-14C]methylmalonyl-CoA gives rise to [3-14C]succinyl-CoA38 andenzymically synthesised [ 1- 14C]- and [3-14C]-methylmalonyl-CoA form31 M. Flavin, P. J. Ortiz, and S. Ochoa, Nature, 1955, 1'76, 823.32 S. Gurmnani, S. P. Mistry, and B. C. Johnson, Biochim. Biophys. Actu, 1960,38, 187.33 J.R. Stern and D. L. Friedman, Biochem. Biophys. Res. Comm., 1960, 2, S2.3 4 D. Lengyel, R. Mazumder, and 8. Ochoa, Proc. Nut. Acad. Sci. U.S.A., 1960,46, 1312.S5 E. R. Stadtman, P. Overath, H. Eggerer, and F. Lynen, Biochenz. Biophys.Res. Comm., 1960, 2, 1; R. Stjernholm and H. G. Wood, Proc. Nut. Acad. Sci. U.S.A.,1961, 47, 303; P. Overath, E. R. Stadtman, G. M. Kellerman, and F. Lynen, Biochem.Z., 1962, 326, 77.315 P. Overath, G. M. Kellerman, and F. Lynen, Biochem. Z., 1962, 335, 500.37 R. Mazumder, T. Sasakawa, Y . Kaziro, and S. Ochoa, J . Biol. Chem., 1962,38 H. Eggerer, E. R. Stadtman, P. Overath, and F. Lynen, Biochem. Z., 1960,237, 3065.333, 1WHITE: VITAMIN B12 405[ 1 - 14C]- and [4-1*C]-succinyl-CoA, respe~tively.~~ A suggestion which agreeswith the above labelling results but would require the isomerisation to bean intermolecular rearrangement has been put forward independently byMarston, Miles, and Smith 39* and by Hegre, Miller, and Lane.39a 2,5-Dioxo-cyclohexane- 1,4-dicarboxylic acid (succinosuccinic acid) (6) is suggested asocCOzHICHZ- CH2 ’ SCoA\ SCoA “O /CHz-CHZCOzHCOZHICOZH+ 2CoASHan intermediate.However, it was not possible to label a pool of thisacid 39b from [ 14C]succinyl-CoA, and further evidence supporting an intra-molecular rearrangement has been forthcoming. 4* An equal mixture ofmethyl-[carboxyZ-13C]- and -[thi0ester-~3C]-malonyl-CoA was utilised for theisomerisation. Analysis by mass spectrometry of the succinate producedgave a 13C enrichment in accord with that calculated for an intramolecu-lar rearrangernent.4Oa Similar results were obtained by Kellermeyer andFree carbon monoxide 4 1 is not released during the isomerisa-tion, nor is there release of a free proton.Sheep and other ruminants utilise propionate produced in the rumen,through methylmalonyl-CoA and succinyl-CoA as an energy source.Vita-min B,, deficiency thus deprives the animal of energy and increases thelevel of circulating methylmalonic acid. This increased level perhapsaccounts for the fact that the animals feel unwell and die of inanition, andit may also be the cause of the neurological disease in sheep known as‘‘ swayback.” These matters have been discussed recently.42Evidence supporting the existence of methylmalonyl-CoA isomerase inman has been reported.Thus vitamin B,, deficiency always raises the levelof excreted methylmalonic acid. 43 During the reticulocyte response result-ing from the administration of folic acid to patients with pernicious anzemiain relapse, the level of excreted methylmalonic acid remained unchanged.It is noteworthy that, whereas the neurological symptoms of perniciousanzemia are alleviated by vitamin B,,, they are not brought into remissionby folic acid. It is tempting to suggest, therefore, by analogy, that in manalso the rise in tissue levels of methylmalonic acid is responsible for theneurological symptoms of vitamin B,, deficiency.Vitamin B1,-deficient Ochromonas malhamensis, a protozoon with arequirement for the vitamin similar to that of rnarnma1~,~4 cannot isomerise39 (a) C.R. Hegre, S. J. Miller, and M. D. Lane, Biochim. Biophys. Ada, 1962, 56,538; ( b ) H. R. Marston, J. A. Mills, and R. M. Smith, Nature, 1962, 193, 240.4 0 (a) E. F. Phares, M. V. Long, and S. F. Carson, Biochem. Biophp. Res. Comm.,1962, 8, 142; ( b ) R. W. Kellermeyer and H. G. Wood, Biochemistry, 1962, 1, 1124.4 1 M. Flavin and C. Slaughter, J . Amer. Chem. SOC., 1961, 83, 397.4 2 H. R. Marston, S. H. Allen, and R. M. Smith, Nature, 1961, 190, 1085.43 A. M. White, Biochem. J . , 1962, 84, 41P; E. V. Cox and A. M. White, Lancet,443%. E. Coates and J. E. Ford, Biochem. SOC. Symposium, 1955, No. 13, p. 36.1962, 853406 BIOLOGICAL CHEMISTRYmethylmalonyl-CoA to succinyl-CoA. However, the metabolic lesion isalleviated, not only by cyanocobalamin, but also by the methylamide 45 ofvitamin B,, which is a specific antagonist of vitamin B,, for the growth ofthe organism.Methylmalonic acid is not a growth factor for OchromonasmaZhamensis.26 The view was therefore expressed 45 that the growth-promoting reaction mediated by vitamin B,, does not involve methyl-malonyl-CoA isomerase. Similar results have been obtained with a marinebacterium. 46In view of the effect of vitamin B,, on propionate metabolism, interest inits possible effect on general lipid metabolism has been rekindled. Thistopic has been discussed, particularly with relation to the chick embryo, byMoore and Doran.*’Metabolism of One-carbon Units,-The demonstration of a coenzymicr61e for vitamin B,, in the general oxidation-reduction of one-carbon unitswhich appeared at one time to be highly probable 4s has not materiali~ed.~~However, work on certain aspects of methionine synthesis in Escherichia coZihas been more fruitfu1.50Methionine appears to be synthesised in E.COG by two pathways, onlyone of which involves vitamin B12. The experimental evidence rests onwork with strains 113-3 and 121/176 (methionine/cyanocobalamin auxo-trophs) and PA 15 (a glycine/serine auxotroph) which has recently beensummarised.50 The pathways from serine are shown in the annexed scheme.51SerinePyridoxal p h o s p h v w o x a l phosphateNWO-Methylene PtH4G NSNIo-Methylene PtH,GIPtHdG PtH,G,NS-MePtHIG NS-MePtH,G3Hornocysteine 4 NaDH2 VHornocy steineFAD, ATP‘Cobarnide enzyme’Methionine Methionine c.PtH,G PtH4G3PtH4G = TetrahydropteroylglutamateN6N10-MethylenePtH,G = Tetrahydro-NSN1O-methylenepteroylglutamateN5-MePtH,G = Tetrahydro-N5-methylpter~ylgl~tamateN6N1O-MethylenePtH4G, = Tetrahydro-N5N10-methylenepteroyltriglutamateN6-MePtH,G, = Tetrahydro-N6-methylpteroyltriglutamate 53FAD = Flavin-adenine dinucleotideNADH, = Reduced nicotinamide -adenine dinucleotideATP = Adenosine 5’-triphosphate46 H. R. V. Amstein and A. M. White, Biochem. J., 1962, 83, 264.46 W. A. Ayers, Arch. Biochem. Biophya., 1962, 96, 210.47 J. H. Moore and B. M. Doran, Biochem. J., 1962, 84, 506.48 H. R. V. Amstein, 4th Internat. Congress Biochemistry, Pergamon Press, 1960,Vol.XI, p. 286; Biochem. J., 1960, 74, 616; J. 8. Dinning and R. S. Young, J. BioE.Chem., 1959, 234, 3241.49 A. M. White and H. R. V. Amstein, 2nd European Symposium on Vitamin Bla,Ferdinand Enke Verlag, Stuttgart, p. 186.60 J. R. Guest and D. D. Woods, ref. 49, p. 686.61 F. T. Hatch, S. Takeyama, R. E. Cathou, A. R. Larrabee, and J. M. Buchanan,J. Amer. Chem. Soc., 1959, 81, 6525; F. T. Hatch, A. L. Larrabee, R. E. Cathou,and J. M. Buchanan, J . Biol. Chem., 1961, 236, 1095WHITE: VITAMIN B12 407The 150-fold purification of the cobamide-containing enzyme has beenaccomplished from strain PA 15.S4 The cobamide derivative does not be-come available as a growth factor for Escherichia coli 113-3 64b or Lacto-bacillus Zeichmunii until released by heat,54 digestion with papain,54b orextraction with hydrogen ~yanide.5~~ While ultraviolet light destroys theactivity of the “ cobamide enzyme,” visible light or activated charcoal iswithout effect.54 Dimethylbenzimidazolylcobamide coenzyme can replacecyanocobalamin for the formation of the “ cobamide enzyme ” in cell-freeextracts but it does not possess “ cobamide enzyme ” activity for methioninesynthesis in vitr0.54~What is almost certainly the same cobamide containing enzyme has beenisolated from Escherichia coli 113-3.55 However, in the in vitro systemsused here dimethylbenzimidazolylcobamide coenzyme was found not to be aprecursor.The spectrum of the cobamide enzyme from E. coli 113-3 55is similar to that of vitamin B12r.Release of the prosthetic group wasachieved with warm alcohol (80%) but insufficient material was availablefor complete characterisation. 55The possibility that the methyl analogue (methyl replacing adenosine)of dimethylbenzimidazolylcobamide coenzyme may be an intermediate inthe formation, or may itself be the prosthetic group, of the “ cobamideenzyme ’’ has been explored.66 The rate of the spontaneous reaction whichoccurs between the methyl analogue and homocysteine in the presence ofmercaptoethanol could be increased up to 10-fold by the purified “ cobamideenzyme.” The [Me-14C]-coenzyme analogue gave methionine with un-changed specific activity in the methyl group, As the authors 66 are aware,the results are open to a number of interpretations but they are not inconflict with the original hypothesis.While it is unlikely from a nutritional point of view that inability tosynthesise methionine is the main lesion in vitamin B,, deficiency, and infact no requirement for vitamin B,, has been found in cell-free methionine-synthesising systems from mammalian sources,57 the possibility remainsthat other methyl groups may require vitamin B,, for their synthesis. Theidentification of the ‘‘ cobamide enzyme ” substrate, tetrahydro-N5-methyl-pteroylmonoglutamate, in various mammalian tissues, 58 including humansupports this view, as does the accumulation of serum Lactobacilluscmei activity in patients with pernicious anzmia.59 It should be pointed5 2 A.R. Larrabee, S. Rosenthal, R.Cathou, and J. M. Buchanan, J. Amer. Chem.SOC., 1961, 83, 4094; W. Sakami and I. Ustkins, J. Biol. Chem., 1961, 236, PC50.5s J. R. Guest, S. Friedman, and M. A. Foster, Biochem. J., 1962, 84, 93P.54 (a) R. J. Kisliuk, J. Biol. Chem., 1961, 236, 817; (b) M. A. Foster, K. M. Jones,and D. D. Woods, Biochem. J., 1961, 80, 519.65 S. Takeyama, F. T. Hatch, and J. M. Buchanan, J. Biol. Chem., 1961, 236,1102; S. Takeyama and J. M. Buchanan, J. Biochem. Tokyo, 1961, 49, 578.5 6 J. R. Guest, S. Friedman, D. D. Woods, and E. L. Smith, Nature, 1962,195, 340.57 A. Nakao and D. M. Greenberg, J. Biol. Chem., 1958, 230, 603; A. Stevens andW. Sakami, ibid., 1959,234,2063; W. Wilmans, B. Rucker, and L. Jaenicke, 2. physiol.chem., 1960, 322, 283.58 (a) L.Jaenicke, 2. physiol. chem., 1961, 326, 168; K. 0. Donaldson and J. C.Keresztesy, Biochem. Biophys. Res. Comm., 1961,5,289; (b) V. Herbert and R. Zalusky,J. Clin. Invest., 1962, 41, 1263.sD D. L. Mollin, A. H. Waters, and E. Harris, 2nd European Symposium on VitaminBIZ, Ferdinand Enke Verlag, Stuttgart, p. 737408 BIOLOGICAL CHEMISTRYout that tetrahydro-N5-methylpteroylmonoglutamate is unique in that itpossesses growth-promoting activity for Lactobacillus casei. 59 Hitherto onlytriglutamates have been thought to possess this property.The incorporation of [14C]formate into DNA thymine in chick bone-marrow preparations was 2.2 times that obtained when the preparation wasfrom vitamin B,,-deficient chicks. A similar effect was observed whenvitamin B12 or the coenzyme was added in vitro.60 No effect was observedwhen either [ 14C]formaldehyde or [3- 14C]serine was used as one-carbonsource.6o Similar stimulation of thymine biosynthesis by vitamin B,, wasobtained with Lactobacillus Zeichmanii rendered deficient by growth ondeoxyribosides.61 However, a recent attempt to confirm the effect ofvitamin B,, on thymine biosynthesis from [ 14C]formate in LactobaciZZusZeichmanii was unsuccessfu1,62 and Floyd and Whitehead 63 presentedevidence indicating that the uracil deoxyriboside level is the limiting factorin this organism in vitamin B,, deficiency. Thymine biosynthesis from[3-14C]serine, in rats, was shown to be slightly stimulated by vitamin B12,but when [14C]formate was the precursor vitamin B,, caused a slight reduc-tion in incorporation.49 Only slight stimulation of thymine synthesis(maximum four-fold) was brought about by vitamin B,, in deficient Ochro-m o w m~lhamensis.~~ In contrast to Dinning’s recently repeated 64 inter-pretation of his results, Arnstein and White take the view that thyminebiosynthesis would have been affected to a much greater extent, if notcompletely blocked, in deficient Ochromow, if vitamin B,, were in fact acoenzyme for its synthesis.However, the possibility that thymine may besynthesised by alternative routes cannot be ruled out, although in thisconnection tetrahydro-N5-methylpteroylmonoglutamate does not appear tobe involved.65Dehydration of Glycols and Lysine Fermentation.-Anaerobically growncultures of Aerobacter aerogenes (ATCC 8724) convert propane-l,2-diol intopropionaldehyde, ethylene glycol into acetaldehyde, and glycerol into3-hydroxypropionaldehyde.66 In cell-free preparations the ability of thesystem to carry out these conversions can be removed if they are treatedwith activated charcoal, and activity for metabolism of propane-l,2-dioland ethylene glycol is restored by addition of dimethylbenzimidazolyl-cobamide coenzyme, adenylcobamide coenzyme, and benzimidazolyl-6 0 J.S. Dinning and R. S . Young, J . Biol. Chem., 1959, 234, 1199; J. S. Dinning,Proc. SOC. Exp. Biol. Med., 1960, 104, 431.62 D. Roberts and C. A. Nichol, J . Biol. Chem., 1962, 237, 2278.1 3 ~ K. W. Floyd and R. W. Whitehead, Biochern. Biophys. Res. Cornm., 1960,3, 220.6 4 J.S. Dinning, Physiol. Rev., 1962, 42, 169.65 Friedkin, quoted by W. S. Beck, New England J . Med., 1962, 206, 708.6 6 R. H. Abeles, A. M. Brownstein, and C . H. Randles, Biochem. Biophys. Acta,J. S. Dinning and R. S. Young, J . Biol. Chern., 1959, 234, 3241.1960, 41, 530WHITE: VITAMIN B12 409cobamide coenzyme.67 A 200-fold purification of the enzyme acceptingpropane-l,2-diol or ethylene glycol has been achieved.s8 The mechanismof the rearrangement has to some extent been elucidated by carrying itout in D,0.6@ No exchange with the solvent occurs, thus suggesting anintramolecular rearrangement.Support for the concept of vitamin B,, coenzyme as part of a transitionstate, in which it carries a hydride ion, is claimed 68 from the observationthat w,,,.for the conversion of [1-2H]propane-1,2-diol is only one-tenth ofthat of the non-deuterated substrate. While the synthetic coenzyme 70 isactive in the Aerobacter aerogenes system a number of other synthetic co-enzyme analogues 7 1 besides cyanocobalamin are powerful competitiveantagonists of the coenzyme. These analogues are not inhibitory for thegrowth of chicks or Ochromonus malhamensis. 71A glycerol dehydrase which requires dimethylbenzimidazolylcobamidecoenzyme, from an acraldehyde-forming Lactobacillus, has also beenidentified. l9The similarity between the production of aldehydes by the dehydrationof vicinal glycols and formation of deoxyribose from ribose is striking.However, convincing proof in a cell-free system of the existence of acobamide-requiring dehydrase (or reductase) for ribotides is still lacking.Work has been mainly concerned with the metabolism of intact Lactobacillusleichmanii after establishment of the nutritional fact that, in the absence ofvitamin B,,, growth requirements for the organism can be met by anydeoxynucleoside. 72 Thus when Lactobacillus leichmanii is grown in thepresence of [l*C]thymidine but in the absence of vitamin B,, the deoxyribosefrom DNA is obtained with undiluted specific activity.In the presenceof the vitamin there is a 10-50-fold decrease in specific activity of the fourdeoxynucleosides, due presumably to increased synthesis from non-radio-active sources in the growth medium.73 Similarly the incorporation of[l-14C]ribose into deoxyribose is not apparent when cells are grown ondeoxycytidine, but can be stimulated when vitamin B,, is added to thegrowth medium.74 Further evidence of a similar nature continues toa c c ~ m u l a t e .~ ~ ~ 75 The observation that the DNA content of cells grown onvitamin B,, is twice that in cells grown on deoxyrib~sides,~~ although dis-p ~ t e d , ~ ~ has been confirmed and extended by others. Thus cultures of thesame turbidity contain three times the number of cells when grown withoptimal concentrations of vitamin B,, than when grown with thymidine,and the RNA: DNA ratio of the cell mass is 6.9 with vitamin B,, and07R. H. Abeles and H. A. Lee, J. Biol. Chem., 1961, 236, PC1, 2347.6 B R. H. Abeles and H.A. Lee, Fed. Proc., 1962, 21, 253.6 9 A. M. Brownstein and R. H. Abeles, J. Biol. Chem., 1961, 236, 1199.7 0 E. Lester Smith, L. Mervyn, A. W. Johnson, and N. Shaw, Nature, 1962, 194,71 E. Lester Smith and L. Mervyn, Biochem. J., 1963, 86, 2P.72 J. Lascelles and M. J. Cross, Biochem. SOC. Symposium, 1955, No. 13, p. 109.73 M. Downing and B. S. Schweigert, J. Biol. Chem., 1956, 220, 521.7 4 W. H. Spell and J. S. Dinning, J. Amer. Chem. SOC., 1959, 81, 3804.75 L. A. Manson, J. Biol. Chem., 1960, 235, 2955; A. Wacker, S. Kirschfeld, and76A. Wacker, D. Pfahl, and I. Schroder, 2. Naturforsch., 1957, 12b, 510.7 7 G. D. Birnie and G. W. Crosbie, Biochim. Biophys. Acta, 1961, 46, 397.1175.L. Triiger, 2. Naturforsch., 1959, 14b, 145410 BIOLOGICAL CHEMISTRY16.0 with thymidine.Vitamin B,, and deoxyriboside limitation operate inan apparently identical manner to produce non-viable filaments of the typeassociated with defective DNA synthesis in other organisms. In thesefilaments the RNA: DNA ratio rises to 34.1 in the case of vitamin BI2-restricted organisms and 41.1 in thymidine-restricted cells. 78 Addition ofan excess of vitamin B,, to previously limited ciiltures of LactobacillusZeichmanii increases the concentration of DNA and the ratios DNA : RNAand DNA : protein. The concentration, per mg. of protein, of acid-solubledeoxyribonucleotides is also increased 3-4 times in 60 minutes.79 Thesuggestion has been made that the megaloblast is in its own way similar tothese filamentous forms of Lactobacillus Zeichmanii and is in a state of im-paired deoxyribonucleotide biosynthesis.80 However, attempts to curepernicious anEmia with thymidine have not proved successful 81 althoughit has been suggested that this failure may have been due to the absence oftram-N-deoxyribosidase in human tissue.65The incorporation of [ 14C]cytidine into deoxycytidine in liver mincesfrom deficient chick embryos is not stimulated by cyanocobalamin.82 Incontrast, synthesis of deoxyribose containing substances in a cell-free extract,containing ATP, AMP, and TPNH, of a murine leukaemic cell L-5178Y isreduced to about a third of the original by treatment with charcoal, andsynthesis is generally restored to about two-thirds of the original level byaddition of cyanocobalamin in vitro : in one case, 100% restoration of activitywas obtained.Restoration of activity is not accomplished with folic acidderivatives.83 It would be interesting to know the effect of the Barkercoenzyme on these mammalian deoxyribotide-synthesising systems.Soluble extracts of an Equadorian clostridium have been obtained whichare capable of degrading lysine to butyrate and acetate when supplementedwith DPN.8* After treatment with charcoal the enzyme preparationexhibited a requirement for boiled extract of fresh cells. The indicationsare that, besides iron(=) and pyruvate, another component of the boiledextract which is necessary for lysine fermentation is the coenzyme ofvitamin BI2.Pyruvate-CO, Exchange.-The requirement for dicyanocobinamide inaerobic incubations designed to show C0,-pyruvate exchange 85 in cell-freeextracts of Clostridium acidi urici and C.butyricum has been further ex-amined 86 with LC strain 1, an aerobe with a pyruvate-oxidising systemclosely resembling C. butyricum. A specific requirement for a high concen-tration (100 pmoles/ml.) of mercaptoethanol was demonstrated 86 and itwas observed 86 that the requirement for vitamin B,, derivatives waseliminated when carbon dioxide exchange was conducted under nitrogen ;7 8 W. S. Beck, S. Hook, and B. €1. Barnett, Biochim. Biophys. Acta, 1962, 55, 455.7 9 W. S . Beck, M. Goulian, and S. Hook, Biochim. Biophys. Acta, 1962, 55, 470.ti2 A. Bolinder and P. Reichard, J. Biol. Chem., 1959, 234, 2723.B3L. A.Manson, 2nd European Symposium on Vitamin BIZ, Ferdinand EnkeVerlag, Stuttgart, 1962, p. 191.8 4 T. C. Stadtman, J . Biol. Chem., 1962, 237, PC2409.s5 J. C. Rabinowitz, J . Biol. Chem., 1960, 235, PC50.86 J. L. Peel, J. Biol. Chem., 1962, 237, PC263.W. S. Beck, J . Clin. Invest., 1961, 40, 1024.G. €1. Spray and L. J. Wills, Lancet, 1958, 2, 869WHIT3: VITAMIN B,, 41 1much lower thiol concentrations also sufficed. Derivatives of vitamin B,,are efficient catalysts for the autoxidation of mercaptoethanol :86,4HO*CH,*CH,*SH + 0, ---+ 2H20 + 2(HO*CH,*CH,*S*),; and thus it hasbeen suggested 86 that vitamin B,, and the thiol act as oxygen-scavenger inthe original aerobic system.85Bioswthesis of Coba,mides.-This topic has been the subject of re-views,g8u, as has been the guided biosynthesis in Propioniibacteria.g8c&Amino[ 1 ,4-14C,]l~wlic acid 89 and [ 14Clporphobilinogen 90 are incorpor-ated intact into microbidly synthesised cobamides, and thus it appears thatthe biosynthesis of the corrin ring follows a similar pattern to that of theporphyrin residue. The “ extra ’’ methyl groups a t positions 2, 5, 7, 12,and 15 are derived from the methyl group of methionine.91 The closure ofthe corrin nucleus between rings A and D probably takes place simultaneouslywith introduction of the cobaltThe aminopropanol residue is derived from threonine,93 but it hasrecently been shown 94 that cobyrin-abcdeg-hexa-amide f-N-DL-threoninephosphate cannot be utilised by Propioniibacteriurn shermanii for the bio-synthesis of cobamides; nor can it replace vitamin B,, for the growth ofEscherichia coli 1 13-3.g4 Thus the decarboxylation of threonine probablyoccurs before its condensation with cobyrin-abcdeg-hexa-amide during theformation of cobinamide.The succession of straightforward biosyntheticreactions between cobinamide and the cobamide ion, postulated by Dellweget aLg5 and later amp15ed,88u namely,Cobinamide -+ Cobinamide phosphateCobamide ion t- Cobinakide ribose phosphatehas had to be modified. The guanosine 5’-pyrophosphoric acid ester ofcobinamide (ribose linked to N-9 of guanine) can be isolated from cobamide-producing strains of Nocardia rugosa 96 and it was shown that the specificactivity of the cobamide (isolated as cyanocobalamin) with S2P incorporatedwas reduced when cobinamide pyrophosphoryl guanosine was included inthe growth medium.97 The annexed scheme was considered to be mostlikely for the biosynthesis of the cobamide ion:96, 9787 J.L. Peel, Biochem. J . , 1962, 85, 17R.88 (a) S. K. Kon and J. Pawelkiewicz, Proceedings 4th Internat. Congress ofBiochemistry, Vol. XI, Pergamon Press, 1960, p. 115; (a) K. Bernhauer, 0. Miiller,and F. Wagner, 2nd European Symposium on Vitamin B12, Ferdinand Enke Verlag,Stuttgart, 1962, p. 37; (c) D. Perlman, J. M. Barrett, and P. W. Jackson, op. cit.,p. 58.D. Shemin, J. W. Corcoran, C. Rosenblum, and I. M. Miller, Science, 1956,124, 272.OO J. W. Corcoran and D. Shemin, Biochiina. Biophys. Acta, 1957, 25, 661.O1 R.Bray and D. Shemin, Biochim. Biophys. Acta, 1958, 30, 647.O 2 R. Bonnet, J. R. Cannon, A, W. Johnson, I. Sutherland, and A. R. Todd, Nature,O3 A. I. Krasna, C. Rosenblum, and D. B. Sprinson, J . BioE. Chem., 1957, 225, 745.04K. Bernhauer and F. Wagner, Biochem. Z . , 1962, 335, 325.O 6 H. Dellweg, E. Becker, and K. Bernhauer, Biochem. Z., 1956, 327, 422.O6 R. Barchielli, G. Boretti, A. DiMarco, P. Julita, A. Migliacci, A. Mmghetti,O 7 G. Boretti, A. DiMarco, L. FUOCO, M. P. Marnati, A. Migliacci, and C. Spalla,1955, 176, 328.and S. Spalla, Biochem. J., 1960, 74, 382.Biochim. Biophys. Acta, 1960, 37, 379412 BIOLOGICAL CHEMISTRYCobinamide ; . P Cobinamide phosphateADPCobinarnide pyrophosphoryl guanosine~ ~ ~ ~ ~ ~ ~ , ~ ~ " ~ i ~ i ~ - riboside5,6-Dimethyl benzimidazolylcobarnide ionConvincing evidence concerning the fhal step has only recently becomeavailable.98, 99 A benzimidazole-requiring strain of Nocardia rugosa whichproduces cobamides in the presence of 5,6-dimethylbenzimidazole or itsriboside, was shown to incorporate the riboside into the cobamide ion withnegligible exchange of the riboside part with [14C]ribose present in themedium.98 Fudher, analogues of benzimidazole were not interchangeablewith 5,6-dimethylbenzimidazole, so that cobamide analogues could not bepr0duced.~8 The accumulation by Propioniibacterium shermunii (in boththe presence and the absence of cobalt) of 5,6-dimethylbenzimidazole ribo-side 99 supports these results, but is in conflict with work based on therelative ease of uptake of the base, as compared with its riboside and ribotidein Escherichia coli 95 and Propioniibacterium shermunii.loo However, perme-ability problems were doubtless involved here.88 It seems unlikely that thefiner points of cobamide biosynthesis will be settled until more work isdone on cell-free systems. In this connexion extracts of acetone powdersfrom E. coli 113-3 have been obtained which incorporate 5,6-dimethyl-benzimidazole 101 into cobamide derivatives.All the biosynthetic intermediates mentioned above have been isolatedby methods which would destroy an organometallic bond of the type presentin the coenzyme. However, it has been possible to isolate from Nocurdiarugosa 466 cobyrin-abcdeg-hexa-amide, a, precursor of cobinamide, linked toan adenine-containing group.102 From Propioniibacterium shermnii, light-sensitive derivatives of cobinamide and related compounds have beenisolated.13, 103It seems highly probable, therefore, that the organometallic bond isformed early in the biogenesis of cobamides.Conversion of Cyanocobalamin into the Coenzyme.-Besides some pre-liminary results in which cell-free extracts of Propioniibacterium shermaniiwere shown to require Mg2f and ATP for the conversion of 5,6-dimethyl-Barbieri, G.Boretti, A. DiMarco, A. Magliacci, and C. Spalla, Biochim.gg H. C. Friedman and D. L. Harris, Biochem. Biophys. Res. Cornm., 1962, 8,loo K. Bernhauer, E. Becher, and G. Wilharm, Arch. Biochem. Biophys., 1959,lol J . Pawelkiewicz and B.Bartosinski, Bull. Acad. polon. Sci., Ser. Sci. Biol.,lo2 A. Migliacci and A. Rusconi, Biochim. Biophys. Acta, 1961, 50, 370; K. Bern-lo3 L. Nowicki and J. Pawelkiewicz, Bull. -4cad. polon. Sci., Ser. Sci. Biol., C1. 11,Biophys. Acta, 1962, 57, 599.164.83, 248.C1. 11, 1960, 8, 5.hauer, F. Wagner, and D. Wahl, Biochem. Z., 1961, 334, 279.1960, 8, 123FAWCETT: THE NICOTINAMIDE COENZYMES 413benzimidazole aquocobamide into the coenzyme, lo4 more detailed work hasrecently appeared. The co-factor requirements for the conversion of 5,6-dimethylbenzimidazolylcobamide cyanide or hydrate into the coenzyme incell-free extracts of Propioniibacterium shermanii include DPNH, GSH,Mn2+, ATP, and FAD,lO5 and confirmation has been obtained lo7 of anearlier finding 106 for similar systems from C.tetanomorphum that thecobalt-bound adenosine in the coenzyme is derived intact from ATP. Italso appears that 5,6-dimethylbenzimidazolylhydroxocobamide is an inter-mediate in the formation of the coenzyme from ~yanocoba1amin.l~~ Re-cently, reduction to the BIzr state was not observed with a more highlypurified enzyme system than previously used, and this is not consideredan obligatory intermediate in the enzymic conversion of cyanocobalamininto the coenzyme.losA. M. W.4. THE NICOTINAMIDE COENZYMES AND THEIR APOENZYMESSEVERAL surveys of this field have appeared during the period from 1959to 1961,1--s although only one related review has previously been presentedin Annual The present Report deals with the chemical and bio-logical properties of the nicotinamide coenzymes and of some of the well-characterised enzymes.The Coenzymes.-In recent reviews of the chemist,ry of the coenzymes,2athe addition compounds formed between nicotinamide adenine dinucleotide(NAD +) (1) and various nucleophiles are formulated either as covalent com-pounds or charge-transfer complexes, and this lack of definition is alsoassociated with many explanations of the biological processes in which thenicotinamide coenzymes are involved.New methods have appeared for the microestimation of the coenzymewhich involve using enzymic-cycling and fluorescent techniques, and forlo* J.Pawelkiewicz, B. Bartosinski, and N. Walerych, Acta Biochem. Polon.,1961, 8, 131; K.Bernhauer, P. Gaiser, 0. Muller, and 0. Wagner, Biochem. Z., 1960,333, 106.lo6 R. 0. Brady and H. A. Barker, Biochem. Biophys. Res. Comm., 1961, 4, 464.lo* A. Peterkofsky, B. Redfield, and H. Weissbach, Biochem. Biophys. Res. Comm.,1961, 3, 213.lo’ R. 0. Brady, E. G. Castanera, and H. A. Barker, J . Biol. Chem., 1962, 237,2325.lo8 H. Weissbach, B. G. Redfield, and A. Peterkofsky, J . Biol. Chem., 1962, 237,3217.Ciba Foundation Study Group No. 2, “ Steric Course of Microbiological Re-actions,” J. & A. Churchill Ltd., London, 1959.(u) N. 0. Kaplan, in “ The Enzymes,” ed. P. D. Boyer, H. A. Lardy, and K.Myrback, Academic Press, New York and London, 1960,2nd edn., Vol. 111, p. 105;E. M. Kosower, op. cit., p. 171; ( b ) B. L. Vallee, op.cit., p. 225.“ Sulphur in Proteins,” ed. R. Benesch et al., Academic Press, New York, 1959,Section IV.S. Shifrin and N. 0. Kaplan, Adv. Enzymol., 1960, 22, 337.S. F. Velick, in Light and Life,” ed. W. D. McElroy and B. Glass, The JohnsE. M. Kosower, “ Molecular Biochemistry,” McGraw-Hill Book Co. Inc., NewAnn. Reports, 1958, 55, 343.0. H. Lomy J . V. Passoneau, D. W. Schultz, and M. K. Rock, J. Biol. Chem.,Hopkins Press, Baltimore, 1961, p. 10s.York. 1962.1961, 236, 2746414 BIOLOGICAL CHEMISTRYthe separation of all fhe four coenzymes by chromatography on diethyl.aminoethylcellulose. The enzymic preparation of NADH has been furthermodified to give a more active product.lO The low resistance of all the co-enzymes to acid and alkaline treatment has been re-investigated l1 and shouldlead to the realisation that the oxidised and the reduced nicotinamide di-nucleotides must not be exposed to high or low pH.The complex series ofreactions which NADH undergoes in acid solution has been considerablyclarified. llC On spectrophotometric grounds, the initial product is thoughtto be the tetrahydro-6-hydroxynicotinamide dinucleotide (2) as had pre-viously been claimed from reactions of model compounds l2 although onereport claimed that 5-hydroxylation had occurred. l3 A second hydroxylgroup is then introduced at position 2 (3), giving a product which can existin tautomeric acyclic forms and which eventually liberates the dialdehyde(4) detected previ0usly.1~HO OrNHzF HRCO.NH2N OHI ‘HR( R = ADP- Ribose )The nature of the mysterious NADH-X remains uncertain. This isformed from NADH enzymically with 3-phosphoglyceraldehyde dehydro-genase in the presence of inorganic phosphate 15 or, more slowly, in a solution9 E.J. Pastore and M. Friedkin, J . Bwl. Chern., 1961, 236, 2314.lo K. Dalziel, Biochern. J., 1962, 84, 240.11 (a) 0. H. Lowry, J. V. Passoneau, and M. K. Rock, J . Biol. Chem., 1961, 236,2756; ( 6 ) I. G. Fels, Science, 1961,134,280; Nature, 1962,195, 704; (c) A. Stock, E. Sam,and G. Pfleiderer, Annalen, 1961, 647, 188.12A. G. Anderson and G. Berkelhammer, J . Arner. Chem. SOC., 1958, 80, 992.13 R. Segal and G. Stein, J., 1960, 6254.1 4 R. M. Burton, ref. 99 quoted in ref. 2a.15 S. Chaykin.J. 0. Meinhart, and E. G. Krebs, J . Bid. Ohem., 1956,220,811, 821FAWCETT : THE NICOTINAMIDE COENZYMES 415of high phosphate concentration.16 Its formation via a labile tetrahydro-6-phosphonicotinamide dinucleotide has been postulated. 110 Thia intermedi-ate 6-phospho-derivative must be closely related to the new phosphoryl-ated NAD derivative which accumulates when NAD f, inorganic phosphate,and succinate are incubated with mitochondriaY17 as it is reported that thenew compound decomposes to NAD+ and phosphate and also to a com-pound similar to the primary acid decomposition product of NADH. Detailsof the oxidation state of the intermediate are not clear. The existence ofthis type of intermediate was postulated in 1951 in a scheme involving apyridone dinucleotide,l8 since when several reports of its existence haveappeared 19 cumulating in the isolation of the compound mentionedabove.The existence of still more compounds related to, or derived from, NADHhas been revealed by the discovery of the appearance of a potent inhibitorof several dehydrogenase enzymes in frozen concentrated solutions of NADHor in solid samples exposed to a moist atmosphere, and even in fresh com-mercial samples.20 The initial suggestion that it was in fact adenosine&phosphate ribose, a breakdown product of both NAD+ and NADH, wasexcluded because of its weak inhibitory properties.The kinetic treatmentof the situation in which a competitive inhibitor is present in constant molarproportion to the coenzyme shows that the decrease in reaction velocity isgiven by the ratio of K , for the coenzyme to KI rather than by KI alone.Thus a very small amount of inhibitor could have a surprisingly large effectwhen NADH judged to be pure by its absorbency ratio at 260 and 340 mpis used, as has been found.lo Some light may have been shed on this situa-tion by the detection of small amounts of hydrogen peroxide in NADH solu-tions.21 The level of peroxide rose greatly on irradiation at 365 mp, or a thigher pH, and in the latter case storing the frozen solution caused a furtherincrease in peroxide content.It remains to be seen whether the peroxidegiving rise to the inhibitor, is formed simultaneously, or is, in fact, at allrelated to it.Further work on the chemical properties of pyridine derivatives con-tinues to give information concerning the mechanism of the enzyme-cata-lysed reaction and has been recently reviewed.22 By using l-alkoxynicotin-amide compounds it has been shown that the dielectric constant of thesolvent significantly promotes addition of cyanide to the 6-position of nicotin-amide. 23 Interesting descriptions of the participation of model compoundsl6 G. Pfleiderer and A.Stock, Biochem. Z., 1962, 336, 66.l7 D. E. GrifKths and R. A. Chaplain, Biochem. Biophys. Res. Comnm., 1962, 8,497, 501.N. 0. Kaplan, in “ Phosphorus Metabolism,” ed. W. D. McElroy and B. Glass,The Johns Hopkiris Press, Baltimore, 1951, Vol. I, p. 428.lD G. B. Pinchot, PTOC. Nat. Acud. Sci. U.S.A., 1960,46, 929; J.L. PurviS, Biochim.Biophys. Acta, 1960, 38, 435; G. B. Pinchot and M. Hormanski, Proc. Nat. Acad. Sci.U.S.A., 1962, 48, 1970.2o K. Dalziel, Biochem. J., 1961, 80, 440; C. P. Fawcett, M. M. Ciotti, and N. 0.Kaplan, Biochim. Biophys. Acta, 1961, 54, 210; P. E. Strandjord, K. J: Clayson, andE. F. Freier, Fed. Proc., 1962, 21, 239.21 M. I . D o h , Biochim. Biophys. Acta, 1962, 63, 219.22 F. H. Westheimer, Adv. Enzymol., 1962, 24, 441.2s Y . Kagawa, J . Biochem. (Japan), 1960, 47, 104416 BIOLOGICAL CHEMISTRYin oxidation and reduction reactions include the reduction of an olefinicdouble bond,24 analogous to the enzymic hydrogenation of androstenedioneto androstanedione by NADPH;25 the reduction of sulphite to hydrogensulphide involving addition to the nicotinamide 6-position, 26 and a briefreport on the complex stereochemistry involved in a model transhydrogenasesystem in which hydrogen is transferred from dihydro- 1 -propylnicotinamideto NAD+.27The relation of ring substitution and electron affinity of a pyridine ringto the wavelength of maximal absorption of the charge-transfer band ofalkylpyridinium iodides has been investigated.28 The suggestion that thebroad absorption band observed when NAD+ is bound to glycersldehyde3-phosphate dehydrogenase may be due to a charge-transfer complex 29 hasreceived new experimental support ;3O the criticism 31 of earlier evidence 32remains valid as it emphasises the dangers of observing artificial spectrawhen difference spectra of concentrated solutions are measured.Coenzyme modi$cations.There now exists a series of enzymically pre-pared coenzyme analogues containing various 3-substituted pyridine groupsin place of ni~otinamide.~~ In general, their chemical properties and bio-logical activities can be correlated with the ability of the 3-substituent toconjugate with the pyridine ring, as is shown in the respective l-methyl-pyridinium bases,34 although these model compounds do not duplicate theinductive effect on the pyridine ring in a riboside 5’-phosphate. The activityshown by these analogues indicates that the 3-amide group in the coenzymerepresents a convenient biological adaptation of the nicotinic acid precursor,to give a small unreactive carbonyl group contributing to the overall electrondistribution of the nicotinamide ring, in both oxidised and reduced forms,requisite for its coenzymic r81e.These analogues have proved to be valuabletools in studies on dehydrogenase differentiation and evolution. 35 Addi-tions to this series include the Fi-amino-, &methyl-, and 4-methyl-nicotin-amide analogues,36 all of which are inactive as coenzymes. Several otheradenine dinucleotides have been prepared containing tertiary bases other24 B. E. Norcross, P. E. Klinedist, jun., and F. H. Westheimer, J. Amer. Chem.25 J. S. McGuire and G. M. Tomkins, Fed. Proc., 1960, 19, 29.26 K. Wallenfels and D. Hofmann, Tetrahedroh Letters, 1962, 151.27 J. Ludoweig and A. Levy, Fed. Proc., 1962, 21, 239.28 E. M. Kosower, J. A. Skorcz, W.M. Schwarz, jun., and J. W. Patton, J. Amer.Chem. Soc., 1960, 82, 2188; E. M. Kosower and J. A. Skorcz, ibid., p. 2195; E. 31.Kosower, D. Hofmann, and K._Wallenfels, ibid., 1962, 84, 2755.2gE. M. Kosower, J. Amer. Chem. SOC., 1956, 78, 3497.30G. Cilento and P. Tedeschi, J. Biol. Chem., 1961, 236, 907; F. Ungar andS. G. A. Alivisatos, Biochim. Biophys. Acta, 1961, 51, 361.31 C. Remily and R. G. Wolfe, Biochem. Biophys. Res. Comm., 1960, 3, 457.32 G. Cilento and P. Giusti, J. Amer. Chem. SOC., 1959, 81,3801; S. G. A. Alivisatos,G. A. Mourkides, and A. Jibnil, Nature, 1960, 186, 718.33 (a) N. 0. Kaplan and M. M. Ciotti, J. Biol. Chem., 1956, 221, 823; ( b ) B. M.Anderson, C. J. Ciotti, and N. 0. Kaplan, ibid., 1959, 234, 1219; (c) B. M.Andersonand N. 0. Kaplan, ibid., p. 1226.34 M. R. Lamborg, R. M. Burton, and N. 0. Kaplan, J. Amer. Chem. Soc., 1957,79, 6173.35 N. 0. Kaplan, M. M. Ciotti, M. Hamolsky, and R. E. Bieber, Science, 1960,131, 392.36 P. Walter, Fed. Proc., 1962, 21, 240.Soc., 1962, 84, 797FAWCETT : THE NICOTINAMIDE COENZYMES 417than pyridine derivatives, such as imidazoles 37 and thiadiaz~les.~~ Anexciting application of this type of compound is the coupling of the 4-methyl-5-2’-hydroxyethylthiazole adenine dinucleotide to horse-liver alcohol de-hydrogenase.39 This was accomplished by opening the thiazole ring underalkaline conditions and forming a disulphide bridge with a thiol group ofthe enzyme. Evidence from the method of formation and the inhibition byNADf indicate that the enzyme-thiol group involved in the dinucleotidedisulphide is normally responsible for coenzyme binding, and isolation ofthe appropriate peptide fragments after hydrolysis may lead to identificationof the primary structure a t part of the coenzyme binding site.It is cer-tainly remarkable that the molar ratio of the adduct (if maximal) approachedthe number of coenzyme-binding sites per mole of enzyme (two). In viewof the number of free thiol groups in this enzyme, demonstration of theabsence of disulphide formation between the thiazole analogue and thiolgroups of a protein other than a dehydrogenase seems desirable.Further modifications of NAD + have been made in the adenine nucleotidepart of the molecule in an attempt to discover the r81e of this portion inenzyme-coenzyme association and, indeed, in any nucleotide-protein inter-action.These new nicotinamide dinucleotides contain 2’-deoxyadeno-~ine~~O-42 hypoxanthine,43 guanine,42, 44 cytosine,42 42 1-2’-h ydroxyethyladenosine , 45 6 - 2’- hydroxyet hylaminopurine , and 6 -mercapt o -p~rine.~6 Exact comparison of the coenzymic activities of these compoundsis diEicult owing to differences in assay conditions, but some fundamentalfacts arise concerning the requirements of the better-known dehydrogenases,Horse-liver alcohol dehydrogenase shows little sensitivity to replacement ormodification of adenine unless the assay is carried out at a pH which causespositive or negative charges on the “ new ” residue. In contrast, the yeast-alcohol dehydrogenase is inactive with analogues containing modificationsin the adenosine part of the coenzyme ex-Ingeneral, the requirements of the lactic andthe glutamic dehydrogenase lie between theextremes of the two alcohol dehydrogenases.The greatly decreased activity of the 2’-de-points to a conformational difference between adenosine and 2‘-deoxy-cept a t the extranuclear amino-group.HO OH ---..-N> N NH2 c:?% H 0 . Woxyadenosine analogue is surprising and (5)37 S. G. A. Alivisatos, L. Lamantia, and B. L. Matijevich, Biochim. Biophys.38 M. M. Ciotti, N. 0. Kaplan, A. Goldin, and S. R. Humphreys, Proc. Amer.39 J. van Eys, R. Kretszchner, W. S. Tseng, and L. W. cunningham, jun., Biochem.40 H. Klenow and B.Anderson, Biochim. Biophys. Acta, 1957, 23, 92.41 C. P. Fawcett and N. 0. Kaplan, J . Biol. Chem., 1962, 237, 1709.42M. Honyo, Y. Furukawa, H. Moriyama, and K. Tanaka, Chem. and Pharm.43 F. Schlenk, F. Hellstrom, and H. von Euler, Ber., 1938, 71, 1471; N. 0. Kaplan,44 M. R. Atkinson, J. F. Jackson, and R. K. Morton, Nature, 1961, 192, 946.4 5 H. G. Windmueller and N. 0. Kaplan, J . Biol. Chem., 1961, 236, 2716.46 M. R. Atkinson, J. F. Jackson, and A. W. Murray, Nature, 1962, 198, 35.Acta, 1962, 58, 201, 209.Assoc. Cancer Res., 1958, 2, 287.Biophys. Res. Comm., 1962, 8, 243.B d l . (Japan), 1962, 10, 73.S. P. Colowick, and M. M. Ciotti, J . Biol. Chem., 1952, 194, 579.418 BIOLOGICAL CHEMISTRYadenosine, possibly due to hydrogen-bond interaction between the 2’-hydroxyl and N-3 of adenine ( 5 ) , as was previously suggested.47 I naddition, differences in the nuclear magnetic resonance spectra of ribo-nucleosides and 2’-deoxyribonucleosides also indicate considerable varia -tion in the pentose ring.48 Inhibition of dehydrogenase activity by coen-zyme analogues has so far been reported to occur only with some of thedinucleotides containing nicotinamide variations 33c, 49 and not with thosemodified in the adenosine group.Evidence for a folded conformation of NADH and its implications hasbeen discussed elsewhere;2a, 5 evidence for a similar shape in the NAD+molecule has been obtained from the electronic interactions in the hmino-nicotinamide adenine dinucleotide, as shown by its fluorescent properties.36The influence of the folded conformation of NADH is seen in its nuclearmagnetic resonance spectrum where the resonance position of the 4-hydrogenatoms is shifted when compared with that of the l-benzylnicotinamidemodel.50 The equivalent resonance of the two hydrogen atoms was, takento mean that the dihydronicotinamide ring is either planar or undergoingrapid interconversion between two boat forms.Further evidence for plan-arity of the ring comes from a study of 1,4-dihydropyridines in which theinherent stabilisation of their n-electrons lowers their basicity compared withthat of other reduced trimethylpyridine compound^.^^ The use of the fluor-escence of NADH to measure its binding to enzymes and for kinetic studies S2has been extended to measurement of polarisation of coenzyme fluorescencefor following complex formation between enzyme and c0enzyme;~3 and ithas been adapted for studying the behaviour of reduced nicotinamide nucleo-tides in suspensions of cellular preparations 54 and in tissues in viv0.55 Thephenomenon of the shift towards lower wavelengths and intensification ofthe coenzyme fluorescence in the presence of enzyme has now been observedwith lactic,5Oa rnalic,5@ and isocitric dehydrogena~es.5~~Of exceptional interest is the determination of the absolute stereochemi-cal configuration at the nicotinamide 4-position in NADH.Comparison ofthe optical rotatory dispersion curves of the deuterosuccinic acids obtainedby degradation of two samples of NADH deuterated at the 4-position onside A and side B, with the curve obtained from a sample prepared inde-pendently and of known absolute configuration, decided between the alter-4 7 P.C. Zamecnik, Biochem. J., 1962, 85, 257.4 8 C. D. Jardetsky, J. Amer. Chem. SOC., 1960, 82, 229; R. U. Lemieux, Canad.49 P. Walter, personal communication.50 W. H. Meyer, H. R. Mahler, and R. H. Ba.ker, jun., Biochim. Biophys. Acta,5l E. M. Kosower and T. S. Sorensen, J. Org. Chem., 1962, 27, 3764.52 H. Theorell and A. D. Winer, Arch. Biochem. Biophys., 1959,83,291; H. Theorell,A. P. Nygaard, and R. Bonnichsen, Acta Chem. Scand., 1955, 9, 1148.53 G. Weber, Adv. Protein Chem., 1953, 8, 415; S. F. Velick, J. Biol. Chem., 1958,233, 1455.5 4 B. Chance and H.Baltchefsky, J. Biol. Chem., 1958, 233, 736; Y. Avidor,J. M. Olson, M. D. Doherty, and N. 0. Kaplan, ibid., 1962, 237, 2377; P. Estabrook,Analyt. Biochem., 1962, 4, 231.Langan, ibid., 1960, 14, 933; (c) T. A. Langan, ibid., p. 936.J . Chem., 1961, 39, 116.1962, 64, 353.55 B. Chance, P. Cohen, F. Jobsis, and B. Schoener, Science, 1962, 136, 325.5 6 (a) A. Carlstrom, Acta Chem. Scund., 1961, 15, 2049; ( b ) H. Theorell and T. AFAWCETT : THE NICOTINAMIDE COENZYMES 419natives for sides A and B of the ring and enabled the following rule to bestated: " When an enzyme of class A transfers hydrogen from a substrateto a nicotinamide nucleotide, the hydrogen is added to that side of thenicotinamide ring on which the ring atoms 1 to 6 appear in anticlockwiseorder." 57Different Forms of the Enzymes.-While detailed consideration of thisphenomenon is outside the scope of this Report, attention is drawn to theevidence that an NAD+-dependent reaction of a given substrate can becatalysed by different enzyme molecules.These enzymes have been collec-tively referred to as heteroenzyme~~5~ and are obtained from unrelatedsources. Differences between the heteroenzymes have been proved both forstructure and catalytic acti0n.~5, 59 A discrete source is, of course, of para-mount importance in obtaining a supposedly pure enzyme; however, a fur-ther complication arises from the heterogeneity of even crystalline enzymesobtained from one tissue of a single species.58, 59 The micro-componentshave been termed isozymes.60 The differences between the isozymes aremore subtle than between the heterozymes and until recently were demon-strable solely by electrophoresis on paper or on solid supporting media.These techniques 6 1 are much used in the search for isozymes, although' artificial enzyme heterogeneity, due to charge differences caused by associa-tion of metal ions 62 or a foreign protein,63 has been demonstrated.Therehave also been reports of misleading observations of heterogeneity whendehydrogenase detection was carried out by coupling the enzymic reactionto dye formation,64 a nzethod often used on electropherograms of rathercrude preparations.Differences in the amino-acid composition of the lactic dehydrogenaseisozymes have recently been reported, thus proving that they are not pre-parative artefacts, and confirming previous reports of differences in physicaland kinetic characteristics.The relations established between the isozymesare more significant than their differences, as has already been suggested.After the order in a given series of isozyrnes has been established on the basisof charge differences, it has been found that without exception each of theproperties studied changes in a regular way throughout that isozyme pat-tern.5s, 65 The isozymes of a given lactic dehydrogenase have been shownto have the same molecular weight 66 and to be dissociable into four sub-units, also of equal molecular weight but possibly of two different chargetypes, by the action of guanidine hydrochloride.67 Immunological evidence6 7 J.W. Cornforth, G. Ryback, G. PopjBk, C. Donninger, and G. Schroepfer,6 8 T. Wieland and G. Pfleiderer, Angew. Claem., 1962, 74, 261; Internat. Edn.,5s Several papers in Ann. N.Y. A c d . Sci., 1961, 94, Article 3, p. 655.6 o C. L. Markert and F. Moller, Proc. Nut. Acad. Sci. U.S.A., 1959, 45, 753.61 0. Smithies, Adv. Protein Chew., 1959, 14, 65.6 2 D. C. Watts and C. Donninger, Analyt. Biochem., 1962, 3, 489.63 G. W. Schwert, D. B. S. Millar, and Y. Takenaka, J. Biol. Clzem., 1962, 237,6 4 E. S. Vesell and A. G. Bearn, J. Gen. Physiol., 1962, 45, 553.6 6 R. D. Cab, N. 0. Kaplan, L. Levine, and E. Zwilling, Science. 1962, 136, 962.8 6 E. Appella and C. L. Markert, Fed. Proc., 1962, 21, 253.6 7 E.Appella and C. L. Markert, Biochem. Biophys. Res. Cmm., 1961, 6, 171.Biochem. Biophys. Res. Comm., 1962, 9, 371.1962, 1, 169.2131420 BIOLOGICAL CHEMISTRYand studies with coenzyme analogues indicated two extreme types of acti-vity with three intermediate types in a pattern of five isozymes.65 Thesefindings led to proposals that each of the five is a hybridised tetrad of twotypes of subunit.Much of the above discussion a t present applies only to the lactic dehydro-genases, although isozymes have also been detected of malicY6* isocitric,69and glutamic dehydrogenases. 70 It therefore seems that selection of anenzyme for chemical study must be preceded either by demonstrationof the absence of isozymes or their separation by the recommendedmeth0ds.6~~ 6gb, 71Horse-liver alcohol dehydrogenase.The standard commercially availablepreparation of this enzyme is used by most investigators for preliminary orqualitative work although further purification by chromatography has beendescribed. 72 Complete amino-acid composition is not yet available although3-2 molecules of tryptophan 73 and 28 free thiol groups have been determinedper molecule of enzyme.72 While multiple forms of this enzyme have notbeen detected, a second alcohol dehydrogenase has been found in liver.Unlike the standard preparation this enzyme is capable of oxidising 2-fluoro-ethanolY7* and it thus seems to be important to demonstrate by using thechromatographically purified enzyme that the dismutation and isomerisa-tion activities attributed to horse-liver alcohol dehydrogenase are in factdue to the same protein.The enzyme thiol groups have received further attention from severalviewpoints.The use of optical rotatory dispersion techniques has shownthat previous observations of inactivation and inhibition of coenzyme bind-ing by p-chloromercuribenzoate is caused by alterations in protein tertiarystructure, which is normally maintained, at least in part, by thiol groups.76The appearance of a Cotton effect during the titration of enzyme with co-enzyme mas used to determine that 2 moles of coenzyme are bound per moleof enzyme. This was confirmed by fluorescence titration of the enzyme andcoenzyme in the presence of an excess of isobutyramide, although atten-tion was drawn t o the diaculty experienced in determining an accuratevalue of enzyme c~ncentration.~~ The binding of zinc is thought to involvea dimercaptide structure,78 and it has been suggested that an enzyme thiolgroup may add to the nicotinamide 6-position in the enzyme-coenzymecomplex.77 The enzyme shows an unusual pH-independence in its reac-6 8 (a) E.S. Vesell and A. G. Beam, Ann. N.Y. Acad. Sci., 1958,75,286; (b) H. Boser6 D J. L. Bell and D. N. Barron, Biochem. J , , 1962, 82, 5P.7 0 H. J. van der Helm, Nature, 1962, 194, 773.7 1 B. Hess and 8. I. Walter, Klin. WoschenschriJt, 1960, 38, 1080; J. S. Nisselbaum,7 a K. Dalziel, Biochem. J., 1961, 80, 440.73P. M. Harrison and T. Hofman, Biochem. J., 1961, 80, 38P.7 4 D. H. Treble, Biochem.J., 1962, 82, 129.75 R. H. Abeles and H. A. Lee, jiin., J. Biol. Chem.., 1960, 235, 1499; J. van Eys,J . Bid. Chem., 1961, 236, 1531; N. K. Gupta and W. G. Robinson, Fed. Proc., 1962,21, 251.7 6 T. K. Li, D. D. Ulmer, and B. L. Vallee, Biochemistry, 1962, 1, 114.7 7 J. S. McKinley-McKee, Biochern. J., 1962, 84, 70P.78R. Druyan and B. L. Vallee, Fed. Proc, 1962, 21, 247.and G. Pawelke, Naturwiss., 1961, 48, 572.Fed. Proc., 1962, 21, 253FA4WCETT : THE NICOTINAMIDE COENZYMES 421tion with iodoacetate which is probably due to special properties of its thiolThe correlation of the changes in optical rotation, fluorescence, and acti-vity of the enzyme caused by heat and urea has emphasised the importanceof secondary and tertiary protein structure to dehydrogenase function andcoenzyme binding.80 Fluorescence enhancement also gave evidence for aternary complex between enzyme, coenzyme, and urea which was possiblyof the type observed with isobutyramide 81 and previously noted in kineticexperiments.82Considerable effort has been devoted to determining the validity of theTheorell-Chance mechanism for this enzyme.This describes a compulsoryinitial association of enzyme and coenzyme followed by. instantaneous inter-conversion of the ternary complexes formed with substrate.83 A series oftheoretical relations between the kinetic parameters has been derived forthis mechanism,84 and subjected to experimental verifi~ation.~~-~' By com-paring data from kinetic experiments with two different substrates it hasbeen shown that the values of certain of the kinetic coefficients are inde-pendent of substrate, suggesting steps common to the two reactions.Thesecould be only the formation and breakdown of the enzymecoenzyme com-plexes, and accordingly their dissociation velocities have been shown tocontrol the maximum rate. Good agreement had also been obtained betweenthe dissociation constants for enzyme and coenzyme, and the equilibriumconstant for the overall process, when calculated from the results of kineticexperiments together with the theoretical relations for the simple mechanism,and when determined by direct measurement. Kinetic discrepancies led tothe consideration of other mechanisms involving alternate pathways withenzyme-substrate intermediates and the formation of inactive enzyme-coenzyme complexes.The observation of an isotope effect on the bindingconstant for NADH labelled at position 4 suggested an interaction betweenthe hydrogen to be transferred and the enzyme. s7c Attempts to demonstratethis revealed an apparent exchange of the label from reduced coenzyme toalcohol firmly bound to the enzyme.88 This probably occurred throughminute contamination of NADH by NAD+ which would then initiate acyclic process. This order of contamination of coenzymes by their oppositeform or by breakdown products seems almost impossible to overcome andhas been invoked to explain other experimental discrepancies such that theTheorell-Chance mechanism is now considered valid for this enzyme.89groups.'97 9 L. Genevois and J. Larroqu&ne, Compt. rend., 1962, 255, 2523.8o L. Brand, J. Everse, and N. 0. Kaplan, Biochemistry, 1962, 1, 423.81 H. Theorell and J. S. McKinley-McKee, Acta Chem. Scand., 1961, 15, 1811.8 2 K. V. Rajopalan, I. Fridovich, and P. Handler, J. Biol. Chem., 1961, 236, 1059.83 H. Theorell and B. Chance, Acta Chem. Xcand., 1951, 5, 1127.84 K. Dalziel, Acta Chem. Xcand., 1957, 11, 1706.85 H. Theorell and J. S. McKinley-McKee, Nature, 1961, 192, 47; Acta Chem.Scand., 1961, 15, 1797.K. Ddziel, Ezochem. J., 1962, 84, 244.(a) R. H. Baker, jun., and H. R. Mahler, Biochemistry, 1962, 1, 35; ( b ) R. H.Baker, jun., ibid., p. 41; ( c ) H. R. Mahler, R. H. Baker, jun., and V. J. Shiner, ibid.,88 V.P. Fernandez, H. R. Mahler, andV. J. Shiner, jun., Biochemistry, 1962, 1, 259.89 K. Dalziel, Biochem. J., 1962, 84, 69P.p. 47422 BIOLOGICAL CHEMISTRYThe structure of the transient ternary complex has been described inseveral ways differing froin one another mainly on the r61e of ~inc.2~ Com-petitive experiments with metal-binding inhibitors have been interpreted toshow that zinc binds either the coenzyme 87c or the coenzyme andsubstrate (6).91 Observations of inhibition by inorganic ions and othermonodentate ligands are best explained by the latter theory.91, 92 The(Reproduced, by permission, from Acta Chem. Scand., 1961, 15, 1863.)opinion that zinc is not concerned in binding the coenzyme pyrophosphategroup depends on the observation that the enzyme is not inhibited by pyro-phosphate,93 which is quite a different ion from that of the coenzyme.Ananalogy for the binding r61e of zinc is shown by the ease of formation g4 ofthe complex salt [Pyridinium]+Zn2+[PO4]3--, and in the existence of 1 : 1chelates between tetrahedral Zn2 + and adenosine 5’-phosphate, involvingpurine and phosphate gr0ups.9~ It should be pointed out, however, thatthe residual charge on the zinc is not known and may be zero if the metal istightly bound to the protein as a dimer~aptide.~~(7)(Reproduced, by permission, from Biochim. Biophys. Acta, 1962, 56, 477.)B. L. Vallee and T. L. Coombs, J. Biol. Chern., 1959, 234, 2615.g l R . A. Plane and H. Theorell, Acta Chem. Scand., 1961, 15, 1866.g2 H. Theorell and J.S. McKinley-McKee, Acta Chena. Scand., 1961, 15, 1834.g3 K. Wallenfels and H. Sund, Biochem. Z., 1957, 8, 329.Q* H. Buss, H. W. Kohlschutter, and W. Ploger, 2. Naturforsch., 1962, 17b, 420.g6 M. M. Taqui Khan and A. E. Martell, J . Amer. Cheni. SOC., 1962, 84, 3307FAWCETT: THE NICOTINAMIDE COENZYMES 423There have been two proposals that quaternary amino-groups are in-volved in binding substrate and coenzyme. Evidence for substrate bindingdepends on inhibition of enzyme action by Roussin’s salt, purported to reactspecifically with such groups,96 and on equilibrium dialysis studies with sp-thetic p0lymers.9~ Evidence for distant interaction between coenzyme anda positively charged amino-group depends on the comparison of the spectralshift observed in the enzyme-NADH complex with that caused by the pres-ence of a quaternary nitrogen atom near an ap-unsaturated ketone system.Postulated zinc-nicotinamide interactions through the amide group havebeen criticised on the grounds of the direction of the spectral shift, and atransition complex has been proposed in which substrate and coenzyme areheld in juxtaposition by quaternary ammonium group (7).98Yeast-alcohol dehydrogenuse.The r81e of zinc in this enzyme is rathermore complex and has been discussed at length The observa-tion that rapid inactivation by metal-chelating agents was retarded by addi-tion of NAD, supported its coenzyme-binding function. Subsequently aslower inactivation by 1 ,lo-phenanthroline, not reversed by coenzyme, hasbeen demonstrated and shown to be accompanied by dissociation into foursub~nits.~Q Similar results were obtained for the action of silver ion andp-chloromercuribenzoate, namely, instantaneous inhibition followed by dis-sociation.loo, 78 This phenomenon of dissociation into inactive subunits is nowcommon among the larger dehydrogenases, and has also been brought aboutby the action of the detergent, sodium dodecyl sulphate, on this enzyme.lo1Optical rotatory dispersion has been used to distinguish between the typeof denaturation caused by urea or alkali and the inhibition caused by 1,lO-phenanthroline.lo2 The resistance of this enzyme t o heat and to treatmentwith urea has been found to be sigdicantly less than that of the horse-liverenzyme,80 but it is not known whether this is connected with the dissociationphenomenon.Further studies on the properties of the thiol groups of this enzyme haverevealed that four, out of a total of twenty-four, are particularly reactive toiodoacetamide.The rate of enzyme inactivation caused by iodoacetamidewas found to be independent of pH over a surprisingly wide range (cf.ref. 79) ; moreover, it was found to be retarded by the coenzymes, yet acceler-ated by acetaldehyde alone. These findings were incorporated into a novelreaction mechanism for alcohol dehydrogenases involving the covalentassociation of NADH with a thiol group whose nucleophilicity is enhancedby hydrogen bonding to an imidazole. It is proposed that the same imid-azole is involved in acetaldehyde binding.103Lactic acid dehydrogenase. Beef heart is the most common source of thisenzyme, and further details have appeared of its purification by chromato-O 6 A.D. Duclaux, Biochim. Biophys. Acta, 1960, 39, 33, 44.O 7 A. D. Duclaux, Biochim. Biophys. Acta, 1961, 54, 76, 84.O * E. M. Kosower, Biochim. Biophys. Acta, 1962, 56, 474.sa F. L. Hoch, R. J. P. Williams, and B. L. Vallee, J . Biol. Chem., 1958, 232, 453;loo P. J. Snodgrass, B. L. Vallee, and F. L. Hoch, J . BioZ. Chem., 1960, 235, 504.lol R. T. Hersh, Biochim. Biophys. Acta, 1962, 58, 353.lo2 D. D. Ulmer and B. L. Vallee, J . BioZ. Chem., 1961, 236, 730.lo3 B. R. Rabin and E. P. Whitehead, Nature, 1962, 196, 658.J. H. R. Kagi and B. L. Vallee, ibid., 1960, 235, 3188424 BIOLOGICAL CHEMISTRYgraphy on hydr~xypatite.~~ This method yields a preparation claimed tohave a monomeric unit with a molecular weight of 72,000 which undergoesdimerisation, dependent on ionic strength and protein concentration.104Electrophoretically obtained lactic dehydrogenase isozymes have a molecularweight of twice this figure and, as mentioned above, are dissociated into foursubunits by the action of guanidine hydrochloride and high urea concentra-t i ~ n . ~ ~ , 67 The enzyme was found not to be protected from denaturation byurea or from chymotryptic digestion by the presence of coenzyme, althoughfluorescence measurements indicated protection against the action of trypsinand nagarse.lo5 The effects of increasing urea concentration on the sedi-mentation, diffusion, and optical rotatory properties of the pig-heart enzymehave been interpreted in terms of an initial aggregation which is then reversedas denaturation occurs.The aggregation is thought to be due to greateropportunity for intermolecular hydrogen bonding during the gradual openingof the molecule caused by changes in electrostatic interactions. l o 6 This maybe contrasted with interpretations of the effect of dimethylformamide on3-phosphoglyceraldehyde dehydrogenase. It is suggested that loosening ofthe molecule is due to increased solvation of apolar side chains.lo7 Thirteenthiol groups per unit of molecular weight 115,000 have been reported for thepig-heart enzyme, of which only three are essential for activity; these threealso have the ability to transfer p-chloromercuribenzoate to other non-essential thiol groups.lo8The results of kinetic studies, by product-inhibition methods, on theenzyme from rabbit muscle supported a mechanism of the alcohol-dehydro-genase type.lo9 Workers using deuterated NADH have found an isotopeeffect on the kinetic constants relating to maximum rate which cannot beexplained on the basis of this mechanism, as rate is supposedly determined bythe final dissociation of the coenzyme, a step which does not involve theisotope. loUltracentrifugal studies have verified that enzyme inhibitors related tothe substrate can form links t o the enzyme only if coenzyme is first bound,and then in molar ratio.1ll The design of inhibitors of lactic dehydro-genase for chemotherapeutic purposes has been used in another explorationof the active site.The inhibitors, also related to the substrate, are modifiedin size and stereochemistry so that an outline of the site may be con-structed.112 Finally, mention should be made of the novel use of photo-oxidation with Methylene Blue of histidine and tryptophan residues in lacticdehydrogenase and its effect on coenzyme binding.ll3lo4 D. 13. S. Millar, J. Biol. Chern., 1962, 237, 2135.lo5 R. H. McKay and N. 0. Kaplan, Biochim. Biophys. Acta, 1961, 52, 156.lo6 R. Jaenicke, G. Pfleiderer, and T. Wieland, Biochem. Z., 1962, 336, 107.lo' P. Elodi, Acta Physwl. Acad. Sci. Hung., 1961, 20, 311.108 W. Gruber, K. Warzecha, 0. Pfleiderer, and T.Wieland, Biochem. Z., 1962,109 V. Zewe and H. J. Fromm, J . Biol. Chem., 1962, 237, 1668.l 1 0 J. F. Thomson and J. J. Darling, Biochem. Biophys. Res. Cmm., 1962, 9, 334.ll1 W. B. Novoa and G. W. Schwert, J . Biol. Chem., 1961, 236, 2150.112 B. R. Baker, W. W. Lee, W. A. Skinner, A. P. Martinez, and E. Tong, J . Mediciiz.113 D. Robinson and D. Stollar, Fed. Proc., 1962, 21, 232; D. B. S. Millar and336, 107.Pharmaceut. Chem., 1960, 2, 633.G. W. Schwert, ibid., p. 233FAWCETT: THE NICOTINAMIDE COENZYMES 425It has been reported that the properties of pig-heart enzyme preparations vary as a result of certain treatments normallyincorporated in standard procedures for enzyme isolation. Evidence hasbeen presented that the changes are due to modifications in the tertiarystructure of the enzyme.ll* The protein is also thought to have a particu-larly high content of a-helix.115 Some disagreement exists concerning thenature of the malic dehydrogenase obtained from other tissues. Homo-genates of beef heart and rat liver each yield two enzymes differing in cata-lytic properties and composition, and a previous report of conversion fromone to the other by butanol-extraction was not confirmed when characteristicinhibition properties were examined, although a decrease in molecular weightwas noted,ll6' Similarities in composition and in kinetic properties werefound during a detailed survey of malic dehydrogenases from differentsources.116b Studies of the kinetic mechanism of the pig-heart enzymeshow that it also involves initial binding of the coenzyme, whose final dis-sociation then appears to determine the overall rate.It was pointed out thatvariation in kinetic constants with pH can be due both to participation ofhydrogen ion as a reactant and to the effects due to ionisation of groups onthe enzyme.l17It is now considered that the value of lo6obtained for the molecular weight of the beef-liver enzyme represents atetramer. This form is associated with maximum glutamic dehydrogenaseactivity 118 although one report has appeared to the contrary.l19 Thechicken-liver enzyme has a molecular weight of about 0.5 x lo6 and is lessable to undergo aggregation.120 The beef enzyme appears to have an innateability to catalyse oxidative deamination of structurally related amino-acids,121 although its substrate specificity may also be influenced by its stateof aggregation.llsb This phenomenon is not well understood at present.The aggregation is influenced by many factors including enzyme concentra-tion and even the presence of the reduced coenzyme.Great care mustaccordingly be observed when results of different experiments are compared,as the number and type of binding sites are thought to be changed by thisaggregation.122 The influence of 1,lO-phenanthroline on the state of aggre-gation was originally interpreted on the basis of its zinc-chelating properties ;a similar effect can be brought about, however, by other polycyclic com-pounds such as steroid hormones and phenanthridine, known to be incapableMaZic dehydrogenase.GEutamic dehydrogenme.114 B.K. Joyce and S. Grisolia, J . Biol. Chem., 1961, 236, 725.115 B. Jirgensons, Photochem. Photobiol., 1962, 1, 59.116 (a) 1;. Siege1 and S. Englard, Biochim. Biophys. Acta, 1961, 54, 67; F. G. Grimmand D. G. Doherty, J . Biol. Chem., 1961, 236, 1980; ( b ) C. J. R. Thorne, Biochim.Biophys. Acta, 1962, 59, 624.11' D. N. Raval and R. G. Wolfe, Biochemistry, 1962, 1, 263, 1112, 1118.(a) H. Kubo, M. Iwatsubo, H. Watari, and T. Soyama, J . Biochem. (Japan),1959, 46, 1171; C. Frieden, J . Biol. Chem., 1962, 237, 2396; ( b ) G. M. Tomkins, K. L.Yielding, and J. Curran, Proc. Nut. Acad. Sci. U.S.A., 1961, 47, 270; S. Grisolia,M. Fernandez, R. Amelunxen, and C. L. Quijada, Biochem.J., 1962, 85, 568.119 H. F. Fisher, D. G. Gross, and L. L. McGregor, Nature, 1962, 196, 895.lZo C. Frieden, Biochim. Biophys. Acta, 1961, 63, 421.121 J. Struck and I. W. Sizer, Arch. Biochem. Bwphys., 1959, 86, 260..l z 2 C. Frieden, Biochim. Biophys. Acta, 1961, 47, 428; G. M. Tompkins, K. L.Yielding, and J. F. Curran, J . Biol. Chem., 1962, 237, 1704426 BIOLOGICAL CHEMISTRYof zinc-chelation and having an effect not destroyed by addition of zincbut destroyed by addition of ADP,123 as is the dissociation brought aboutby thyroxine and tri-iod0thyr0nine.l~~ The levels of the hormones requiredto promote dissociation make it unlikely that their effects are of physio-logical significance ; nevertheless the effect 05 ADP, the stimulation of acti-vity by other amino-a~ids,~~~ and the inhibition by guanosine nucleo-tide~,1~~3 126 may yield clues to the metabolic control of this enzyme.Presentexplanations of these observations visualise activating and inhibiting sitesfor nucleotides as well as the catalytic site.Irreversible dissociation of this enzyme into many subunits has beenachieved by severe “ physical” treatment such as heat, urea, deter-gent,11sa9 1243 127 and extremes of pH,128 to disturb the inter-chain bonds.C. P. F.5. METABOLISM OF STEROID HORMONESTHE pathways of steroid anabolism and catabolism have been investigatedextensively over the last few years, and the general pattern now seemsfairly well established. However, much is still to be learned concerning thedetails of the various stages, and the quantitative aspects of alternativepathways.Further, little is known about the details of steroid metabolismin the foetus and new-born. Considerable interest also attaches to theelucidation of metabolic errors, and studies of aberrations in biosyntheticmechanisms have yielded information of both clinical and fundamentalvalue.For several years much endocrine research has had the aim of assessingthe hormonal status of patients with endocrine or other disease: extensivestudies of urinary steroid metabolites have been made, and some progresshas been achieved. Administration of labelled hormones offers the possi-bility of revealing specific urinary metabolites and of assessing their rateof secretion of various steroids by endocrine tissues.A complementaryapproach arose from the concept that metabolic activity may be related toplasma concentration of hormonally active compounds, and considerableefforts have been made to determine quantitatively the minute concentra-tions of circulating steroids. The problem originally posed, of relatingbiological activity to some parameter such as secretion rate, peripheralconcentration, or rate of formation of an active material, remains a t leastpartly unsolved, as indeed is the related matter of the intimate r81e ofsteroid and other hormones in intermediary metabolism.General.-The scope of a recent conference on hormonal steroids indi-cates the very broad range of interest in this field. Several useful accounts123 K.L. Yielding and G. M. Tomkins, Biochirn. Biophys. Acta, 1962, 62, 327.124 J. Wolf, J . Biol. Chem., 1962, 237, 230, 236.125 K. L. Yielding and G. M. Tomkins, Proc. Nat. Acad. Sci. U.S.A., 1961, 47, 983.126 C. Frieden, Biochk. Biophys. Acta, 1962, 59, 484.12’ B. Jirgensons, J . Amer. Chem. Soc., 1961, 83, 3162.12* H. F. Fisher, L. L. McGregor, and U. Power, Biochem. Biophys. Res. Comnt.,1962, 8, 402; H. F. Fisher, L. L. McGregor, and D. G. Gross, Biochim. Biophys. Acta,1962, 65, 175.Exerpta Medica, 1962, 52, 1JAMES: METABOLISM O F STEROID HORMONES 427of various aspects of steroid metabolism are now available, dealing withsteroids in blood,2 general and clinical aspects of adrenal steroids,3 cestro-gens,4 rneth~dology,~ and steroid chromatography.6 Binding of steroids toproteins,’ the control of adrenocortical secretion,g and the biosynthesis ofsteroid hormones 9 have also been reviewed.It now seems highly probable that path-ways not involving cholesterol play a minor r61e in corticosteroid biosyn-thesis by the adrenal cortex.Werbin and Chaikoff 10 fed [ 14C]cholesterolto guinea-pigs for a time sufficient to achieve uniform labelling of thecholesterol pool, and the specific activities of the blood cholesterol, adrenalcholesterol, and urine cortisol were then determined. The results indicatedthat 60% of the adrenal-gland cholesterol were derived from the blood, andalso, since the specific activities of the adrenal cholesterol and urinary cortisolwere practically identical, the latter must be formed principally from thecholesterol in the adrenal gland.No alteration of specific activity wasobserved after administration of corticotrophin, suggesting that the trophichormone does not alter the biosynthetic pathways. Further evidence thatcholesterol is the main precursor of cortisol is offered by studies l1 of thelabelling of the individual carbon atoms of cortisol biosynthesised from[l*C]acetate, which show a distribution of radioactivity identical with thatfound in cholesterol derived from [ 14C]acetate. Mevalonate is an establishedintermediate in cholesterol biosynthesis, and has been reported as a precursorof (3-19 steroids in wivo;l2 surprisingly, however, it was not incorporatedinto corticosteroids by an adrenal h0m0genate.l~The sequence cholesterol -+ pregnenolone (1) + progesterone (2) -+17a-hydroxyprogesterone (3) is established as an important major pathwayin the synthesis of cortisol (4).Under some circumstances, however, analternative pathway, cholesterol + pregnenolone (1) + 3p,17a-dihydroxy-pregn-5-en-20-one ( 5 ) ---+ 17a-hydroxyprogesterone (3), may assume im-portance. Normal, hyperplastic, and neoplastic adrenal glands all convert3~,17a-dihydroxypregn-5-en-ZO-one into cortisol l4 and in some instancesBios~thesis.-C2, Steroids.a H. N. Antoniades, “ Hormones in Human Plasma,’’ J. A. Churchill, London,1960; C. H. Gray and A. L. Bacharach, “ Hormones in Blood,” Academic Press, Inc.,New York, 1961.L. J. Soffer, R. I. Dorfman, and J.L. Gabrilove, “ The Human Adrenal Gland,”Henry Kimpton, London, 1961; F. T. G. Prunty, Brit. Med. Bull., 1962, 18, No. 2.4 E. Diczfalusy and C. Lauritzen, “ Ostrogene h i m Menschen,” Springer, Berlin,1961; H. Breuer, Vitamins and Hormones, 1962, 20, 285.M. F. Jayle, “ Analyse des Steroides Hormonaux,” Masson, Paris, 1961; R. I.Dorfman, “ Methods in Hormone Research,” Academic Press, London, 1962, Vol. I.R. Neher, Chromatog. Rev., 1959, 1, 99; I. E. Bush, “ The Chromatography ofSteroids,” Pergamon Press, London, 1961.W. H. Daughaday, Physiol. Rev., 1959, 39, 885.F. E. Yates and J. Urquhart, Physiol. Rev., 1962, 42, 359.A. Wettstein, Experientia, 1961, 17, 329:lo H. Werbin and I. L. Chaikoff, Arch. Bzochern. Biophys., 1961, 93, 476.llE.Caspi, R. I. Dorfman, B. T. Khan, G. Rosenfeld, and W. Schmid, J . Biol.l2 S. Burstmein and R. I. Dorfman, Acta Endocrinol., 1962, 40, 188.l3 M. J. Bryson and M. L. Sweat, Arch. Biochem. Biophys., 1962, 96, 1.l4 M. B. Lipsett and B. Hokfelt, Experientia, 1961, 17, 449; P. J. Mulrow, G. L.Cohn, and A. Kuljian, J . Clin. Invest., 1962, 41, 1584; I. Weliky and L. L. Engel,J. Biol. Chem., 1962, 237, 2089.Chem., 1962, 237, 2085428 BIOLOGICAL CHEMISTRYCholesterol Acetatethis precursor was superior to progesterone as a substrate. The relativeimportance of these pathways and the extent to which they may operateunder different conditions in viwo remains to be defined. It seems likelythat small amounts of 3/3,17a-dihydroxypregn-5-en-20-one are secreted bythe normal adrenal cortex, since a metabolite of this compound, namely,pregn-5-ene-3,!3,17~,2Oa-triol, occurs regularly in human urine.15The suggestion, based on experiments in vitro, that thesequence, cholesterol -+ pregnenolone + progesterone -+ l'l-hydroxypro-gesterone -+ androst-4-ene-3,17-dione (6) -+ testosterone (7), operates inthe synthesis of testicular androgens is supported by the detection of thelast three of these compounds in bull spermatic vein blood.16 A similarpathway probably exists in adrenal tissue since it has now been demon-strated that hornogenates of normal human adrenal tissue convert progester-one and 17-hydroxyprogesterone into androstenedione and testosterone.l7It is improbable, however, that an appreciable quantity of testosterone issecreted by the normal adrenal, since this steroid has not yet been demon-strated in normal adrenal glands or in adrenal vein blood, although it hasbeen isolated from an adrenal tumour.18 Since androstenedione is wellestablished as an adrenal secretory product (cf.Short 19), the h a 1 conversion,of androstenedione into testosterone, seems to be characteristic of testiculartissue.l5 K. Fotherby, Biochem. J., 1959, 69, 596; H. Wilson, M. B. Lipsett, and D. W.Ryan, J . Clin. Endocrinol., 1961, 21, 1304.l7 N. Kase and J. Kowal, J . Clin. Endocrinol., 1962, 22, 925.l9 R. V. Short, Biochem. Soc. Symposia, 1960, Vol. XVIII, p. 59.C,, Steroids.H. R. Lindner, J. Endocrinol., 1961, 23, 139.R. Anliker, 0. Rohr, and M.Marti, Helv. Chirn. Acta, 1957, 39, 1100JAMES: METABOLISM O F STEROID HORMONES 429The alternative pathway, pregnenolone --+ 3/3,17x-dihydroxypregn-5-en-20-one + dehydroepiandrosterone (8) --+ androstenedione, appears toproceed in both testis and the adrenal gland. The first two stages havebeen demonstrated with homogenates of both bovine adrenal and testiculartissue,20 and the dihydroxypregnenone was found in bovine adrenal glands.21Dehydroepiandrosterone has been detected in bovine testes,21 and there isindirect evidence for its gonadal secretion.22 Here again, the quantitativesignificance of these alternative routes is not known, but it seems necessaryto assume that the pathway to dehydroepiandrosterone must be of con-siderable importance in the adrenal cortex (see below).The conversion of acetate, cholesterol, and progesteroneinto estrogens by human ovaries in yields of 0.02%, 0-1%, and lo%, respec-tively, has been dem~nstrated.~~ The progressive increase in yield is inaccordance with a biosynthetic route in the ovary which is similar to thosefor adrenocortical and testicular steroids. It is necessary in these, as in'all experiments in uitro, to accept that results with tissues outside the body,and thus under artificial conditions, reflect processes occurring in vivo.Inthis instance, a preparation that was active in vitro was obtained by ad-ministration of follicle-stimulating hormone before surgical removal of theovaries.There is also further evidence to show that C,, neutral steroids are inter-mediates in the conversion of progesterone into estrogens.24 Androst-4-ene-3,17-dione has been isolated from human ovarian follicles and corporalutea,25 and ovarian biosyntheses of this compound from acetate 24 and fromprogesterone 26 have been demonstrated. Testosterone has been detectedin the follicular fluid of the cow 27 and in ovarian tumour tissue,28 andtestosterone biosynthesis from various precursors by normal 29 and abnormalovarian tissue 30 has been shown. Dehydroepiandrosterone occurs in equinefollicular fluid 30a and in cystic human ovaries.31 In appropriate conditionsall three C,, steroids may serve as precursors for estrogen.32 The finalstages of estrogen formation, in which ring A of the steroid nucleus isaromatised, requires oxidation at (3-19, and both 19-hydroxyandrost-4-ene-3,17-dione (9) and androst-4-ene-3,17,19-trione (10) are converted intoestrone (11) and cestradiol (12) in good yield by placental microsomes;2o F.W. Kahnt, R. Neher, K. Schmid, and A. Wettstein, Ezperientia, 1961, 17, 19.21 R. Neher and A. Wettstein, Acta Endocrinol., 1960, 35, 1.2 3 S. Lieberman, P. Macdonald, and R. L. Vandewiele, Exerpta Medica, 1962,51, 16.23 K. J. Ryan and 0. W. Smith, J . Biol. Chem., 1961, 236, 705, 710, 2204.2 4 K. J. Ryan and 0. W. Smith, J . Biol. Chem., 1961, 236, 2207.25 J. J. Zander, J . Biol. Chem., 1958, 232, 117.26 M. L. Sweat, D. L. Berliner, M. J. Bryson, C. Nabors, J. Haskell, and E. G.Holmstrom, Biochim. Biophys. Acta, 1960, 40, 289.27 R.V. Short, J . Endocrinol., 1962, 23, 401.28 R. Anliker, 0. Rohr, and L. Ruzicka, Annalen, 1957, 603, 109.2s N. Kase, E. Forchielli, and R. I. Dorfman, Acta Endocrinol., 1961, 3'7, 19.30 K. Savard, M. Gut, R. I. Dorfman, J. L. Gabrilove, and L. J. Soffer, J . Clin.Endocrinol., 1961, 21, 165; A. A. Sandberg, W. R. Slaunwhite, J. E. Jackson, andT. F. Frawley, ibid., 1962, 22, 929; V. B. Mahesh and R. B. Greenblatt, ibid., p. 441.C,, Steroids.30aR. V. Short, J . Endocrinol., 1961, 23, 277.31 R. V. Short, J . Endocrinol., 1962, 24, 359.32K. J. Ryan, J . Biol. Chem., 1959, 234, 268; C. D. West and A. H. Naville,Biochemistry, 1962, 1, 645430 BIOLOGICAL CHEMISTRYDehydroepi androsterone Androstenedione TestosteroneOH..OH0OHHO.H2C0 &J, J,HOother possible intermediates, including 19-nortestosterone or androsta- 1,4-diene-3, 17-dione, were only poor substrates.33 The mechanism of aromatisa-tion appears to involve trans-diaxial elimination of (7-19 and la-hydr0gen.3~There is some evidence, however, that free 19-hydroxyandrostenedione maynot participate in the reaction.35 The route to oestriol (13) via 16-hydroxy-testosterone (14) 36 may be of significance in placental tissue, since the lattercompound was the most abundant steroid detected in placental extracts.37Catabolism.-C,, Steroids.(i) Aldosterone. The preparation of [7-3H]-aldosterone of high specific activity has made possible the study of thecatabolism of this hormone at “ physiological ” concentrations.38 About14% of the secreted hormone appears in urine as the ‘‘ 3-oxo-conjugate.”The structure of this compound is unknown, and the term “ 3-oxo-conju-gate ” implies only that the A4-3-oxo-grouping is not irreversibly reduced.The major metabolites of aldosterone are excreted as glucuronides (55% ofthe dose). Original studies of the structure of the major metabolite sug-gested formulation as 3~,18,21-trihydroxy-5~-pregnane-ll,20-dione,39 butthis material was later shown t o be a mixture of 3a,l8,21-trihydroxy-58-33 C.Gual, T. Morato, M. Hayano, M. Gut, and R. I. Dorfman, Endocrinology,34 L. R. Axelrod and J. W. Goldzieher, J . CZin. EndocrinoZ., 1962, 22, 537.35 N. Hollander, Endocrinology, 1962, 71, 723.36 K. J. Ryan, J. BioZ. Chem., 1959, 234, 2006.8 7 R.Neher and G. Stark, Experientia, 1961, 17, 510.58 C. Flood, D. S. Layne, S . Ramcharan, E. Rossipal, J. F. Tait, and S . A. S.Tait, Acta Endocrinol., 1961, 36, 237.3 9 S. Ulick and 5. Lieberman, J . Amer. Chem. Soc., 1957, 79, 6567.1962, 71, 921JAMES: METABOLISM O F STEROID HORMONES 431pregnane-1 1,2O-dione (derived from corticosterone) and 3a,l1/?,21-tri-hydroxy-20-oxo-5~-pregnan- 18-a1 (tetrahydroaldo~terone).~~ The latter com-pound accounts for about 40% of the total urinary metabolites. Othercompounds, isolated after the administration of very large quantities ofaldosterone, were identified as 11,18,20-cyclic diacetalsY41 and some 3p- and5a-compounds were found.42Only small and highly variable quantities of aldosterone are secretedby the adrenal cortex.The mean value for a small number of normal sub-jects was 138 ,~g./day.~3 Measuring the concentration of aldosterone inperipheral blood is very difficult because of the low values involved, andgreat skill is required (procedures are reviewed by Tait and Tait 44). Bojesenand Degn 45 have reported concentrations of 2 4 x g. per 100 ml.in the peripheral plasma of dogs, and up to 2.5 x g. per 100 ml. wasfound by Bojesen in human plasma (cf. ref. 44).(ii) Cortisol. The major paths involved in the catabolism of cortisolare now well established. Reduction of the A4-3-0x0-grouping in ring Aproceeds to a major extent and is largely stereospecific, yielding a 3aY5/l-structure [tetrahydrocortisol (15)]. Oxidation at C-11 of alcohol to ketonealso occurs, producing tetrahydrocortisone (16).A proportion of the steroidis reduced further, at C-20, to give the hexahydro-metabolites (17) (“ cor-to1 ”) and (18) (“ cortolone ”). After administration of [14C]cortisol tohuman subjects, these four compounds accounted for 90% of the activityin the neutral extract obtained after treatment of the urine with glucuron-idase, followed by acid.46 A minor mode of metabolism involves removal40 S. UIick, K. Kusch, and J. T. August, J. Amer. Chem. Xoc., 1961, 83, 4482.41 W. G. Kelly, L. Bandi, J. N. Shoolery, and Sf Lieberman, Biochemistry, 1962,4 2 W. G. Kelly, L. Bandi, and S. Lieberman, Biocherniutry, 1962, 1, 792.43 J. N. Mills, Brit. Med. Bull., 1962, 18, No;‘ 2, 170.4 4 S.A. S. Tait, J. F. Tait and R. I. Dorfman,45 E. Bojesen and H. Degn, Acta Endocrinol., 1961, 37, 541.4 6 D. K. Fukushima, M. L. Bradlow, L. Hellman, B. Zumoff, and T. F. Gallagher,1, 172.Methods in Hormone Research,”Academic Press, London, 1962, Vol. I, p. 265.J . Biol. Chem., 1960, 235, 2246432 BIOLOGICAL CHEMISTRYof the steroid side chain to yield 17-oxo-steroids, and these compoundstogether with other minor metabolites probably account for all the residualactivity in the extract. A small proportion (7-28%) of the excreted radio-activity remained in the urine after hydrolysis and extraction and presum-ably represents metabolites of cortisol which resist known methods ofhydrolysis, or compounds which are not extracted by the usual organicsolvents.These compounds may become quantitatively more important a thigher secretion rates, since Gold 47 was unable to account completely forthe metabolites of administered cortisol when 200 mg./day were given.The amount of cortisol or corticosterone which is excreted unchanged isextremely small. After administration of large doses of these compoundssome conjugation at C-21 with sulphuric acid is rep0rted.~8 Other minormetabolites of cortisol are 5a-cortol and 5a-cortolone, isolated after admin-istration of 500 mg. of cortisone acetate.46 Hydroxylation at C-6 alsooccurs to a small extent but may be increased when normal metabolic routesare impaired 49 or in the metabolism of synthetic steroids.50C, Steroids. Although dehydroepiandrosterone was among the firststeroids to be isolated from human urine and there is unequivocal evidenceavailable that this compound or its precursor originates from the adrenalcortex, it is still not known in what form it is secreted or whether it resultsfrom peripheral degradation of another compound.The poor conversionin wivo of administered 38,17a-dihydroxypregn-5-en-20-one suggests this isan unlikely peripheral source of urinary dehydroandrosterone. 51 In anattempt to study this problem further, Lieberman’s group administered[7-3H]dehydroepiandrosterone to a series of normal subjects. Androsterone,aetiocholanolone, and dehydroepiandrosterone were then isolated from theurines, and their specific activities were determined : all three metaboliteshad almost the same specific activity.52 This implies that these three com-pounds arise from the same precursor, i.e., dehydroepiandrosterone, and thatno other precursor contributes to a large extent to the urinary androsteroneand ztiocholanolone.Dehydroepiandrosterone thus assumes considerableimportance as the major precursor of the C,, steroids in human urine. Thisfinding was unexpected since it has been difKcult to detect dehydroepi-androsterone regularly in adrenal vein blood, and because of the implicationthat compounds such as testosterone and androstenedione must thereforebe secreted in very small amounts. From the dilution of the administeredisotope, it was calculated 52 that the production of dehydroepiandrosteroneranged from 12 to 50 mg./day in the subjects studied.Unfortunately, this simple interpretation does not appear to be validin all cases, since Brooks and Prunty 53 reported that in four out of five4 7 N.I. Gold, J . Clin. Invest., 1962, 41, 1871.48 J. R. Pasqualini, “ Contribution B l’lhude Biochimique des Corticosteroides,”4 9 F. H. Katz, M. M. Lipman, A. G. Frantz, and J. W. Jailer, J . Clin. Endocrinol.,50 J . R. Florini, L. L. Smith, and D. A. Buyske, J . Biol. Chem., 1961, 236, 1038.51 S. Solomon, A. C. Carter, and S. Lieberman, J . Bicl. Chem., 1960, 235, 351.5 2 R. L. Vandewiele, P. C. MacDonald, E. Bolte, and S. Lieberman, J. Clin.53R. V. Brooks and F. T. G. Prunty, Exerpta Medica, 1962, 51, 174.Foulon, Paris, 1962.1962, 22, 71.Endocrinol., 1962, 22, 1207J A M E S : METABOLISM O F STEROID HORMONES 433cases studied by the same method the specific activity of the urinarydehydroepiandrosterone was lower than that of the urinary aetiocholanoloneand androsterone : in this situation some other precursor of urinary dehydro-epiandrosterone must be involved.Clarification of this problem revolvesaround the composition of normal adrenal venous effluent; it is by no meansclear to what extent the detection of dehydroepiandrosterone and andro-stenedione in adrenal vein blood represents the situation in the normal sub-ject, since the majority of observations have been made in conditions wherethe adrenal gland has been stimulated either endogenously or exogenouslywith corticotrophin. The matter is further complicated by Baulieu's obser-vations 54 that, whereas no free dehydroepiandrosterone could be detectedin an adrenal tumour or in the venous blood from the tumour, dehydroepi-androsterone sulphate was detected in both, and in higher concentrationthan in peripheral blood. The possibility therefore exists that dehydroepi-androsterone is secreted as its sulphate also under normal conditions.Studies of the metabolism of dehydroepiandrosterone sulphate have alreadyshown that it is converted into aetiocholanolone glucuronide and androsteroneglucuronide,55 thus implying that dehydroepiandrosterone and its sulphateare interconvertible in vivo. It may therefore be necessary to reassess theconcept that compounds such as dehydroepiandrosterone sulphate representinactive end-products of steroid metabolism, and it has been reported 56that administration of either dehydroepiandrosterone or androstenedioneleads to increased levels of plasma testosterone.Testosterone secretion rates have been estimated by administering[ 14C]testosterone and subsequently measuring the specific activity of theurinary test~sterone.~' This method led to estimates of secretion rates of3-8 mg./day in normal adult males and 0.5-2 mg./day in normal females.Administration, to two female subjects, of [ 17-3H]cestradiolprovided confirmation that its direct hydroxylation is a minor pathway tooestriol. The urinary oestriol isolated contained only minimal radioactivityand must therefore be formed by the route, oestradiol-+ oestrone --+oestriol. 58The conversion of oestrone into oestriol probably involves initial hydroxyl-ation at position 16. Studies of the metabolism of 16~-hydroxyoestronehave demonstrated significant conversion into oestriol in vivo 59 and to asmaller extent into 16-epiestriol and 17-epioestriol (for structures see thechart).60 16/I-Hydroxyoestrone was converted into oestriol and 16-epi-oestriol, 16,17-epioestriol being a minor product.60 Both the ketols canthus serve as precursors of oestriol, reduction of the 17-ketone proceedinglargely to yield the 17/?-alcohol. However, epimerisation at C-16 alsooccurs, which suggests that a 16-ketone is an intermediate in this conversion.s4E. E. Baulieu, J. Clin. Endocrinol., 1962, 22, 501.5 5 K. D. Roberts, R. L. Vandewiele, and S. Lieberman, J. Bid. Chem., 1961, 236,5 6 V. B. Mahesh and R. B. Greenblatt, Acta Endocrinol., 1962, 41, 400.5 7 B. Hudson, Public Lecture at St. Mary's Hospital, London, May 31st, 1962.58 J. Fishman, H. L. Bradlow, B. Zumoff, L. Hellman, and T. F. Gallagher, Acta5 9 J. B. Brown and G. F. Marrian, J . Endocrinol., 1957,. 15, 307.6 o W. Nocke, H. Breuer, and R. Knuppen, Acta Endocrznol., 1961, 36, 393.(218 Steroids.2213; A. E. Kellie, J. Endocrinol., 1961, 22, i.Endocrinol., 1961, 37, 57434 BIOLOGICAL CHEMISTRYOEstradiolJlG s t r o n e40JIOHOEstriol 16-Ep ice s t r i o IAll the compounds shown in the chart have been detected in human urine,although the majority appear to be relatively minor metabolites in relationto estrone and estriol. A further metabolic route yields the Z-methoxy-derivatives of estrone, estradiol, and estriol, probably through the2-hydroxy-compounds. Although the picture is still incomplete, it is likelythat a fair proportion of the total estrogen metabolites can now be accountedfor. It is not clear what is the scale of faecal elimination but in some casesit appears to be considerable.61Peripheral conversion of other steroids into estrogens is probably ofminor importance in relation to endogenous estrogen production, but maybe significant where the latter is decreased, e.g., after endocrine surgery formalignant disease. 11 -Hydroxylated estrogens have been isolated afteradministration of cortisone acetate although, surprisingly, cortisol was notsimilarly converted. 62Studies of estrogen metabolism in pregnancy indicate that conversionof radioactive estradiol into estrone and cestriol is similar to that found innon-pregnant subjects. In pregnancy, however, the specific activity of theurinary cestriol is considerably lower than that of the other two metabol-ites;619 63 this accords with the view that the placental-foetal compartmentproduces oestriol directly, but it may be also an expression of differentmetabolic routes for estrogen in the fetus. Foetal metabolism of estrogenshas been studied extensively by Diczfalusy and his co-workers, and theirwork reveals a remarkably high degree of conjugation by a variety oftissues. Work both in vivo and in vitro demonstrated that fetal lungs, liver,kidney, adrenals, and intestine are major sites of estrogen c0njugation.6~61 J. Fishman, J. B. Brown, L. Hellman, B. Zumoff, and T. F. Gallagher, J . Biol.E. Chang and T. L. Dao, J . Clin. Endocrinol., 1961, 21, 624; Biochim. Biophys.63 E. Gurpide, M. Angers, R. L. Vandewiele, and S. Lieberman, J . Clin. Endo-6 4 E. Diczfalusy, 0. Cassmar, C. Alonso, M. de Miquel, and B. Westin, Acta Endo-Chem., 1962, 237, 1489.Acta, 1962, 57, 609.crinol., 1962, 22, 935.crinol., 1961, 37, 516J A M E S : METABOLISM O F S T E R O I D HORMONES 435This picture contrasts markedly with the situation in the adult, where theliver is probably the major site of steroid metabolism, and implies, theauthors suggest, a r6!e for conjugated steroids other than that of detoxifica-tion products.V. H. T. J.D. F. ELLIOTT.C. P. FAWCETT.V. H. T. JAMES.G. S. WRKS.A. M. WHITE

ISSN:0365-6217    

DOI:10.1039/AR9625900384

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY1. INTRODUCTIONSOME twenty years ago it was remarked that the analytical laboratory wasregarded as the bottle-neck of production in metallurgical work. This musthave found a heartfelt echo in many other industries, and it is, of course,the perennial opinion of research workers in any field.Since then much has been done to improve matters. In these Reportsthere is recurring emphasis on methods which decrease time without sacri-ficing accuracy, although perhaps they are not so widely adopted as toexclude some twinges of envy at the mention, in the following pages, of acomplex industry in which no analysis takes more than 24 hours.Part of the improvement in the last two decades has been due to therefinement of classical methods and the spread of neo-classical ones such assolvent extraction and complexometric titrimetry, but most of it is clearlydue to the adoption by the analyst of agreat variety of instrumental methods,mostly borrowed from the fields of structural investigations.Their advan-tage lies not so much in speed of measurement (a titration is as quick as mostof them) but in standardisation of measurement so that it can be done as aroutine and, above all, in the elimination of involved chemical separationswhich control the time and often the accuracy. Their disadvantage is thatmany of them survive with little or no change from their versatility asfundamental tools, and so the analyst is paying for a complexity, a degreeof invention, and often (dare we say?) an instability which he could in mostcases do without.He may need the first two qualities, and have to put upwith the third, if he is developing an analytical method from first princi-ples, but he is usually the first to progress beyond this and to simplify themachine to routine requirements.There are happy exceptions,but manufacturers might be more generally persuaded at an early stage inthe development of an instrument, and in consultation with the analyticalchemist, to produce a not-too-abridged “ paper-back ” edition which couldspread his development costs and open new horizons to the less wealthylaboratories. The era of the pocket n.m.r. or X-ray fluorescence spectro-meter is not yet, but strange things happen in analysis, and manufacturersshould be thinking of it.More analytical papers have been published, in more and more journals.The first volume of AnaZyticaZ Abstracts,2 published in 1954, contained about3000 references.Last year there were 5000, and this rose in 1961 to 5500.No analytical chemist could find his way among such a wide coverage ofjournals without their guidance, and your Reporters record their thanksto the Abstracts’ Editors, and their apologies to the multitude of authorswhose worthy papers have had to be excluded.Seldom does the manufacturer do this.1E. J. Vaughan, Roy. Imt. Chem. Monograph, 1941.2 Analytical Abstracts, Society for Analytical ChemistryCARTWRIGHT, WESTWOOD, AND WILSON 437The arrangement of the Report is: (1) Introduction. (2) General.(3) Basic operations and apparatus.(4) Qualitative analysis. ( 5 ) Methodsof separation. (6) Gravimetric and titrimetric analysis. (7) Instrumentalend-point determinations. (8) Determination of elements in organic com-pounds. (9) Spectroscopic analysis. (10) Electrical methods. (1 1) Ther-mal methods.2. GENERALAlthough the seventh Bernard Dyer Memorial Lecture to the Societyfor Analytical Chemistry dealt with the broad field of research in BritainY3the analytical chemist will find pertinent and illuminating this account ofthe economic backpound to the contributions of industry, research associa-tions, universities, and Government research stations. The early develop-ment of analytical chemistry has been reviewed by Greena~ay,~ andaccounts of modern progress in general fields have been published.Babkohas described new reactions and their applications in inorganic analysis,with corresponding developments in theory, and an account by G. den Boefdeals mainly with advances in non-instrumental titrimetry.This year it is the turn of fundamental developments in analysis toreceive attention in the annual reviews in AnaZyticaZ Chemistry. Under38 headings, they cover significant advances made during 1960-61, andwith a total of some 12,000 references they are clearly essential materialfor the analyst.A number of review papers have comprehensively described the stateof more limited fields of analysis. Cockbill * has given a critical account ofclassical and instrumental methods for determining niobium and tantalum,and has proposed a general method based on isolating these metals togetherfrom hydrofluoric acid solution on a cellulose column or strip, with subse-quent separation and determination according to the proportions present.The analysis of high-purity gold has been t'he subject of a symposium, andcritical reviews of methods of determining gold and a large number ofmetallic impurities have subsequently been published.These papers under-line the development and applications of such methods as emission andatomic absorption spectroscopy, flame photometry, and polarography.Modern methods of paint analysis have been described by Lamprecht 10who indicates the increasing use of instrumental methods such as potentio-metric titrations for pigments and infrared absorption for solvents.Anaccount has been given of the detailed processes adopted in the Frenchuranium industry for the control of quality and of safety.11 All analysesare completed in 24 hours, and to this end automation has been widelyD. W. Hill, Analyst, 1962, 87, 334.F. Greenaway, Endeavour, 1962, 21, 91.G. den Boef, Chem. Weekblad, 1962, 58, 21.Annual Reviews, Analyt. Chem., 1962, 34, No. 5.J . S. African Inst. Mining Met., 1962, 62, 700.5A. K. Babko, Zavodskaya Lab., 1962, 28, 773.* M. H. Cockbill, Analyst, 1962, 87, 611.lo W. Lamprecht, Parbe u. Lack, 1961, 67, 560.l1 J. Pruguard, Chinz. analyt., 1962, 44, 143438 ANALYTICAL CHEMISTRYadopted, and instmental methods predominate over chemical.Exampleshave been given of modern analytical techniques with a description of howthey can best be co-ordinated in industrial research.12 Methods of analysingperoxy-acids and hydrogen peroxide in presence of each other have beencompared,13 and a review has been given of the analysis of glass by methodswhich gain in speed without loss of accuracy.14Analytical applications of the mercury electrode have been discussed ina review l5 which covers reduction processes with and without externalcontrol of electrode potential, coulometric determinations a t controlledcurrent, and amalgamometry (where formation of an amalgam is put todirect analytical use for quantitative separation or determination).Other reviews which have direct bearing on the individual topics of thisReport are mentioned in their appropriate section.3.BASIC OPERATIONS AND APPARATUSThe dissolution of samples and the oxidation of organic material havereceived attention. Weisz has described a method for treating a samplewith successive solvents on platinum foil, each solution being in turnabsorbed on filter paper for ring-oven analysis. Metallic samples containingtraces of boron can be dissolved without loss of boron l7 by using anhydrousmethanol with gradual addition of sulphuric or phosphoric acid solutionsin methanol; volatile boron compounds are trapped in a sodium hydroxidesolution in aqueous glycerol. Beyermann lS has examined the analyticalbehaviour of micro-quantities of chromium. He determined losses incurredin dissolving and in evaporating the sample, and the effectiveness of oxida-tion, extraction, volatilisation, and co-precipitation procedures, and reportedon the chromium content of 14 reagents.For oxidation of organic material, in particular celluloses, Monk l9 hasadvised altering the usual perchloric acid procedure by adding a nitric acidsolution of the material in small portions to a boiling 72% perchloric acidsolution; this is claimed to avoid hazards due t o accumulation of resistantorganic matter in the perchloric acid solution.Volatilisation of a numberof trace elements during oxidation of organic matter in the presence of someinorganic chlorides has been investigated by Gorsuch 2o using radiochemicalmethods. Heating with sodium chloride did not cause losses with antimony,chromium, iron(m), lead, and zinc.With ammonium chloride there wassubstantial loss of antimony and zinc, and some loss of lead. Loss of zincwas small with magnesium chloride, substantial with calcium chloride, butnegligible with barium chloride. Methods of preventing loss of halogens,12R. C. Chirnside, Svenslc kern. Tidskr., 1961, 73, 265.l3 B. D. Sully and P. L. Williams. Analyst, 1962, 87, 653.l4 H. Lattermann, Silikat Tech., 1962, 13, 50.l5 J. A. Page, J. A. Maxwell, and R. P. Graham, Analyst, 1962, 87, 246.l6 H. Weisz, Mikrochim. A d a , 1962, 922.l7 L. R. Pitwell, Analyst, 1962, 87, 684.l8 K. B6Y6rman11, 2. analyt. Chem., 1962, 190, 4.R. G. Monk, Analyst, 1962, 87, 64.2o T. T. Gorsuch, Analyst, 1962, 87, 112CART WRIGHT , WE STWO 0 D ; -4N D WILSON 439phosphorus, and sulphur during oxidation of organic compounds have alsobeen described.21Revisions have been made in the values at various temperatures of eachof the seven pH standards recommended by the National Bureau of Stan-dards.The preparation, properties, and uses of the standards are given.22Duval has continued his investigations,23usig thermogravimetric and infra-red absorption methods, of the thermal stabilities of a number of standardsused in analysis. A list of analytical standards in use in Czechoslovakiahas been published.24 The applications and limitations of silicones in suchdiverse laboratory rbles as heat exchangers, molecular weight solvents,glass treatment, and lubricants have been discussed.25Attention has been drawn to the analytical uses of exfoliated vermiculite.Holland 26 has recommended it as a general analytical aid in the absorptionof water from samples before extraction of oils and fats with organic solvents,claiming easier and more complete extraction.Smith and Diehl 27 havedescribed the properties of a highly efficient desiccant, prepared from vermi-culite and phosphorus pentoxide, which remains granular in use. Theregeneration of magnesium perchlorate desiccant in the laboratory isclaimed 28 to be facilitated by vermiculite.Modifications have been made to methods and apparatus for determiningwater. A simple apparatus has been described 29 which enables the KarlFischer determination to be carried out with 0-2-3 mg.water, and thedetermination of total water in rocks by a simplified diffusion method 30facilitates the heating of the sample and the collection and weighing of thewater produced.Methods have been recommended for testing laboratory glassware forresistance to chemical attack 3 l and to thermal sh0ck,~2 and standards havebeen issued for a range of graduated pipettes calibrated for delivery orcontent.33 Errors involved in using graduated cylinders for delivery insteadof content have been investigated and procedures for minimising themdiscussed. 34Recent trends in the design of analytical balances have been described,35and a quartz-beam microbalance has been produced 36 which electricallyregisters on a meter or recorder with variable sensitivity down to 1 PA.= 1 pg.It has a capacity of 1 to 2 g. and is particularly suited to follow changes inweight even at high temperatures and low pressures.21 D. Pristavka, Chem. Zvesti, 1961, 15, 865.2 2 R. G. Bates, J . Res. Nat. Bur. Stand., 1962,. A, 66, 179.23 C. Duval, Mikrochim. Acta, 1962, 268, 947.2 4 V. Mayer, Hutn. Listy, 1961, 895.25 W. Simmler, Glas.-Instrum.-Technik, 1962, 6, 101.26 G. J. Holland, Andyst, 1962, 87, 797.27 G. F. Smith and H. Diehl, Talanta, 1962, 9, 84.28 G. F. Smith, Talanta, 1962, 9, 65.29 A. Dirscherl and F. Erne, Mikrochim. Acta, 1962, 794.30A. D. Wilson, Analyst, 1962, 87, 598.31 B.S. 3473: 1962, British Standards Institution.32 B.S. 3517: 1962, British Standards Institution.33 B.S.700: 1962, British Standards Institution.34 G. A. Dean, Analyst, 1962, 87, 503.35 D. Patterson, R <f: D, 1962, 34.36 Bias.-Instrzcm.-Technik, 1962, 6, 196440 ANALYTICAL CHEMISTRYAn increase in the precision of ebulliometric molecular weight deter-mination is given by a differential method. Problems in ebulliometry havebeen disc~ssed,~' together with the design of a differential apparatus usinga sensitive a.c. bridge, which gives a precision of &0-77% on a molecularweight of less than 500.Among apparatus which may fulfil some of the varied requirements ofthe analyst are it vacuum evaporator for completion of solvent removal, 38a thermistor device for controlling rate of evaporation in fractional distilla-t i ~ n , ~ ~ a simple addition to a micrometer-syringe burette which enables itto be used for occasional determinations with air-sensitive solutions,40 anda tapless polyethylene separatory funnel for small-scale work, in which theseparation of aqueous and organic phases is cleanly performed by filter paperwhich may be silicone treated.41 Causes of variation in the performanceof a continuous automatic analyser have been investigated, 42 the deter-mination of streptomycin being used as the control.Garmon and Reilley 43 have discussed the possibility of simultaneouslydetermining two components of a mixture by their differing rates of reactionwith a single reagent.From measurements of a property of the reactionmade at two intervals of time, and known reaction rates, concentrationsmay be calculated. Doerffel 44 and Youden 45 have given accounts oferrors and accuracy in analysis, and the interpretation of analytical results.4.QUALITATIVE ANALYSISInorganic.-SeveraI papers of general interest have been published andthese will be reviewed before dealing with examples of more specific tests.Some analytical reactions of polyhydric phenols have been studied 46 andcertain of them have been used 47 for the detection of iron(m), titanium(Iv),vanadium(v), niobium(v), uranium(vI), molybdenum(vI), cerium(1v) , andchromium(v1). The masking action of 20 complexans on the course of testsused in qualitative inorganic analysis has been studied,48 and an investiga-tion has been made of the use of Variamine Blue in spot-test analysis.49Chlorpromazine hydrochloride has been suggested as a spot-test reagent forgold, cerium, iron, chromate, bromate, iodate, nitrite, bromide, iodide,manganate, platinum, and palladium.50 A qualitative test for sodium inthe presence of heavy metals by precipitation as antimonate is of interest37 F.Trowell, H. G. Taylor, and W. I. Brown, Analyst, 1962, 87, 677.38 M. H. Coleman, Lab. Practice, 1962, 11, 543.40 A. D. Wilson and G. A. Sergeant, Analyst, 1962, 87, 152.41 H. Marchart, Mikrochim. Acta, 1962, 913.42 W. H. C. Shaw and I. Fortune, Analyst, 1962, 87, 187.43 R. G. Garmon and C. PIT. Reilley, Analyt. Chem., 1962, 34, 600.44 K. Doerffel, 8. analyt. Chem., 1962, 185, 1.45 W. J. Youden, J. Assoc. Ofic. Agric. Chemists, 1962, 45, 169.46 L.Sommer, 2;. analyt. Chem., 1962, 187, 7.4'L. Sommer, 2. analyt. Chem., 1962, 187, 263.48 W. Hoyle, I. P. Sanderson, and T. S. West, Analyt. Chi.m. Acta, 1962, 26,290.49 L. Erdey and I. Buzbs, Mikrochim. Acta, 1962, 340.K. T. Lee, Analyt. Chim. Acta, 1962, 26, 285.E. C. Kuehner and R. T. Leslie, Analyt. Chem., 1962, 34, 1155CARTWRIGHT, WESTWOOD, AND WILSON 441since interference by many other metals may be overcome by the maskingaction of a mixture of EDTA and dihydr~xyethylglycine.~~A new selective catalytic reaction for copper has been proposed involvingaqueous ammonia and alcoholic guaiacol valerate solutions. 52 Isatin 3-p-nitrophenylhydrazone forms a blue acid-soluble lake which may be usedfor the detection of magnesium in alkaline s0lution,5~ and 3-hydroxy- l-o-nitrophenyl-3-phenyltriazen has been suggested for the detection of zinc andnickel.54Aluminium may be detected by using Eriochrome Cyanine (C.I. MordantBlue 3),55 and also by the inhibiting effect of the formation of an aluminium-alizarin complex on the catalysed oxidation of alizarin by hydrogen per-oxide.56 A new micro-test for gallium has been described which makes useof the colour reaction between gallium and Xylenol Orange at pH 1.0 inthe presence of triethanolamine and ammonium fluoride. 57It has been reported that p-sulphanilic acid is fairly specific for the detec-tion of cerium(Iv), giving a red colour with more than 6 p.p.m. of themetal. 68A sensitive test for nitrate has been described 59 and a method has beendeveloped for the detection of nitrate and nitrite by the formation of aviolet-purple colour with N - 1 -naphthylethylenediamine and concentratedsulpliuric acid.60 The method can be used for the detection of nitrate ornitrite in the absence of one or the other, or for the detection of nitrate inthe presence of nitrite after destruction of the latter by sulphamic acid.Vanadium(v) may be detected by the violet colour produced with a 1%solution of maltol (3-hydroxy-2-methylpyan-4-one) in 40% phosphoric acidmedium.61 The selective detection of niobium using Methyl Thymol Bluehas been described.O2The addition of an ethanolic solution of resacetophenone oxime to solu-tions of uranium(vI) in weak mineral acids produces a reddish-brown colourwhich may be used for the detection of the metal.Uranium(Iv), aluminium,zirconium, and thorium do not interfere, but tervalent iron gives a deeppurple colour.63Organic.-Microgram quantities of ethanol may be detected by oxida-tion at the boiling point to acetaldehyde. Nitrogen and air are passedthrough the solution and the acetaldehyde is detected on a paper stripby using the nitroprusside-morpholine reagent. 64 Formation of adducts51 S . Takamoto, Japan Analyst, 1960, 9, 281.5 2 M. Y . Shapiro, Zhur. analit. Khim., 1962, 17, 248.53 D. Goldstein and E. Libergott, Mikrochim. Acta, 1962, 352.5 4 I. P. Khazova, Sb. Nauch. Trud. Magnito gorsk. Gorno metallurg. Inst., 1961,98; Ref. Zhur. Khim., 1962, Abs. No. 7D45.6 5 H. Gamsjilger and E.Schwarz-Bergkampf, Mikrochim. Acta, 1962, 194.56 J. Laszlovsky, Mikrochim. Acta, 1962, 441.5 7 R. Pzibil and M. Kopanica, Mikrochim. Acta, 1962, 29.5 8 P. L. Sarma, Analyt. Chim. Acta, 1962, 27, 370.59 G. de Vries and A. A. A. M. Brinkman, Analyt. Chim. Acta, 1962, 26, 498.6oA. Irudayasamy and A. R. Natarajan, Analyst, 1962, 87, 236.61 L. Sommer, Z . analyt. Chem., 1962, 185, 263.E. Lassner, Chemist-Analyst, 1962, 51, 14.63 C. Rama Rao, Talanta, 1962, 9, 81.8 4 A. Dirscherl, Mikrochim. Acta, 1962, 155442 ANALYTICAL CHEMISTRYbetween various alcohols and vanadium 8-hydroxyquinoline complexes hasbeen studied and the best conditions for detecting alcohols by this reactionhave been ~onsidered.~~ An investigation has been made of methods forthe detection of alcohols by colour reactions with a number of additiona.gent s .Feigl and Libergott have described a spot-test for phloroglucinol basedon pyrolytic a m i n a t i ~ n .~ ~ Pyrogallol and benzene-1,2,4-triol do not inter-fere since they are not aminated under the conditions of the test.The identification of a number of nitrogen compounds by reaction with asilver-manganese reagent has been investigated, 68 and a new sensitive colourreaction for the detection of secondary amines by use of methanolic pheno-thiazine solution and methanol-bromine solution has been described.69 -4procedure has been given for the detection of a-amino-alcohols and 1,2-diamines involving the production of iodic acid by reduction of potassiuniperiodate in sulphuric acid solution followed by precipitation of silver iodatewith silver nitrate in nitric acid solution.70Organic disulphides and diselenides are selectively reduced in the pres-ence of Raney alloys in alcoholic hydrochloric acid to give thiols andselenols which may be detected by the iodine-azide reaction.71 The detectionof thiocyanates in organic compounds has been studied by Feigl andHaguenauer-Castro, taking ethylene dithiocyanate and 2,4-dinitro-l -thio-cyanatobenzene as model substances. 72Cysteine can be detected in the presence of cystine, methionine, andtaurine by reduction in an aqueous solution of osmium tetroxide to give apink or reddish-brown colour ; glutathione interferes. 73N-Halogenosulphonamides can be detected by the violet colour producedwhen their aqueous solutions are spotted on to paper impregnated with a2% ethereal solution of phen~thiazine.~~ A study has been made of theuse of potassium p-phenylazophenoxide for the identification of organichalogen compounds.The reagent reacts with primary and secondaryhalides, straight- and branched-chain halogen esters, halogenohydrins,halogeno-ketones and -ethers, and chloroformates. 75I n a method for the detection of ferrocenes the sample is first mixed withwater and extracted with chloroform; the extract is then treated with aceticacid and aqueous potassium ferricyanide to give a green colour or a darkblue precipitate depending upon the concentration of ferrocene present. 76A spot-test for the detection of arylmercury nitrate and other aryl-mercury salts has been described.7' The sample is heated to 160" withe6 R.Montequi, A. Doadrio, and J. Serrano, Inf. Quim. Anal., 1962, 16, 31.68 G. M. Christensen, Analyt. Chem., 1962, 34, 1030.6 7 F. Feigl and E. Libergott, Microchem. J., 1962, 6, 17.68 M. Pesez, J. Bartos, and J.-C. Lampetaz, BuZ7. SOP. chim. France, 1962, 719.60 H. Bro11 and G. Fischer, Mikrochim. Acta, 1962, 249.'O T. S. Ma and H. MOSS, Mikrochim. Acta, 1962, 111.71 V. Anger and G. Fischer, Milcrochim. Acta, 1962, 501.7 2 F. Feigl and D. Haguenauer-Castro, Milcrochim. Acta, 1962, 701.73 W. Wawrzyczek, 2. analyt. Chem., 1962, 185, 446.7 4 F. Feigl and D. Hagusnauer-Castro, Chemkt-Analyst, 1962, 51, 7.76 E. 0. Woolfolk, E.Donaldson, and M. Payne, J . Org. Chem., 1962, 27, 2653.7 6 J. D. Behun, Talanta, 1962, 9, 83.7 7 F. Feigl, Chemist-Analyst, 1962, 51, 4CARTWRIGHT, WESTWOOD, AND WILSON 443benzoin, and the nitrous acid formed is detected with a filter-paper treatedwith Griess reagent.5. METHODS OF SEPARATIONSolvent Extraction.-As a method of separating metals which is usuallyselective and can sometimes be made specific, and which with very simpleprocedures can concentrate traces in a form suitable for direct instrumentaldetermination, solvent extraction provides an inviting substitute for avariety of tedious chemical operations. It is only to be expected, therefore,that there is a great volume of published work; and probably to be expected,too, that a proportion of it is repetitive and inessential.Morrison and Ffeiser 78 have provided a valuable table of recentlypublished data for a large number of metals, and have reviewed extractionsystems employing the main chelating agents used in solvent extraction:dithizone, pyridylazonaphthol, the oximes, l-nitroso-2-naphthol, and cup-ferron and its analogues, together with other chelating and ion-associationreagents. The use of paper chromatography to indicate if solvent extractionis feasible in given circumstances has been suggested 79 as a result of correla-tion found when tributyl phosphate was used as a developing medium inpaper chromatography, and as an extractive solvent for iron(m), cobalt,and copper, at varying concentrations of hydrochloric acid.Formulae forthe efficiency of extraction have been derived8O from a study of metalcomplex-solvent systems, and supported by a study of the extraction ofradiocadmium from water into chloroform with 18 different chelatingagents. The use of trifluorothenoylacetone as an extractive solvent hasbeen reviewed 81 and optimum conditions have been tabulated for extractionof 40 metals. Selective extraction of 35 metals has provided the basis fora scheme of qualitative cation analysis,82 and published information on thepartition between water and organic solvents of 42 metal-oxine complexesa t varying pH values has been critically discu~sed.~~ The batch extractionof dithizone complexes in chloroform with silica gel as a supporting solidphase has been described, with particular investigation of the separationof mercury.Most of the transition metals and many of the main-group metals havebeen the subject of solvent-extraction studies; only a few of the mostinteresting applications can be mentioned.Neptunium( IV) can be separatedfrom other transuranic elements and from fission products by extractionwith tri-iso-octylamine in xylene from dilute nitric acid solution ; s 5 satis-factorily quantitative results can only be obtained, however, by a secondextraction, with trifluorothenoylacetone in xylene. Uranium can be ex-tracted with tri-n-butyl phosphate, but traces remain; these can be removedG. H. Morrison and H. Freiser, Analyt. Chem., 1962, 34, 65R.G. K. Schweitzer and D. R. Randolph, Analyt.Chim. Acta, 1962, 26, 567.A. K. De and S. M. Khopkar, J . Sci. I n d . Res., India, A , 1962, 21, 131.7 9 A. Musil, W. Haas, and G. Weidmann, Mikrochim. Acta, 1962, 833.82 G. Tolg, 2. analyt. Chem., 1962, 190, 161.8 3 F. Umland, 2. analyt. Chem., 1962, 190, 180. ** T. B. Pierce and P. F. Peck, Analyt. Chhn. Acta, 1962, 26, 557.8 5 R. A. Schneider, Analyt. Chem., 1962, 34, 522444 ANALYTICAL CHEMISTRYby a second extraction, with oxine.s6 An acidified trioctylphosphine oxidecyclohexane system has been used in the separation of zirconium, hafnium,niobium, and tantalum, 87 and zirconium can be quantitatively extractedfrom concentrated hydrochloric acid with trioctylamine, with direct colori-metric determination possible in the organic phase.s* A simple method fordetermining chromium in corrosion products involves extraction of thetetrabutylammonium chromate into isobutyl methyl ketone.89Iron has been separated from zirconium, and from the large number ofelements which do not form anionic chloro-complexes, by extraction fromhydrochloric acid into a solution of a tertiary amine such as tribenzylamine.90When small quantities of iron are extracted from aluminium chloride solu-tions, the use of isobutyl methyl ketone at low acidities overcomes diffi-culties of emulsion formation.With solutions of higher acidity a mixtureof isobutyl methyl ketone and benzene is re~ommended.~~ Copper may beextracted from boiler feed-water into chloroform as the yellow dibenzyl-dithiocarbamate complex, with no appreciable interference from other likelyconstituents. 92 Tributyl phosphate has been used to extract mercury fromvery dilute hydrochloric acid solutions containing other metals ;93 theefficiency of the separation with varying concenhration of hydrochloric acidwas studied by using radioactive tracers.Nowadays the term solvent extraction brings to mind almost exclusivelyprocedures for metals, such as those described above.It should not beforgotten that it still applies to the simple extraction of organic compoundswhich was its former province. In this connexion dimethyl sulphoxide hasbeen recommended as an extractant for polynuclear and highly chlorinatedhydrocarbons,9* with applications in the food and pesticide fields.Chromatography.-Many methods overlap the borders between chromato-graphy, electrophoresis, and ion exchange, particularly where ion-exchangematerials are used in column separations or are incorporated into chromato-graphic or electrophoretic papers or films.Nevertheless, for convenienceelectrophoresis and ion exchange, together with gas chromatography, areconsidered separately, and this section deals only with conventional liquidchromatographic separations on columns, papers, gels, and thin films.CoEumn chrmtography. Among the continuing investigations intofundamental principles are the correlation of chromatographic behaviourwith the surface energy and gel structure of the adsorbent, and the r6les ofactivation and deactivation in selection of the best column perforrnan~e,~~and an attempt to connect pH gradient and ionic-strength gradient in acol~11~1.96 An investigation has been made of the factors which influenceS S V .T. Athavale, R. L. Bhasin, and B. L. Jangida, Analyst, 1962, 87, 217.87 Hideo Saisho, Bull. Chem. SOC. Japan, 1962, 35, 514.8 8 E. Cerrai and C. Testa, Analyt. Chim. Acta, 1962, 26, 204.W. J. Maeck, M. E. Kussy, and J. E. Rein, Analyt. Chem., 1962, 34, 1602.A. V. Baeckmann and 0. Glemser, 2. analyt. Chem., 1962, 187, 429.91 H. Jackson and D. S. Phillips, Analyst, 1962, 87, 712, 718.9 2 A. L. Wilson, Analyst, 1962, 87, 884.9 3 D. F. C. Morris and J. H. Williams, Talanta, 1963, 9, 623.94 E. 0. Haenni, J. W. Howard, and F. L. Joe, jun., J . Assoc. OBc. Agric. Chemists,95 P.D. Klein, Analyt. Chem., 1962, 34, -733.96 6. M. Reiner and B. Reiner, Anal. Bzochem., 1962, 4, 1.1962, 45, 67CARTW-RIGHT, WESTWO 0 D , AND WILSON 445the elution of rock and sediment organic matter containing components ofhigh molecular ~ e i g h t . 9 ~The preparation and uses of various types of silica gel have been des-cribed 98 and a method of preparing a uniformly absorbent gel is detailed.99A device for gradient elution which permits complex but predictable gradi-ents, or alternatively step-wise elution, depends on the relative heights of aseries of containers which feed into a common line.100 In another method lolthe gradient is controlled by means of solenoid-operated clips.For many inorganic separations, column chromatography has been re-placed by more convenient and more selective solvent-extraction methods.It has, however, maintained its position in a wide range of organic separa-tions, as is shown by the large number of published methods in which itplays a part.The various paper techniques retain their popu -larity in both inorganic and organic work because of the speed of elutionand ease of identification of the separated spots.Only a few of the inter-esting applications can be reported.The general procedures of paper chromatography, ascending, descending,horizontal, and circular, have been reviewed ; a comparison for particularseparations showed that a modified circular technique gave better separa-tions and was simpler than the ascending or descending method.lo2 Theuse of a laboratory centrifuge for radial paper chromatography has beendescribed; the solvent is applied to the centre from a burette.lo3 Therelative merits of using transmitted and reflected light on dry and trans-parent papers has been investigated. For the copper-dithio-oxamide com-plex the best results were given by reflectance measurements on dry paper,and a method was developed for the determination of copper.104 By usingcommercial photographic copy-paper, spots which absorb ultraviolet lightcan readily be recorded.105 Other simple methods for recording chromato-grams are described in the section on thin-layer techniques.Concentrationof material in a chromatogram spot to such an extent that a solid or crystal-line aggregate may be obtained is achieved by cutting out the spot so that atail of paper is formed, clamping the spot between two microscope slides sothat the tail protrudes, and allowing solvent to rise between the slides.losA general method for detecting inorganic ions depends on spraying thepaper chromatogram with benzidine solution in acetic acid and then exposingit to furfuraldehyde vapour, whereupon characteristic colours are developedby many elements.lo7 Four phosphorus acids have been resolved bydevelopment on paper with an isopropyl alcohol-isobutyl alcohol-water-Paper chromatography.97 P.Hamway, M. Cefola, and B. Nagy, Analyt. Chem., 1962, 34, 43.98 J . Pitra, Chem. Listy, 1962, 56, 495.g D J. Pitra and J. StGrba, Chem. Listy, 1962, 56, 544.loo N.G. Anderson, H. E. Bond, and R. E. Canning, Anal. Biochem., 1962, 3, 472.lol R. A. Teekell, W. H. Boling, W. A. Lyke, and J. Chiriboga, J . Chromatog.,lo2 A. Grune, Riechstoffe u. Aromen, 1962, 12, 42, 104.lo3 G. M. Christensen and R. Swor, J. Chem. Educ., 1962, 39, 347.lo4 R. B. Ingle and E. Minshall, J. Chromatog., 1962, 8, 369, 386.lo5 A. S. Milton, J. Chromatog., 1962, 8, 417.lo6 I?. Davis, C. A. Dubbs, and W. S. Adams, Analyt. Chem., 1962, 34, 175.lo' T. Ghti and E. NovAk, Magyar K6m. Folydirat, 1962, 68, 293.1962, 7, 424446 ANALYTICAL CHEMISTRYammonia system, the spots being located by treatment with ammoniummolybdate and reduction by hydrogen sulphide to Molybdenum Blue.108Separation of the elements between actinium and americium has beenachieved by elution with acidified methanol, ethanol, propanol, or acidifiedbutanol.1099 110Five elution systems were compared for the resolution of a syntheticmixture of 32 amino-acids. The best, butanol-acetic acid-water and phenol-water, separated 29 spots, of which 4 were mixed.ll1 The separationof 12 free phenolic acids in cigarette smoke and tobacco was carried outby using a two-dimensional descending technique, the spots being identifiedby ultraviolet light and by staining.l12 Optical brighteners, stripped fromtextiles, have been characterised by separation on paper and observationunder ultraviolet light.l13 Microgram quantities of the more importantchlorinated insecticides and of some of their metabolites have been separatedby reverse-phase paper chromatography, with liquid paraffin as the fixedphase and aqueous acetone as the mobile pha~e.11~Advantages of speed, sharpness, and versa-tility inherent in this method have been widely appreciated.A review ofthe principles and techniques, with mention of a large number of applica-tions, has been published.115 Work with microgram quantities of materialson microscope slides as supports has advantages in rapid preparation ofthe film and elution of the material.116-118The relation between the area of the spot and weight of material presenthas been investigated, and a comparison made of the accuracy of graphicaland algebraic methods of determining quantities. 119 Sideways diffusionof thin-layer chromatograms can be reduced by using ridged glass plates.lZ0The cautious use of sodium dichromate or potassium permanganate in sul-phuric acid is advocated for the general location of spots of oxidisablematerials in thin-layer chromatograms, 121 and permanent records of chrom-atograms can be made by using a commercial photo-copier 122 or xerographiccopier.123 Layers made by spreading a paste of cellulose powder and wateron plates and drying them quickly in an oven have allowed speedy separa-tions of dyes to be made,124 and a separation typical of hundreds in theliterature is that of methoxypiperonylic acids on silica-gel layers, withdevelopment with ethyl acetate-hexane-acetic acid, and, after evaporationThin-layer chromatography.lo8 M.Ebert and A.Varhanikovit, Chem. prumysl, 1962, 12, 192.loo C. Keller, J. Chromatog., 1962, 7, 535.110 F. Clanet, J. Chromatog., 1962, 7, 373.111 Wei-Hsien Chang, Bull. Assoc. Agric. Chem. Nut. Taiwan Univ., 1961, 10, 32.112 Chao-Hwa Yang and 5. H. Wender, J. Chromatog., 1962, 8, 82.113 L. Meckel, Textil-Praxis, 1961, 16, 737.11* W. H. Evans, Analyst, 1962, 87, 569.115 C. A. Teijgeler, Pharm. Weekblad, 1962, 97, 43, 401.116 R. Wasicky, Analyt. Chem., 1962, 34, 1346.117 A. F. Hofmann, Anal. Biochem., 1962, 3, 145.118 J. J. Peifer, Mikrochim. Acta, 1962, 529.119 S. J. Purdy and E. V. Truter, Analyst, 1962, 87, 802.120 A. Gamp, P. Studer, 13. Linde, and K. Meyer, Experientia, 1962, 18, 292.121 H. Ertel and L. Homer, J. Chromatog., 1962, 7, 268.122 H. R. Getz and D.D. Lawson, J. Chromatog., 1962, 7, 266.124 P. Wollenweber, J. Chromatog., 1962, 7, 557.J. Hilton and W. B. Hall, J. Chromatog., 1962, 7, 266CARTWRIGHT, WESTWOOD, AND WILSON 447of the solvent, identification by spraying with an acid solution of chroizlo-tropic acid and heating.Electrophoresis.-The organic applications to such materials as serumconstituents, amino-acids, and sugars and their derivatives heavily outweighthe ionophoresis of inorganic materials. Advances have been directed moreto the improvement of apparatus than to new uses.A review of starch-gel electrophoresis, with 163 references, has beenpublished and a technique for making starch gel transparent, for easeof location of zones, has been described.12' Polymerised acrylamide gelhas been used as a medium in a vertical cell for resolution of serum com-ponents.*A micro-electrophoresis apparatus needing only 12 ml. of buffer solution,and allowing separations in 30 minutes, has been described,129 and at theother end of the scale is a preparative apparatus in which electrophoresis iscarried out on slabs of starch gel in which grooves are cut to carry an elutingbuffer solution that removes the fractions as they reach the gr00ve.l~~An automatic apparatus has been described which controls the duration ofelectrophoresis, removes the paper from the electrolyte, dries the chromato-gram and switches itself 0ff.131 The dual advantage of providing coolingand uniform pressure on the paper is afforded by an inflatable rubber bladderthrough which can be passed a stream of air or More compactspots are claimed to result if the sample solution is applied to a circle re-moved with a cork-borer from the sheet, and re-inserted when the run isabout to start.l33Ion Exchange.-In a review of the subject 134 it is stated that ion-exchange procedures have been devised for separations involving everyelement in the Periodic Table, except the inert gases.A great variety ofexchange materials is now available, and desired properties of cross-linkingand particle size are easier to obtain; characteristics of 370 resins have beenlisted. 135The obvious overlap of ion-exchange procedures with chromatographyis extending by introduction of more modified celluloses and papers loadedwith ion-exchange resins.Another overlap, this time into solvent-extractionprocedures, is provided by liquid ion exchangers such as alkylamines andquaternary ammonium compounds for anions, and organophosphorus acidsfor cations; an account of their merits and a considerable list of representa-tive applications have been given.136Typical of inorganic uses of ion exchange have been separations of therare-earth elements from anion-exchange columns by using acid-methanollz5 M. Beroza and W. A. Jones, Analyt. Chem., 1962, 34, 1029.lZ6 c. Altaner, Chem. Listy, 1962, 56, 334.lZ7 E. Vahvaselkii, Nature, 1962, 193, 474.lZ8 S. Raymond, Masumi Nakamichi, and B. Aurell, Nature, 1962, 195, 697.lZ9 J. Fischl, Clinica Chim. Acta, 1962, 7, 537.130 K.Murray, Ar,alyt. Biochem., 1962, 3, 415.131 J. Hrdina, M. Pechman, and J. Skoda, COIL Czech. Chem. Comm., 1962, 27, 969.132 S. W. Bailey and R. H. Hackman, J . Chromatog., 1962, 8, 52.133 J. Popowicz, J. Chromatog., 1962, 7, 271.134 R. Kunin and F. X. McGarvey, Analyt. Chem., 1962, 34, 48R, 101R.135 M. Marhol, Chem. Listy, 1962, 58, 728.136 C. F. Coleman, C. A. Blake, jun., and K. B. Brown, Talatata, 1962, 9, 297448 ANALYTICAL CHEMISTRYelution,137 and elution of their complexes with EDTA 138 and sulphosalicylicacid;139 the removal of cations and anions before determining silica;l40separations of very many small groups of metals; and extension of thelower limits of detection of metals by using particles of resin as a supportfor spot tests: nanogram quantities of iron have thus been identified.141In many fields of organic analysis, and particularly in biochemistry, ionexchange has proved its worth, as, for example, in the separation of hydroxy-acids,lP2 aldonic acids, and sugars,le3 amino-acids,lP4~ 145 and mixturesof barbiturates many of these separations are performed on treatedpapers.Gas Chromatography.-The number of papers continues to increase, bothon the development of theoretical principles and on applications. Negri 147has reviewed advances in technique, including the use of different adsorbentsin parallel and in series, temperature regulation of the thermistor and thecolumn, phases suitable for high-temperature work, improvements in detec-tors, the use of capillary columns, and the reaction of the test substanceimmediately before chromatography.Maier and Karpathy 148 have at-tempted, with results sufficiently accurate for most practical problems, tosystematise the choice of column and conditions in terms of charts of data.A mathematical survey of the factors affecting efficiency of gas chromato-graphy for analysis, with a brief review of techniques, has been published,149and applications have been described to work in nuclear technology, includingthe advantages of temperature programming and the use of molecularsieves. OComparative investigations have been made of the merits of varioussupport materials; performance with a non-polar, a polar, and a stronglypolar stationary phase was studied,151 and, with the criteria for an idealsupport in view, the practical characteristics of a number of materials wereinvestigated.152Discontinuity of the liquid phase can affect to an unpredictable extentthe values of retention times and volumes, and if the support is uncovereda t any point spurious peaks are produced; this subject has been discussedin detai1.153 The behaviour of 10 inorganic gases on halogenated hydro-carbon columns, with hydrogen as carrier and thermal-conductivity detec-137 J. P. Faris and J. W. Warton, Analyt. Chem., 1962, 34, 1077.13* J. Minczewski and R. Dybczyliski, J. Chromatog., 1962, 7, 98, 568.140 L. H. Andemson, Arkiv Kemi, 1962, 19, 223.141 Masatoshi Fujimoto and Yukio Nakatsukasa, Analyt. Chim. Acta, 1962, 26,142 B.Alfredsson, L. Gedda, and 0. Samuelson, Analyt. Chim. Acta, 1962, 27, 63.143 0. Samuelson and R. Simonson, Svemk Papperstidn., 1962, 65, 363.144 C. S. Knight, J. Chromatog., 1962, 8, 205.145A. B. Svendsen and E. Brochmann-Haussen, J. Pharm. Sci., 1962, 51, 514.146 H. V. Street and S. K. Niyogi, J. Pharm. Sci., 1962, 51, 666.147 R. C. Negri, dfinidad, 1961, 18, 383.14* H. J. Maier and 0. C. Karpathy, J . Chromatog., 1962, 8, 308.149 M. A. Khan, Lab. Practice, 1962, 11, 120.lz0 A. D. Horton, Nucl. Sci. Engng., 1962, 13, 103.151 R. Staszewski and J. Janak, Coll. Czech. Chem. Comm., 1962, 27, 532.152 D. T. Sawyer and J. K. Barr, Analyt. Chem., 1962, 34, 1518.153 R. A. Keller, R. Bate, B. Costa, and P. Forman, J. Chromatog., 1962, 8, 157.J. S.Fritz and T. A. Palmer, Talanta, 1962, 9, 393.427CARTWRIGHT, WESTWOOD, AND WILSON 449tors, has been investigated,154 and ionisation detectors have been used todetect trace quantities of permanent gases. 155A considerable volume of useful papers has been concerned with establish-ing in a practical manner the best column materials and operating conditionsfor particular separations. Among these are separations of isomeric ali-phatic alcohols,156 isomeric disubstituted benzenes,l57 methylsilanes, 15*high-boiling amine~,l5~ and dissolved gases in aqueous solution, l60 and thedetermination of atmospheric pollutants 161 and blood-alcohol.1626. GRAVIMETRIC AND TITRIMETRIC ANALYSISGravimetric Analysis.-Instrumental analysis is nowadays so much tothe fore that many analysts may understandably ask, whither gravimetry ?It may well be that gravimetric methods will be finally relegated to occa-sional use for reference purposes, but for the moment there is still con-siderable activity to report in the field of inorganic analysis.In experiments to determine the weight constancy of porcelainfilter crucibles Braddock 163 found that the crucibles used maintained con-stant weight after being heated to various temperatures in the range135-SOO", and that weights were not affected by the use of either water orethanol wash liquids.Increasing interest has been shown in the use of masking agents to effectseparations of metal ions, and Hulanicki 164 has described the derivationof a new term, the masking coefficient, to predict whether masking orprecipitation occurs.The reactions of aliphatic mercapto-alcohols and mercapto-acids withinorganic cations have been investigated,l65 and methods have been de-veloped for the determination by precipitation of silver, cadmium, lead,and thallium(1) and for the qualitative detection of other elements.A study has been made of the influence of certain foreignions on the determination of potassium as the tetraphenylborate.166 Highresults were obtained in the presence of sodium persulphate and low valuesin solutions containing sodium periodate ; no appreciable errors were causedby the presence of sodium perchlorate.Embelin (2,5-dihydroxy-3-undecyl-l,4-benzoquinone) has been found togive insoluble complexes with copper and cadmium in the pH ranges 2-5-65General.Inorganic.154 H.Runge, 2. analyt. Chem., 1962, 189, 111.155 G. Gnauck, 2. analyt. Chem., 1962, 189, 124.156 B. Drews, H. Specht, and G. Offer, 2. analyt. Chem., 1962, 189, 325.15'A. E. Habbousch and B. 0. C. Norman, J . Chromatog., 1962, 7, 438.158 T. Garzb, F. Till, and I. Till, Magyar Kim. Polydirat, 1962, 68, 327.159 J. Vessman and G. Schill, Svensk farm. Tidslcr., 1962, 66, 601.160 J. W. Swinnerton, V. J. Linnenbom, and C. H. Cheek, Analyt. Chem., 1962,161 T. Bellar, J. E. Sigsby, C. A. Clemons, and A. P. Altshuller, Analyt. Chem.,lSZ G. Machata, Mikrochinz. Acta, 1962, 691.163 L. I. Braddock, Chemist-Analyst, 1962, 51, 79.16* A. Hulanicki, Talanta, 1962, 9, 549.165 E. Casassas and F. Buscarbns, Chinz.analyt., 1962, 44, 20.lS6 J. D. R. Thomas, Analyst, 1962, 87, 151.34, 483.1962, 34, 763.450 ANALYTICAL CHEMISTRYand 6.0-6-5, respectively. 167 The precipitates are suitable for gravimetricpurposes and the method can be used for the separation of the two metals.Copper is precipitated a t pH 2.5-3.0 and the complex is ignited to oxide;cadmium is precipitated in the filtrate at pH 6.0-6-5. Copper can also bequantitatively precipitated by NN'-disalicylidene-ethylenediamine,168 andweighed after drying a t 100-120".A method has been described for the separation of strontium and calciumby precipitation of strontium with an ethanolic solution of rhodizonic acidin the presence of N - hydroxyetliylethylenediaminetriacetic acid as achelating agent.A double precipitation is necessary when large amountsof calcium are present.A new method has been proposed for the determination of scandiumand its separation from rare earths and thorium by precipitation withmandelic acid.170 Satisfactory results were obtained over the pH range1.8-3.2, but a t higher pH values coprecipitation of thorium took place.The precipitate was ignited at 800" and weighed as Sc,O,. Lanthanumferrocyanide has been shown to be quantitatively precipitated from solutionby the addition of an excess of potassium ferrocj-anide. 171 The precipitatemay be weighed as LaKFe(CN), or the lanthanum can be determined bytitrating the excess of potassium ferrocyanide solution. The determinationof cerium(1v) and its separation from rare earths with 1 -hydroxy-3-methoxy-9-xanthone has been described.172 I n an investigation of the influence ofalkali metals and ammonium ions on the precipitation of thallium dichromateit has been found that potassium, rubidium, czesium, and ammonium, butnot lithium or sodium, are ~oprecipitated.~~~ This may be overcome tosome extent by precipitation from hot acid solution, but reprecipitation ofthe thallium dichromate is necessary when the concentration of the inter-fering ions is high.Germanium has been precipitated as the tetraphenylarsonium germano-molybdate complex 174 having the formula Ge(Mo,O,,),[ ( C6H5)BA~]I, and astudy has been made of interfering ions.The use of N-benzoylphenylhydroxylamine (BPHA) for the determina-tion of zirconium and its separation from iron, aluminium, chromium,titanium, niobium, and tantalum has been described.175 The precipitatecan be weighed as Zr(BPHA), which is stable up to 240", or as ZrO, afterheating to above 500".Two new reagents, tartrazine and flavazine, havebeen proposed for the precipitation of zirconium.176 The reagents werefound to be more sensitive than mandelic acid and the precipitates settledmore rapidly. Zirconium has also been quantitatively precipitated in the167 C. Bheemasankara Rao, V. Venkateswara Rao, and V. Venkateswarlu, 2. analyt.Chem., 1962, 185, 216.168 B. R. Singh and S. Kumar, 2. analyt. Chem., 1962, 185, 259.1 6 9 L. Hainberger and S. C. Shnchez, Mikrochim. Acta, 1962, 760.I7O I.P. Alimarin and Shen Han-Si, Talanta, 1962, 9, 1.1'1 5. N. Gaur, 2. analyt. Chem., 1962, 185, 357.172 B. Dev and R. D. Jain, Proc. Indian Acad. Xci., 1962, 55, A, 213.173 N. I. .Bashilova, Zhur. analit. Khim., 1962, 17, 190.1'4 J. P. LabbB, Mikrochim. Acta, 1962, 283.1 7 5 I. P. Alimarin and Tze Yung-Schaing, Talanta, 1962, 9, 9.1 7 6 G . Popa, F. Popea, D. Cluceru, and G. Baiulescu, Analyt. Chim. Acta, 1962,26, 434C ART W RIG H T , WE S T W 0 0 D , AN D W I L S 0 NpH range 1 4 by the addition of diammonium indigo-5,5’-disulphonate. l7Iron, titanium, aluminium, beryllium, uranium, cerium(rn), nickel, andcobalt do not interfere. The separation and gra.vimetric determination ofthorium and cerium(Ir1) with vanillin has been described. 178A study has been made of the gravimetric determination of uranium(v1) byprecipitation with N - benzoyl-N-phenylhydroxylamine .I7 9 The precipitatemay be weighed directly or as U308 after ignition. Cerium(In), thorium,lead, and bismuth may be masked with magnesium-EDTA complex.Iron(m), titanium(Iv), zirconium, molybdenum(vI), and small amounts ofaluminium may be removed before the determination of uranium by pre-cipitating them with the reagent in more acid solution, but fluoride, carbon-ate, and organic acids interfere.Uranium has also been determined byprecipitation with hexaminecobalt nitrate.Is0 Fluoride does not interfereand the method is said to be suitable for the determination of uranium inuranium fluoride and uranium alloys.Palladium can be quantitatively precipitated in acid solution by theaddition of a 1 yo solution of quinolinimide (pyridine-2,3-dicarboxim-ide).181 Interference by tin may be prevented by the addition of citricacid, but the presence of oxalate, tartrate, or EDTA causes incompleteprecipitation.Reference has been made inprevious Reports to the r61e of nucleation in precipitation from homogeneoussolution, but this aspect does not appear to have received much recent atten-tion, and the published papers deal mainly with the application of the tech-nique to the precipitation of specific compounds with occasional referencesto nucleation.An account of precipitation from homogeneous solution hasbeen given by Dams71g2 and Williams 183 has reviewed recent advances inthe field.I n further studies of precipitation at constant pH by cation release frommetal-EDTA complexes consideration has been given to the importanceof complex stability and the solubility of the precipitate.184 An examplehas been given of the use of EDTA as a masking agent in the separationof calcium and barium.EDTA has also been used as a masking agent inthe homogeneous precipitation of sulphides by hydrolysis of thioacetamide. lg5The fractional precipitation of lanthanum praseodymium iodate, involvingdouble complex-formation and replacement, has been described. lS6 Equalamounts are complexed by [ (carboxymethylamino)di( ethy1eneimino)ltetra-acetic acid and N-(carboxymethyl)-N‘-2-hydroxyethyl-~~-ethylenedi-glycine, and iodate is added.Lanthanum is released by slow dropwiseaddition with stirring of cadmium chloride solution.177 B. D. Jain and J. J. Singh, J. Less-Common Metals, 1962, 4, 145.178 B. D. Jain and J. J. Singh, Analyt. Chim. Acta, 1962, 27, 359.179 J. Das and S. C. Shome, Analyt. China. Acta, 1962, 27, 58.lSo A. V. Vinogradov and R. M. Apirina, Zhur. analit. Khirn., 1962, 17, 222.lS1 A. K. Majumdar and S. P. Bag, Z. analyt. Chem., 1962, 188, 347.Is2 R. Dams, Mededel. vlmm. chem. Ver., Nr. 3, 1961, 65.la3 M. Williams, I n d . Chem., 1962, 38, 134, 186.lS4 P. F. S. Cartwright, Analyst, 1962, 87, 163.lS5 G. C. Krijn, Chem. Weekblad, 1962, 58, 127.lS6 F. H. Firsching, Analyt. Chem., 1962, 34, 1696.451Precipitation from homogeneous solution452 ANALYTICAL CHEMISTRYContinued interest is shown in methods involving the formation of theprecipitant in situ.The reaction between salicylaldehyde and hydroxyl-amine hydrochloride in the presence of copper ions has been used to pre-cipitate copper sali~ylaldoxim.~~~ A dense precipitate was obtainedwhich was dried to constant weight a t 110". A study has been made of thehydrolysis of 8-acetoxyquinoline,lS8 and the method has been used for theprecipitation of magnesium 8-hydroxyquinoline. lS9 A good separationfrom sodium, potassium, and barium was obtained a t pH 10.0, but it wasfound necessary also to cool the solutions in an ice-bath, and to add the8-acetoxyquinoline slowly with stirring to obtain a satisfactory rate ofhydrolysis. Precipitation usually occurred when the last of the reagent hadbeen added.The hydrolysis of 8-acetoxyquinoline has also been investigated by Weissand Shipman lgo who have applied the method to the study of co-crystallisa-tion of ultramicro-quantities of iron and other elements.The reaction between biacetyl and hydroxylamine to form dimethyl-glyoxime has been used to precipitate nickel dimethylglyoximate. l91 Duringthe investigation evidence was found of the existence of a complex betweennickel and biacetyl monoxime.The persistent supersaturation with respectt o dimethylglyoximate which was found to be present in the system wasconsidered t o be the explanation of the incomplete precipitation of smallamounts of nickel with dimethylglyoxime.It has been reported that niobium and tantalum can be precipitated fromtheir solutions in hydrogen peroxide and nitric acid by thermal decom-position of the soluble peroxide ;I92 coprecipitation of titanium is negligible.When thermal decomposition is carried out in slightly alkaline medium,niobium, tantalum, and titanium are precipitated with only low coprecipita-tion of tungsten.Molybdenum has been precipitated as sulphide by hydrolysis of thio-acetamide.193 The precipitate was ignited a t 500-550" and weighed asthe trioxide.A nuclear magnetic resonance method has been used to study the pre-cipitation of manganese sulphide from homogeneous solution.lg4Titrimetric Analysis.-This Report is divided, as in previous years, accord-ing to the class of titrimetric determination. A new section has been addeddealing with photometric titrations and certain papers have been includedwhich appear to be of fundamental interest but were omitted in earlierReports.Reviews have been published describing the applications ofvanadate as an oxidimetric reagent lg5 and the use of quinol (hydroquinone)General.18' R.F. Pietrzak and L. Gordon, Talanta, 1962, 9, 327.la8 D. Elliot, L. C. Howick, B. G. Hudson, and W. K. Noyce, Talanta, 1962, 9,189 J. T. Corkins, R. F. Pietrzak, and L. Gordon, Talanta, 1962, 9, 49.190 H. V. Weiss and W. H. Shipman, Analyt. Chem., 1962, 34, 1010.l91 E. D. Salesin, E. W. Abrahamson, and L. Gordon, Talanta, 1962, 9, 699.192 R. Dams and J. Hoste, Talanta, 1962, 9, 86.l93 F. Burriel-Marti and A.Maciera Vidan, Analyt. Chirn. Acta, 1962, 26, 163.194 R. L. Causey and R. M. Maza, Analyt. Chem., 1962, 34, 1630.195 A. Berka, J. Vulterin, and J. Zfka, Chemist-Analyst, 1962, 51, 24.723CARTWRIGHT, WESTWOOD, AND WILSON 453as a reductimetric reagent in titrimetric analysis. lg6 Two neutral mixedligand complexes, dicyanobis-( 1 , 10-phenanthroline)iron(rr) and dicyanobis-(e,Z’-bipyridyl)iron(n), have been used as indicators for the titration ofvarious weak bases in non-aqueous solvents and also for certain redoxtitrations in aqueous solution.lS7 It has been recommended that mor-pholinium 3-oxapentamethylenedithiocarbamate is a suitable primary sub-stance for the preparation of standard solutions of acids. lg8Bishop and Jennings have continued their investigations of the use ofchloramine-T and have published papers describing titrations in hydro-chloric acid media with iodine monochloride as a reaction intermediate,lS9the chloramine-T-antimony reaction,200 the chloramine-T-hydrazine re-actionY2O1 and the chloramine-T-thallium and -thiocyanate reactions.202A study of the titration of silver with halide orthiocyanate ions has shown that satisfactorily sharp end-points may beobtained at pH 4-5 by using p-ethoxychrysoidine as an adsorptionindicator.203Magnesium may be precipitated as magnesium ammonium arsenate, theprecipitate dissolved in sulphuric acid, and the resulting arsenic acid titratediodimetrically.20* The method has been found to be more rapid and togive more reproducible results than determination by precipitation as8-hydroxyquinoline complex.A similar technique has been proposed forthe rapid determination of thorium after precipitation of thorium hydrogenar~enate.~O5A rapid method for the determination of persulphate has been described,based on the reaction between persulphate and thiosulphate in the presenceof copper ions.206 An excess of thiosulphate is added and the excess istitrated with standard iodine solution.A bromometric method has been used for the determination of formatesby oxidation with bromine,207 and hydrazine in 35% hydrazine solutionshas been determined by titration with potassium iodate after acidificationwith hydrochloric acid.208Bishop has discussed the precise calculation ofdata for redox titration curves 209 and the influence of absolute concentra-tion on the parameters of redox titrimetry.210 The use of Variamine Blueas a redox indicator in the determination of thiocyanate and mercury(n)Halogen titrations.Other redox titrations.lS6 A.Berka, J. Vulterin, and J. Z$ka, Ghemist-Analyst, 1962, 51, 88.lS7 A. A. Schilt, Analyt. Chim. Acta, 1962, 26, 134.lS8 W. Haas, Mikrochim. Acta, 1962, 738.ls9 E. Bishop and V. J. Jennings, TaZanta, 1962, 9, 581.2oo E. Bishop and V. J. Jennings, Talanta, 1962, 9, 593.201 E. Bishop and V. J. Jennings, Talanta, 1962, 9, 603.202 E. Bishop and V. J. Jennings, Talanta, 1962, 9, 679.203 K. N. Tandon and R. C. Mehrotra, Analyt. Chim. Acta, 1962, 27, 15.204 G. 13. Shakhtakhtinskz and G.A. Aslanov, Azerb. Khim. Zhur., 1961, 63; Ref.2051. A. Mamedov and G. B. Shakhtakhtinskii, Azerb. Khim. Zhur., 1961, 99;206 C. D. Bisht and S. P. Shrivastava, 2. analyt. Chem., 1962, 188, 23.207 R. M. Verma and S. Bose, J . Indian Chern. Soc., 1962, 39, 329.2 0 8 U.K.A.E.A. Report PG 342(W), 1962.209 E. Bishop, Analyt. Chirn. Acta, 1962, 26, 397.210 E. Bishop, Analyt. Chirn. Acta, 1962, 27, 253.Zhur. Khim., 1962, Abs. No. 5D51.Ref. Zhur. Khim., 1962, Abs. No. 4D99454 ANALYTICAL CHEMISTRYions has been investigated.2ll Thiocyanate may be determined by titratingwith mercuric nitrate, or mercuric ions can be determined by adding aknown volume of potassium thiocyanate solution and titrating the excess.Vanadium(1v) can be determined by titration with cerium(1v) sulphate byusing Rhodamine 6G as a fluorescent indicator;212 the fluorescence is sud-denly quenched by a slight excess of oxidant.A method has been described for the determination of niobium in thepresence of tantalum.213 Niobium(v) is reduced in a Jones reductor toniobium(m) which is collected in ammonium ferric sulphate solution toproduce ferrous iron equivalent to the niobium present.The ferrous ironis then determined by titration with dichromate solution.Iron, uranium, or plutonium can be determined by titration withcerium(1v) solution in nitric acid media.214Ammonium hexanitratocerate(1v) has been used for the titration ofoxalic and mandelic acids in nitric acid or hydrochloric acid by using ferroinindicator, 215 and a volumetric method for the determination of quinol(hydroquinone) using ferric alum and potassium dichromate has beendescribed.216The determination of fluorine by titration, with alumin-ium nitrate solution, arsenazo I (see below) being used as the indicator, hasbeen investigated.Tungstate has been determined by direct titration with lead nitratesolution with 6,13-dihydro-6,13-dihydroxy- 1,4:8,11 -pentacenediquinone-2,9-disulphonic acid as indicator.218Lindstrom and Stephens 219 have suggested theuse of magnesium iodate tetrahydrate as a standard for the preparation ofEDTA solutions for calcium and magnesium titrations.The use of metalliccopper as a primary standard for EDTA has also been studied.220 PFibiland Veseljr 2 2 1 have reported the use of a new titrimetric reagent, triethylene-tetramine-NNN’N”N‘’‘N’”-hexa-acetic acid (TTHA).The applicationof two arsono-type indicators has been studied.Z22 The first, 3-(2-arsono-phenylazo)-4,5-dihydroxynaphthalene-2,7-disulphonic acid (arsenazo I), canbe used for the determination of thorium(Iv), lanthanum(m), cerium(m),yttrium(m), and erlsium(1n) in acid solution, and magnesium in alkalinesolution. The second, 4-(2-arsonophenylazo)-3-hydroxynaphthalene-2,7-di-sulphonic acid disodium salt (thoron I), may be used to determine thoriumin acid solution.MisceZZaneous.Chebtometric titrations.211 Z. Gregorowicz, F. Buhl, and B. Piwowarska, 2. analyt. Chem., 1962, 188, 2.212 G. G. Rao and L. S. A. Dikshitulu, Talanta, 1962, 9, 289.213 J.B. Headridge and M. S. Taylor, Analyst, 1962, 87, 43.215 G. G. Rao, P. V. K. Rao, and K. S. Murty, Talanta, 1962, 9, 835.216 K. B. Rao, 2. analyt. Chem., 1962, 185, 286.217 V. M. Brodskaya, A. F. Kutelnkov, and G. A. Lanskoi, Byull. Nauch.-Tekh.Inform., Min. Geol. i Okhran N d r . , S.S.S.R., 1961, 104; Ref. Zhur. Khim., 1962, Abs.No. 9D93.218 H. Brantner, Mikrochirn. Acta, 1962, 125.219 F. Lindstrom and B. G. Stephens, Analyt. Chem., 1962, 34, 993.220 T. Iwamoto and K. Kanamori, Analyt. Chim. Acta, 1962, 28, 167.221 R. PFibil and V. Veself, Talanta, 1962, 9, 939.222 0. Gimesi, G. R&dy, and L. Erdey, Period. Polytech., 1962, 6, 15.J. Corpel and F. Regnaud, Analyt. Chim. Acta, 1962, 2’7, 36CARTWRIGHT, WESTWOOD, AND WILSON 455A procedure has been given for the determination of copper in thepresence of manganese and iron,223 and a new chelatometric determinationof mixtures of silver and lead has been described.224Barium EDTA has been used in new methods for the determination ofmixtures of zinc and chromium(m) and of zinc and aluminium.225Considerable attention has been given to the determination of aluminium.Pfibil and Vesely 226 have studied the use of 1,2-diaminocyclohexanetetra-acetic acid which reacts almost instantaneously with aluminium in the cold.Aluminium is determined by adding an excess of reagent and back-titratingwith lead nitrate solution, Xylenol Orange being used as indicator.Froma comparison of three methods for the determination of aluminium, Malissaand Kotzian 227 have concluded that a method due to PFibil et was tobe preferred. Other papers have described the determination of aluminiumin uranium metal 229 and in aluminosilicates.230The direct chelatometric determination of gallium with EDTA is possibleby using 8- hydroxy-7 - 1 ’-nap ht hylazo quinoline- 5- sulphonic acid as indicatorin the pH range 2.2-5; calcium, magnesium, cadmium, and zinc do notinterfere, and interference by aluminium can be avoided by the additionof fluoride.231 Thallium may be determined with EDTA with 8-hydroxy-7-2’-pyridylazoquinoline as indicator.232The selective determination of titanium in the presence of niobium andtantalum by a back-titration of an excess of diaminocyclohexanetetra-acetic acid with copper in the presence of hydrogen peroxide and PAN asindicator has been improved by the use of Methyl Calcein or Methyl CalceinBlue as metal fluorochromic indicator.233Reduction of chromium( VI) with sodium hydrogen sulphite in thepresence of a slight excess of EDTA leads to the quantitative formation ofchromium(n1)-EDTA complex.234 Chromium can be determined by backtitrating the excess of EDTA with thorium solution at pH 2-5-3-5.Chelatometric methods have been used to a limited extent in the deter-mination of organic compounds. Hennart has described the titrimetricdetermination of alkylmagnesium halides, 235 the determination of sul-p h ~ n a r n i d e s , ~ ~ ~ and the determination of purine-6-thi01.~~~223 D. A. Doornbos, G. Ab, and J.S. Faber, Phama. Weekblad, 1962, 97, 257.226 F. Sierra and J. Heriiandez Caiiavate, Anales real Xoc. espa6. Pis. QuiTn.,226 F. Sierra [and C. Sanchez Pedreno, Anales real SOC. espaii. Fi8. Quim., 19B2,226 R. P?ibil and V. Veself, Talanta, 1962, 9, 23.2 2 7 H. Malissa and H. Kotzian, Analyt. Chim. Acta, 1962, 26, 128.228 R. Piibil et al., Chem. Listy, 1957, 51, 2135.2 2 9 U.K.A.E.A. Report PG 293(S), 1962.230 H. Bennett, W. G. Hawley, and R. P. Eardley, Trans. Brit. Ceram. SOC., 1962,61, 201.231 A. I. Busev, L. L. Talipova, and L. M. Shrebkova, Zhur. analit. Khirn., 1962,17, 180.232 A. I. BUSBV, L. L. Talipova, and V. M. Ivanov, Zhur. Vsesoyuz. Khirn. obshch. im.D. I. Mendeleeva, 1961, 6, 598; Ref. Zhur. Khim., 1962, Abs. No. 9D58.233 E.Lassner and R. Scharf, Chernwt-Analyst, 1962, 51, 49.234 D. A. Aikens and C. N. Redly, Analyt. Chem., 1962, 34, 1707.235 C. Hennart, Chim. analyt., 1962, 44, 7.236 C. Hennart, Chim. analyt., 1962, 44, 8.1962, 58, B , 219.58, B, 223.C. Hennart, Talanta. 1962, 9, 97456 ANALYTICAL CHEMISTRYSpectrophotometric titrations. Many, but not all, of the methods discussedin this section are chelatometric; all have in common the use of photometricmethods for the determination of end points. Some references are given topapers which appeared last year and were not reported, but which are nowmentioned because of their particular interest.The theory of chelatometric titrations with a photometric end-point hasbeen discussed,238 and the construction of a simple photometric titrator hasbeen described.239 Details have been given of an instrument having in-creased sensitivity which embodies two photocells that simultaneouslyregister both colours of the indicator.240 The use of differential spectro-photometric methods for determining the end points in aqueous and non-aqueous acid-base titrations and in chelatometric titrations has been re-ported.241 The method has been applied to the titration of phosphoric acid,acetic acid, L-phenylalanine, L-leucine, and DL-alanine with sodium hydroxidein aqueous solution, to the titration of sodium acetate and o-chloroanilinewith perchloric acid in glacial acetic acid, and to the determination ofmagnesium with EDTA.The consecutive titration of calcium and magnesium has been investi-gated.242 Calcium was first titrated a t pH 10 by using ethyleneglycol-bis(aminoethy1)tetra-acetic acid with murexide indicator, followed by titra-tion of magnesium with EDTA and Eriochrome Black T indicator to aphotometric end point.The chelatometric determination of submicrogramamounts of calcium and magnesium has also been described.243Cadmium has been determined in the presence of zinc by titration to aphotometric end point with 1 ,Z-di- (2-aminoethoxy)ethane-NNN’N’-tetra-acetic acid and ammoniacal copper solution as indicator. 244Titanium has been determined in the presence of aluminium,245 andthorium, in amounts as low as 10 micrograms, has been determined bytitrations with EDTA, @-SNADNS-6 being the indicator.246The chelatometric determination of plutonium in reactor-fuel processingplant solutions has been described ;z47 after suitable extraction, an excessof EDTA is added and the remaining EDTA is titrated with zinc chloridesolution, dithizone being used as indicator.Microgram amounts of fluoride have been determined by titration withthorium nitrate solution to which sodium alizarinmonosulphate indicator isadded.248Flaschka and Ganchoff have described the selective chelatometric deter-mination of cobalt, using a photometric method for the detection of theend point.249238 H. Flaschka, Talanta, €961, 8, 381.23s H. Flaschka and P. Sawyer, Talanta, 1961, 8, 521.240 J. Fog and E. Jellum, Analyst, 1962, 87, 302.241 S. Bruckenstein and M.M. T. K. Gracias, Analyt. Chem., 1962, 34, 975.242 H. Flaschka and J. Ganchoff, TuZuntu, 1961, 8, 720.243 H. Flaschka and P. Sawyer, Tuhnta, 1962, 9, 249.2 4 4 H. Flaschka and J. Ganchoff, Taluntu, 1962, 9, 76.245 L. Giuffre and F. M. Capizzi, Ann. Chim. (Italy), 1962, 52, 398.2 4 6 S. K. Datta and S. N. Saha, Chemist-Analyst, 1962, 51, 49.2 4 7 D. G. Boase, J. I<. Foreman, and J. L. Drummond, Talanta, 1962, 9, 53.248 W. P. Pickhardt, Analyt. Chem., 1962, 34, 863.2 4 9 H. Flaschka and J. Ganchoff, Talantu, 1961, 8, 885CARTWRIGHT, WESTWOOD, AND WILSON 457The theoreti-cal basis of titration in non-aqueous media has been reviewed,250 and ageneral study has been made of the influence of cation structure on thetitration characteristics of quaternary ammonium titrants 251 and of factorsaffecting the stability of non-aqueous quaternary ammonium tit rant^.^^^The purification of pyridine for use in non-aqueous titrations has beendescribed,253 and details have been given of the preparation of non-aqueoustitrants by reaction of quaternary ammonium chlorides with potassiumhydroxide in isopropyl alcohol solution. 254Cerimetric methods in non-aqueous media have been applied to theoxidation and determination of ascorbic acid.255 The semimicro-deter-mination of the neutralisations equivalents of higher fatty acids has beenstudied and the method has been applied to the determination of lauric,myristic, palmitic, elaidic, stearic, oleic, and linoleicNN'-Disubstituted p-phenylenediamines have been determined byneutralisation with perchloric acid,257 and the determination of codeineand phenobarbitone by titration with perchloric acid in dioxan has beendescribed.258Non-aqueous titrations and functional-group determinations.7. INSTRUMENTAL END-POINT DETERMINATIONSGeneral.-Under this heading conductometric, amperometric, coulo-metric, potentiometric, and high-frequency methods have been grouped.Probably because of its simplicity, direct potentiometry has continued tobe the most popular technique and a very large number of papers haveappeared on its applications. Only those of particular interest to analystscan be considered in this Report.Chronopotentiometry has been developing, though little work appearsto have been done in this country.New work has appeared on differentialelectrolytic potentiometry, which is capable of application with accuracy toextremely dilute solutions and nanogram quantities. Applications ofamperometric titration methods have continued to increase and several novelprocedures have been reported.Conductometric and high-frequency methods have only found occasionalnew uses, and interest in them has generally declined, probably owing totheir lack of specificity. Coulometric methods, on the other hand, have con-tinued to develop and there has been an increasing volume of papers ontheory and practical applications. Completely automatic titrators havebeen devised, some of which can be used for continuous recording.Conductometric-Interest in this technique has continued to decline and2 5 0 A.P. Kreshkov, Zhur. analit. Khim., 1962, 17, 6.251 G. A. Harlow, Analyt. Chem., 1962, 34, 1482.2 5 2 G. A. Harlow, Analyt. Chem., 1962, 34, 1487.253 W. M. Banick, jun., Analyt. Chem., 1962, 34, 296.254 G. A. Harlow and G. E. A, Wyld, Analyt. Chem., 1962, 34, 172.255 G. P. Rao and A. R. V. Murthy, 2. analyt. Chem., 1962, 187, 96.256 R. D. Tiwari, K. C. Srivastava, and J. P. Sharma, 2. analyt. Chem., 1962,257 0. Lorenz and C. R. Parks, Analyt. Chem., 1962, 34, 394.258 R. Vasiliev, V. Scintee, and E. Sisman, Rev. Chim. (Roumania), 1962, 13, 56.187, 161458 ANALYTICAL CHEMISTRYfew significant developments have occurred since the last Report. A generalreview by Pungor, giving principles and applications to precipitation, com-plex formation, and redox titrations, has been and reviewshave appeared recording the use of this method in non-aqueous titra-tions.260s 261 A four-cell conductivity bridge has been used as a continuousdetector for the eluents from a chromatographic column.The peak heightsmeasured on a recorder were correlated with the amount of sample with astandard deviation of k0.25 pmole. A frequency of 10 kc.sec.-l was used,with silver tubes for cells, and peak height-concentration graphs were linear forsodium nitrate.262 The carbon content of the atmosphere has been measuredby using a special absorption cell and recorder, giving values in close agree-ment with those by other, more time-consuming, methods.263 With use ofa special cell with a very large cell constant, conductometric titrations havebeen carried out in the presence of a considerable excess of an indifferentelectrolyte.Titrations of dilute hydrochloric acid in 5~-sodium chloride anddilute alkali in 7~-sodium nitrate have been de~cribed.26~ Small amountsof bicarbonate have been determined in an excess of carbonate by a similarmeth0d.2~5Barium has been determined by titration with potassium tellurite astitrant in aqueous solution. I n the presence of 40-50% alcohol the endpoints were quite sharp; the reverse titration was also satisfactory.266 Aspart of a fundamental study of silicosis the rates of dissolution of varioussilica powders in 0.1M-hydrofluoric acid were studied. An increase in con-ductance occurred owing to formation of fluorosilicic acid.Evidence wasadduced against the " solubility theory " of silicosis.267 Weak inorganic acidsand ammonium salts in aqueous solution containing an excess of ammoniahave been titrated with lithium hydroxide. The method relied on the factthat the acid strength increased since the reaction AH + NH,+ A- + NH,+occurred to a greater extent than AH + H20 + A- + €€,Of. The Bron-sted acid NH,+ is neutralised by alkali. Among 16 compounds titrated weregermanium, arsenic, osmium, and chromic oxides, and boric, selenious, sul-phurous, and pyrophosphoric acids. In most cases excellent end pointswere obtained.268 Sulphate has been determined by titration with bariumacetate in an acetic acid medium; and, as an alternative, an excess ofbarium acetate was added and the excess back-titrated with perchloric acid.Both methods gave good end points though the presence of sulphates ofpotassium and nickel produced poor results ; .ferric sulphate, however, causedno interference.269 Carbon has been determined in the less common metalsand in stainless steels by absorption of the dioxide evolved, after combustion259 E.Pungor, J. Electroanalyt. Chem., 1962, 3, 289.260 J. T. Stock and W. C. Purdy, Lab. Practice, 1962, 11, 21.261 C. A. Streuli, Analyt. Chem., 1962, 34, 302R.262 C. Duhne and 0. S. De Ita, Analyt. Chern., 1962, 34, 1074.263 H. Malissa and G. Wagner, Mikrochim. Acta, 1962, 332.264 H. L. Kies and S. H. Tan, 2. analyt. Chem., 1962, 186, 201.265 Z.HoBklek and F. Kutek, Chem. pumysE, 1962, 12, 128.266 S. Prasad and B. L. Khandelwal, J. Indian Chem. SOC., 1962, 39, 84.213'1. Bergman, J. Appl. Chem., 1962, 12, 336.268 F. Gaslini and I,. Z. Nahum, J. Electroanalyt. Chem., 1962, 3, 85.2139 G. Goldstein, D. L. Manning, and H. E. Zittel, Analyt. Chem., 1962, 34, 1169CARTWRIGHT, WESTWOOD, AND WILSON 459in a high-frequency furnace, in 2% sodium hydroxide solution. Calibrationwas made by absorption of known weights of carbon dioxide in the absorp-tion cell and the construction of a conductance-time g r a ~ h . 2 ~ ~ Carbon hasalso been determined in organic compounds by oxidation in the presence ofCo30, and absorption of the CO, in barium hydroxide solution with measure-ment of change of conductivity.The method was claimed to be rapid, witha mean error within &0.22y0 of carb0n.2~1 A complete investigation of amodified Unterzaucher method for the determination of oxygen in organiccompounds has been carried out, a conductometric detection of the endpoint being used. It was applicable to oxygen contents from 0.02 to 50%in samples containing halogens, nitrogen, and A method hasbeen described for the determination of hydrogen in organic compounds inwhich the conventional water absorption tube was replaced by a conducto-metric cell containing sulphuric acid. This utilised the fact that, overthe concentration range 99-83 t o 99.75% w/v of sulphuric acid, a linearchange in conductance occurred. A reproducibility of &0.19 pg.was~lairned.~~3Fluorosulphuric acid in acetic acid behaved as a stronger acid than per-chloric acid, and titrations were carried out with diethylaniline, pyridine, andcc-picoline with good end points. The results were checked with potentio-metric and visual titrations.274 Epoxyethane was determined by additionof an excess of hydrochloric acid and back-titration with sodium acetate inaqueous-alcoholic solution. Appreciable amounts of methacrylic acid andferric chloride caused no interference.275 Trimethylaluminium has beentitrated conductometrically with isoquinoline, and the method has beenclaimed suitable for routine control of the purity of this compound.276Amperometric.-There has been a continued interest in this techniqueduring the last year.Laitinen has again reviewed the method with its appli-cations in oxidation-reduction and ion-combination reactions and reactionsinvolving organic reagents.277 The use of electrochemical indicators inelectrometric analysis, particularly amperometric titrations with ferric, mer-curic, and zincate ions as indicators, has also been reviewed.278A potentiostat has been devised for studying reaction kinetics ampero-metrically. The change in potential of a solution as ions are reduced wasbalanced by the automatic anodic regeneration of similar ions, so that theredox potential of the solution remained constant. The current consumedin the electrolysis was then directly proportional to the reaction rate. Aseparate indicator and reference electrode were used to ensure that the redoxpotential of the bulk solution rather than that of the working electrode was270 I.R. Green, J. E. Still, and R. C. Chirnside, Analys.t, 1962, 87, 530.271 M. VeEera, J. Lakomf, and L. Lehar, Coll. Czech. Chem. Comm., 1962, 27, 1033.2 7 2 F. Salzer, Mikrochim. Acta, 1962, 835.273 S. Greenfield and R. A. D. Smith, Analyst, 1962, 87, 875.274 R. C. Paul, S. K. Vasisht, K. C. Malhotra, and S. S. Pahil, Analyt. Chem., 1962,2 7 5 T. A. Khudyakova, L. I. Namtseva, and M. A. Balandina, Zhur. priklad. Khirn.,2 7 6 R. E. Bonitz and W. Huber, Z . analyt. Chem., 1962, 186, 206.277 H. A. Laitinen, Analyt. Chem., 1962, 34, 307R.278 G. Charlot and B. Trhrnillon, J. Electroanalyt. Chem., 1962, 3, 1.34, 820.1962, 35, 824460 ANALYTICAL CHEMISTRYrecorded.279 Preliminary work on a mercury-film electrode has shown it tobe suitable for amperometric measurements a t very low concentrations.280Cadmium and nickel in alkaline accumulator liquid have been deter-mined by a double-titration method.The solution was made ammoniacaland after addition of an excess of dimethylglyoxime cadmium was titratedwith EDTA. A few drops of cadmium were then added to ensure there wasno excess of EDTA and the nickel was determined by titrating the excessof dimethylglyoxime with nickel solution. 281 Cobalt has been determineddown to 0-lmM-concentration in 0.h-potassium chloride by reaction withtungstate a t - 1.5 v (s.c.e.).282 Separation and determination of thoriumin monazite sand has been carried out by precipitation as oxalate and titra-tion with ammonium paramolybdate. Details of interferences and methodsof dealing with these were investigated. Good results were claimed, and themethods were stated to have advantages of simplicity and speed.283Thorium has also been determined as selenite a t pH 6.2-6.4 in an acetatesolution containing 60-70y0 of alcohol.The pH and alcohol concentrationwere critical, but good end points were attained. Nitrate and sulphate werewithout influence, but chlorate produced a precipitate. Appreciable ex-cesses of ceric and mercuric ions were also tolerated.284 Vanadium, asvanadyl sulphate, has also been determined with selenite solution a t pH 5.3-5-5 and a t -1.10 v (s.c.e.); 5-30 mg. of vanadium were determined withan error of <0.09%.285 Copper and zinc in cyanide electrolytes were deter-mined by a double titration.After removal of the cyanide with acid, sul-phite was added and the copper was determined with 0.1M-thiocyanate a t-0-5 v (s.c.e.). Another aliquot part was titrated a t -1-2 v with thio-cyanate in the presence of pyridine to give the total of copper and zinc.2s6Copper has also been determined by titration with o-( toluene-p-sulphon-amido)-aniline at pH 7.5 in a tartrate medium, and the method has beenused for the analyses of brasses and tested on alloys NBS 37E and NBS 63C.Appreciable amounts of cadmium, lead, or zinc gave no interference. 287Tetraethylenepentamine has also proved to be an excellent titrant for coppera t pH 4.1 in acetate buffer.Only mercury(I1) and cyanide gave anytrouble.288 Amperometric titrations using two polarised electrodes havebeen applied to determine cobalt with EDTA in acid solution with 100 mvbetween the electrodes,2*9 and nickel with iodine in the presence of dimethyl-glyoxime in ammoniacal solution, the redox potential of the Ni2+-Ni3+ systembeing lowered by complex formation.290 Thallium has also been titrated2 7 9 J. M. Matsen and H. B. Linford, Analyt. Chem., 1962, 34, 142.280 S. A. Moros, Analyt. Chem., 1962, 34, 1584.2 8 1 E . G. Novakovskaya, Zavodskaya Lab., 1962, 28, 28.282 V. D. Anand, G. S. Deshmukh, and A. Joseph, Bull. Chem. SOC. Japan, 1962,283 J. J. Burastero and R. W. Martres, Analyt. Chem., 1962, 34, 378.284 G.S. Deshmukh and 0. P. Asthana, Z. analyt. Chem., 1962, 187, 81.285 G. S. Deshmukh, 0. P. Asthana, and V. 8. N. Pillai, 2. analyt. Chem., 1962,286 A. T. Marunina, Zavodskaya Lab., 1962, 28, 25.287 T. R. Williams and F. G. Burton, Analyt. Chzm. Acta, 1962, 27, 351.2*8 E. Jacobsen and K. Schroder, Analyt. Chim. Acta, 1962, 27, 179.289 A. Varma, J . Sci. Ind. Res. India, 1962, 21, B, 142.290 D. Singh and A. Varma, 2. analyt. Chem., 1962, 188, 6.35, 1.185, 429CARTWRIGHT, WESTWOOD, AND WILSON 461with this electrode system by using ceric sulphate solution; only chromic ionsinterfered. The end point was sharp, well-defined, and accurate to _+ly0.291A similar determination was performed with bromine as oxidant and involv-ing back-titration of the iodine liberated from potassium iodide with thio-sulphate solution; it was rapid and accurate for 1 0 - 2 ~ - to 10-4~-solutions,where ordinary indicator methods were unsatisfactory.292 The square-wavepolarograph has been adopted as a detecting device for carrying out theamperometric titration of indium with EDTA and used to determineindium in mixtures with cadmium or lead over wide molar ratios.I n1iw-sodium bromide at pH 1 to 1.5, the peak current being read at -0.580 V(s.c.e.), indium was determined down to 8 x 1 0 - 6 ~ in the presence ofcadmium and in lM-potassium chloride a t -0.600 v in the presence oflead.293 A number of metals have been determined with EDTA by usingiron(n) as indicator ion in a medium of pH 2-5. Provided that the stabilityconstant of the complex formed was greater than 1017, the method was suit-able.Thorium was thus determined in the presence of uranium or zir-conium. Sulphate and fluoride caused no interference.294 Anodic chelonwaves have been used in the amperometric titrations of metals. EDTA,HEDTA, DTPA, DCYTA, trien, and tetren have all been used, and havebeen applied to the determination of calcium, magnesium, zinc, cadmium,nickel, copper, bismuth, and lead, singly and in mixtures. Procedures havebeen worked out for various combinations and are claimed t o be more rapidand selective than methods given heretofore.295Nitrite ions have been determined a t 1 0 - 3 ~ in sulphuric acid a t +1.1 v(s.c.e.) by a permanganometric titration and gave sharp end points, but themethod was not specific.296 The rotating platinum electrode was appliedto the determination of cyanide ions and was used t o study the magnitudeof the formation constant of the Ag(CN)(OH)- ion and the best conditions forcyanide determination.By working in OalM-sodium sulphite a t -0.20 v(s.c.e.), interference from chloride or bromide was avoided, and a t -0.85 vfrom iodide or ~ulphide.~~’ Dissolved oxygen in boiler feed water was deter-mined by trapping in water containing sodium hydroxide and potassiumiodate and iodide to which manganese sulphate was added. On acidification,free iodine was produced and an excess of thiosulphate was immediatelyadded. The excess was then titrated with O.O2~-potassium iodate. Themethod was applicable to waters containing 0.003-0.03 p.p.m. of oxygen.298I n a similar method chromous chloride was the titrant and this was usedt o check the efficiency of various methods for deoxygenating aqueous solu-tions. Inorganic ions produced no difficulties but benzoic acid and benzoatescaused discrepancies. 299291 D. Shgh and V. S. Agarwala, J. Sci. Ind. Res. India, 1962, 21, B, 212.292 R. Bhatnagar, M. L. Bhatnagar, and N. K. Mathur, Talanta, 1962, 9, 455.293 R. E. Hamm and C. T. Furse, Analyt. Chem., 1962, 34, 219.2 9 4 G. Goldstein, D. L. Manning, and H. E. Zittel, Analyt. Chem., 1962, 34,2 9 5 R. T. Campbell and C. N. Reilley, Talanta, 1962, 9, 153.296 J. T. Stock and R. G. Bjork, Microchem. J., 1962, 6, 219.297 F. Shinozuka and J.T. Stock, AnaZyt. Chenz., 1962, 34, 926.298 U.K.A.E.A. Report PG 335(W), 1962.2 9 9 G. P. Gilroy and J. E. 0. Mayne, J. Appl. Chem., 1962, 12, 382.358462 ANALYTICAL CHEMISTRYThe phosphorus content of organic substances has been determined bydecomposition with potassium and oxidation of the phosphide formed tophosphate. Amperometric titration of the phosphate was carried out withuranyl acetate in acid solution. No interference was caused by nitrogen,sulphur, or silicon, and an accuracy of -+0.3% was claimed.300 Mercapto-groups in ascorbic acid oxidase and other proteins have been estimated bytitration with 10-3~-silver nitrate. As little as 0.01 pmole of mercapto-group has been measured.301Aldrin has been determined in fertilisers following a simple extractionwith a nitric acid-methanol mixture.The extract was burnt in oxygen andthe chlorine determined by a '' dead-stop " amperometric titration withsilver nitrate; the method was claimed to be rapid and accurate.302 Organo-silicon compounds containing the zSiH group were determined in benzene-methanol solution containing 0+3~-lithium chloride by titration with mer-curic chloride. The method relied on the formation of the rSiCl group:d i H + 2HgC1, = %iCl+ Hg2C12 + HC1. Only 0.07 g. of sample wasrequired, and the procedure was rapid.303Coulome.tric.-A considerable development of this method has occurredsince the last Report, particularly in instrumentation. Comprehensivereviews of methods of measurement of net charge transfer, coulometry withcontrolled potential and current, and the development of continuous analysismethods have appeared.304, 305 Other reviews have concerned coulometricapplications of the mercury electrode,306 titrations in non-aqueous sol-vents,261 current integrati~n,~~' and determination of trace metal~.~O~A number of completely automatic coulometric titration units, suitablefor continuous determinations, have appeared. A device for determiningsulphur dioxide in gases from 0.1 to 100~o was based on oxidation of thesulphite formed in alkali solution by the Br3- ion generated anodically frombromide in acid solution. The quantity of electricity consumed was linearlyrelated to the sulphur dioxide content and was automatically recorded. 309A rotating platinum electrode was used as the generating electrode and only5 ml.of gas were required. In another apparatus potassium bromide flowedat a controlled rate through a generating cell and passed to a titration cellwhere it was mixed with a stream of the test liquid. A platinum-saturatedcalomel electrode pair monitored the bromide concentration and controlledthe output current of the generating cell. Full details of the apparatus,circuit, and theory of operation were given;310 the optimum conditions forworking and the relationship between current and concentration of the test300 M. N. Chwnachenko and V. P. Burlaka, Izzvest. Akad. Nauk S.S.S.R., 1962, 560.301 G. R. Stark and C. R. Dawson, J . Biol. Chem., 1962, 237, 712.3oa H. N. Wilson and M.Phillipson, Analyst. 1962, 87, 441.303 A. P. Kreshkov, V. A. Bork, and L. A. ShvTrkova, Zhur. unalit. Khim., 1962,3 0 4 H. L. Kies, J . Xlectroanalyt. Chem., 1962, 4, 257.305 A. J. Bard, Analyt. Chem., 1962, 34, 57R.306 J. A. Page, J. A. Maxwell, and R. P. Graham, Analyst, 1962, 87, 245.307 C. Schoedlei, J . Electroanalyt. Chem., 1962, 3, 390.308 J. J. Engelsman, Chern. Weekblad, 1962, 58, 113.309 E. Barendrecht and W. Martens, Analyt. Chem., 1962, 34, 138.310 T. Tekahashi, E. Niki, and H. Snkurai, J . Electroanalyt. Chem., 1962, 3, 373.17, 359CARTWRIGHT, WESTWOOD, AND WILSON 463species were evaluated.311 Continuous analyses of the chlorine content ofbleach solutions over the range 20 p.p.m. t o 3% were carried out by usingthe cathodic generation of ferrous ions ; detecting electrodes monitored theredox potential of the solution and the signal operated a control unit whichregulated the current .312 A continuous Karl Fischer unit similarly deter-mined the moisture content of organic liquids from 0.002 to l*Oyo, usingiodine being generated at a rotating platinum electrode.313 Other automaticcoulometric titrators reported include an instrument suitable for samplechecking in plant operations, in which the coulometric generation of thetitrant occurred in an external ~ e l l . ~ l 4 This was very rapid, and an accu-racy of -J=0-2% was claimed ; full details of current integrator, end-pointdetection, sequence controller, and calibration were given. An assembly forconstant-current coulometry used an electronic device for current integra-tion and adapted a conventional titrator controller to decrease the currenta t a pre-set potential.Determinations of chromium with electrogeneratedFez+ and C1- with Ag + were described.315 A simplified multivibratorcircuit has been used to provide a pulse technique for coulometry and wasapplied to the determination of arsenic(m) and 8-hydroxyquinoline withelectrogenerated br0mine.3~6 By a slight modification of a polarographiccircuit which involved the use of solid electrodes and a standard resistanceacross the cell, a simple manual apparatus was devised and applied to solu-tions of 0-5-2.0 x 1 0 - 3 ~ with an accuracy comparable with that of thepolarographic method.317 Other developments include an I-& recorder,where the length of chart was a measure of the number of afully transistorised p o t e n t i o ~ t a t , ~ ~ ~ and a coulometer based on a voltage-to-frequency conversion, which was tested on silver a t a concentration of 25pequiv., and was claimed to be capable of measuring 2 x 10-7 coulombs.320The use of a dropping-mercury electrode employing a constant-current micro-coulometric technique has been fully examined; the method was applied tothe determination of the number of electrons involved in reduction processes.Consistent values were obtained for cobalt, lead, nickel, thallium, l-nitroso-2-naphthol, and maleic acid.321I n a study of the current efficiency of electrogenerated chromium(rr) asa coulometric titrant, copper(I1) was determined quantitatively. A mediumof 0-lw-chromic sulphate and 0-lnn-potassium chloride with a mercurycathode was found to be most effective; the presence of appreciable chloride-311 T.Takahashi and H. Sakurai, J. Electroanalyt. Chem., 1962, 3, 381.312 E. L. Eckfeldt and E. R. Kuczynski, J. Electrochem. Soc., 1962, 109, 427.313 E. Barendrecht and J. G. F. Doornekamp, 2. analyt. Chem., 1962, 186, 176.314 K. Jeffcoat and M. Akhtar, Analyst, 1962, 87, 455.315 P. G. W. Scott and T. A. Strivens, Analyst, 1962, 87, 356.316 Q. Fernando, M. A. V. Devanathan, J. C. Rasiah, J. A. Calpin, and K. Nakul-317 A. L. Beilby and A. L. Budd, Analyr. Chena., 1962, 34, 493.318 S. Hanamura, Talanta, 1962, 9, 901.319 J. E. Harrar, F. B.Stephens, and R. E. Pechacek, Analyt. Chem., 1962, 34,320 A. J. Bard and E. Solon, Analyt. Chem., 1962, 34, 1181; R. Ammann and321 H. B. Mark, E. M. Smith, and C. N. Reilley, J . ElectroanaZyt. Chem., 1962, 3,esparan, J. Electroanalyt. Chem., 1962, 3, 46.1036.J. Desbarres, J. Electroandyt. Chem., 1962, 4, 121.98464 ANALYTICAL CHEMISTRYion concentration was essential. 322 A Booman potential-controlled coulo-meter being used, gold was determined in the milligram range by depositionon to a platinum cathode from a solution of 0-5~-hydrochloric acid a t+0.48 v (s.c.e.). No corrections were necessary and there was no interfer-ence from oxygen. Only iridium(Iv), ruthenium(Iv), silver, and vanadium(v)interfered. 323 Iridium has been similarly determined as chloroiridate inhydrochloric acid solution a t -0.20 v (s.c.e.), controlled potential beingused; again, the presence of chloride ion was essential.Sulphuric acid andperchlorate media gave inconsistent results.324 Uranium has been reducedquantitatively a t a silver gauze electrode a t a voltage extending from +0-150to -0.150 v (s.c.e.) in a sulphuric acid medium, but bismuth, copper,molybdenum, and- mercury interfered. Methods of removing these werediscussed.325 Lead, cadmium, and zinc were determined in glass, by meansof a stirred mercury cathode and platinum anode, in the milligram range.Arsenic and antimony were both tolerable in appreciable concentrations.326Controlled-potential coulometry has been applied to the determination ofpg.quantities of iron in sulphuric and hydrochloric acid media. The sul-phuric acid solution was preferred except for solutions of high calcium con-tent where hydrochloric acid was more satisfactory. The method wasapplied to analyses of ferrous and non-ferrous alloys, in standard silicaterocks G.1 and W.l, and in fluorspar, dolomite, limestone, and magnesite.327Iron in water has also been determined by a continuous coulometric methodin which electrogenerated bromine is used in an acetate buffer with platinumand calomel indicating electrodes.328 Electrogenerated tin@) is a suitabletitrant for ceric ions, iodine, and bromine. At -0.3 to -0.4 v (s.c.e.),0.814-21.275 mequiv. of cerium(1v) were determined with <2y0 err0r.3~~Antimony has been titrated by two procedures a t controlled potential.The first involved reduction of antimony(rr1) a t a mercury cathode at-0.28 v (s.c.e.) in a 0*4~-tartaric + 0-lwhydrochloric acid medium, andthe second reduction of antimony(v) to antimony(n1) in 0.4M-tartaric + 6M-hydrochloric acid a t -0.21 v (s.c.e.).Both valency states in asolution could thus be evaluated and an accuracy of 0670 a t the 5 mg.level was ~laimed.3~~ Several elements have been determined by a micro-coulometric method involving the generation of EDTA by electrolysis of itsmercury chelate ; procedures involved either ammoniacal solutions a t pH 10.5or acetate buffers a t pH 5.5 and used end-point detection for 0.025-0.5 pequiv. of the elements. Full details of the cell and working conditionswere given.331 Zinc and cadmium were evaluated in a fused lithium chloride-potassium chloride melt a t 450°, a bismuth-pool electrode being used.Anaccuracy of & 1 Yo was claimed in the 10-4~-range ; cadmium was deposited322 A. J. Bard and A. G. Petropoulos, Analyt. Chim. Acta, 1962, 27, 44.323 J. E. Harrar and F. B. Stephens, J. Electroanalyt. Chem., 1962, 3, 112.3 2 4 J. A. Page, Talanta, 1962, 9, 365.325 G. W. C. Milner and J. W. Edwards, A.E.R.E. Report, 3951, 1962.326 P. R. Segatto, J. Amer. Ceram. SOC., 1962, 45, 102.327 G. W. C. Milner and J. W. Edwards, Analyst, 1962, 87, 125.32t3 T. Takahashi and H. Sakurai, Talanta, 1962, 9, 195.329 T. Takahashi and H. Sakurai, Talanta, 1962, 9, 74.330 L. B. Dunlap and W. D. Shults, Analyt.Chem., 1962, 34, 499.s31 R. G. Monk and K. C. Steed, Analyt. Chim. Acta, 1962, 28, 305CARTWRIOHT, WESTWOOD, AND WILSON 465at -1.11 v and zinc at -1.41 v (vs. Pt-ele~trode).~~~ A coulometric methodfor determining water in liquid ammonia relied on passing the ammoniathrough potassium. This reacted with the water present and a rapid changein conductance occurred at the endpoint. This was used to cut off theelectrolysis current. A sensitivity of 1 p.p.m. was claimed and the methodwas suitable up to 100 p.p.m. of water.333 Water was also determined inorganic liquids by passage through a cell having a film of phosphoric oxideas reacting medium and was applicable to the range 1.0-4.5 xResults in close agreement with those of the Karl Fischer method were~tated.3~4 Hydrogen peroxide and hydroxylamine have been determinedby a constant-current coulometric procedure based on the reduction ofiron(@ to iron(n).The latter was reoxidised by electrogenerated cerium(1v).A 0-OlN-cerous sulphate + 0-OlN-ferric sulphate + lw-sulphuric acid solu-tion was used with 10 mA. imposed across the platinum electrodes.335In the organic field, olefins have been evaluated in vapours over therange 20-1000 p.p.m. by absorption in an acetic acid-ethanol-water-potas-sium bromide solution. Constant-current conditions were used and electro-generated bromine was the oxidant. A series of propenes, propadienes,butenes, butadienes, and pentenes was investigated, and an accuracy com-parable with those of colorimetric methods was claimed.336 p-Benzoquinonedioxime has been determined with electrogenerated titanium@) as titrantin the milligram range; the method was stated to be rapid and ac~urate.~3'Phenol has been determined by a bromination procedure involving a con-stant-current pulse technique. Solutions containing to 7 x 1 0 - 6 ~ -phenol were determined with an accuracy of &1%. The kinetics of thebromination were also studied by this method. 338 Anti-cholinesterase, andorganophosphorus compounds such as systox, sarin, parathion, and malathion,have been evaluated in the pg. range by a constant-current method basedon the enzymic hydrolysis of butyrylthiocholine iodide by cholinesterase.Catalytic activity by the above compounds directly affected the depolarisa-tion rate.339Reserpine has been assayed in tablets after a simple acetic acid ex-traction.Oxidation was carried out by electrogeneration of chlorine from3% hydrochloric acid solution and an accuracy of &l.3y0 was claimed on0.2 mg. of reserpine. 340 Various organomercurials and mercury-containingcompounds have been determined by using a O-O5~-solution of mercuricthioglycollate solution buffered at pH 5 as generating solution. Thio-glycollic acid was produced in electrolysis. A maximum potential betweena platinum electrode and the mercury electrode signalled the end point.The method was rapid but un~elective.~4'3 3 2 J. D. van Norman, Analyt. Chem., 1962, 34, 594.333 W. C. Klingelhoefer, Analyt. Chem., 1962, 34, 1751.334 J.SouEok, M. Pfibil, and K. Nov&k, Coll. Czech. Chem. Comm., 1962, 27, 400.335 T. Takahashi and H. Sakurai, Talanta, 1962, 9, 189.336 A. P. Altshuller and S. F . Sleva, Analyt. Chem., 1962, 34, 418.337 S. L. Dobychin and A. P. Zozulya, Zhur. analit. Khim., 1962, 17, 148.338 G. S. Kozak and Q. Fernando, Analyt. Chim. Acta, 1962, 26, 541.339 G. G. Guilbault, D. N. Kramer, and P. L. Cannon, Analyt. Chem., 1962,34,1437.3 4 0 Z . E. Kalinowska and J. Bartnik-Kurzawinska, Acta Polon. Pharm., 1962,19,45.341 F . H. Merkle and C. A . Discher, J . Pharm. Sci., 1962, 57, 117466 ANALYTICAL CHEMISTRYPotentiometric.-This technique has still remained the most popuh~method for electrometric determination of end points and the volume ofpublished work is still increasing.A comprehensive review by Murray andReilley has covered the theoretical developments, apparatus, and applica-t i o n ~ . ~ ~ ~ Other reviews have described the application of the mercury elec-t r ~ d e , ~ O ~ the antimony-antimony oxide electrode,343 titrations in non-aqueous and the use of electrochemical indicators.344 Thecalculation of data for redox titration curves 209 and the effect of concentra-tion on the parameters for redox titrimetry have been discussed theoreti-cally.210 A study of the buffer capacity of solutions during acid-base andredox titrations has also been made.345 Forecasting end points in titrationshas been achieved by a simple and rapid method which involves a few pre-liminary measurements and calculations; it has been applied with success tothe titration of manganese(I1) by permanganate, chloride by silver nitrate,and iron@) by chromate, vanadate, or ~erate.~~GAn automatic recording titration apparatus suitable for use with slowreactions has been reported. Titrant was delivered over a period of 30-180 minutes and the rate could be varied.The chart- and burette-drive weregeared so that the same length of chart always represented the same volumeof titrant. Full details of circuits and mode of operation were given.347Circuit details of a fully-transistorised automatic titrator have been reportedwhich incorporated end-point anticipation and a device for switching froma fast to a slow rate of delivery.348 A simple pH-stat incorporating a specialburette control has been devised with a claim of constancy to &0.01 pH.349Considerable interest has been shown in glass electrodes responsive to sodiumand potassium.A study of two special glasses, BH 68 and BH 104, has beenmade over a range 1 0 - 5 ~ - to 1M-sodium-ion concentration. The effects ofpH , other cations, anions, and temperature have been recorded. Repro-ducibilities were similar to those for pH glass electrodes but the responsetime was somewhat longer. The BH 68 glass was considered suitable forplant use and the BH 104 for more accurate laboratory use.35o Silver,lithium, and thallium also affected the BH 68 glass, and indeed pAg valuescould be obtained over a range of silver-ion concentration^.^^^ Other sodium-and potassium-selective glasses have been investigated especially for measur-ing changes in concentration of these ions in biological work.A capillaryflow and a probe-type electrode were deveIoped.352 Lithium aluminium sili-cate glasses have also been tested for sodium response. Potassium andlithium, however, caused difliculties and so did pH, but alkaline-earth metals342 R. W. Murray and C. N. Reilley, Analyt. Chern., 1962, 34, 313R.343 J. T. Stock and W. C. Purdy, Lab. Practice, 1962, 11, 290.344 C. Schoedler, J . Electroanalyt. Chem., 1962, 3, 390.345 F. L. Hahn, Analyt. Chim. Acta, 1962, 26, 258.346 J. F. Herringshaw, Analyst, 1962, 87, 463.347 L. R. Leake and G. F. Reynolds, Talanta, 1962, 9, 421.348 J. T. Stock, Analyst, 1962, 87, 908.349 L.Josefsson, C. E. Ryberg, and R. Svensson, Analyt. Chem., 1962, 34,350 G. Mattock, Analyst, 1962, 87, 930.351 G. Mattock and R. Uncles, Analyst, 1962, 87, 977.352 H. D. Portnoy, L. M. Thomas, and E. S. Gurdjian, Talanta, 1962, 9, 119.173CARTWRIGHT, WESTWOOD, AND WILSON 467did not.353 Second-order electrodes of the silver-silver halide and silver-silver thiocyanate type have been shown t o be suitable for determinationsof bromide, iodide, and thiocyanate ions in the concentration range 10-t-l o - 4 ~ with an accuracy comparable with that of the usual potentiometricrneth0d.35~ A simple cell with silver cathode and cadmium anode in 5 ~ -potassium hydroxide was used for detecting oxygen in argon. The currentproduced in the cell, measured as a p.d.by means of a millivoltmeter, gavea direct measure of oxygen concentration; a range of 1-500 p.p.m. for oxy-gen concentration was claimed.355 Nitromethane has been tested as a solventfor constant-current voltammetry with platinum electrodes. Anodic oxida-tion of iodine occurred in two steps, and reduction of ferric chloride, benzo-quinone, and a nurnber of chlorinated organic compounds gave good re-s~lts.35~ Tetramethylguanidine has been recommended as a preferablesolvent for titration of weak acids with pyridine, and this was successfullyapplied to the titration of @-naphthol, benzoic acid, and several halogenatedphenols with tetrabutylammonium hydroxide. Up to 3% of water couldbe tolerated without spoiling the inflections in the potential-titre curves.357A considerable number of oxidation-reduction titrations have beenreported.Titrimetric analyses with chloramine-T as oxidant have beenthoroughly investigated by Bishop and Jennings and applied to the studyof reactions with arsenic, antimony, thallium, hydrazine, and thiocyanate.Optimum conditions were established and the addition of a little iodine mono-chloride as reaction intermediate was essential for accurate work. 3M-Hydrochloric acid was found to be the best medium for antimony and thal-lium, and 5M for arsenic and 4M for thallium.199 More detailed studies ofthe antimony system showed that good results could also be obtained in atartrate medium a t pH 6.5-7-5,200 and for thallium in the presence ofO . l ~ - b r o m i d e .~ ~ ~ Lead tetra-acetate has been used as oxidant in the deter-mination of molybdenum(II1) in strongly acid solution,359 and of uranium-(m)or -(Iv) by oxidising with iron(1rc) and back-titrating the iron(I1) formedpotentiometrically. 360 Oxidations with ceric sulphate have been popular.Vanadium(1v) in an orthophosphoric acid-sulphuric acid medium has beentitrated with this reagent and gave a sharp end point, and iron also gavegood results down to 0-293 mM-~olution.~~~ A similar investigation into thevalency states of vanadium on polyolefin catalysts utilised the same oxid-ant.362 Tungsten was determined in the (v) state after reduction withbismuth amalgam and oxidation in concentrated hydrochloric acid. Themethod was successfully applied to the analysis of a standardPlutonium has also been determined in a sulphuric acid medium after reduc-353 J.E. Leonard, Analyser, 1962, 3, 5.354 J. 0. Frohliger and R. T. Pflaum, Talanta, 1962, 9, 755.355 K. Noviik and V. Slavik, Chern. prurnysl, 1962, 12, 193.356 J. D. Voorhies and E. J. Schurdak, Analyt. Chem., 1962, 34, 939.s57 T. R. Williams and J. Cuter, Talanta, 1962, 9, 175.358 E. Bishop and V. J. Jennings, Talanta, 1962, 9, 679.359 A. Berka, J. Doleial, I. NBmec, and J. Zfka, J . Electroanalyt. Chew.., 1962, 3,A. Berka, J. Doleial, I. Nr?mec, and J. Zgika, Analyt. Chim. Acta, 1962, 26, 148.361 L. S. A. Dikshitulu and G. G. Rao, Talanta, 1962, 9, 857.362 J. E. Barney, Analyt. Chirn. Ada, 1962, 27, 320.363 A. S. Witwit and R.J. Magee, Analyt. Chirn. Acta, 1962, 27, 366.278468 -4 N AL Y TI C AL C H E M I S TRYtion to the (111) state with chromous chloride. Iron tended to interfere butcorrections could be a ~ p l i e d . ~ 6 ~ Tervalent cerium has been oxidised quanti-tatively by periodate in a bicarbonate buffer solution. The method wasunaffected by many metals, but bismuth, cobalt, iron, chromium, copper,nickel, and zinc gave trouble at high concentration^.^^^ Tin(I1) has beendetermined by an indirect procedure involving ferric ion and titration of theferrous ion formed with d i ~ h r o m a t e . ~ ~ ~ Manganese in glasses has been deter-mined after dissolution in an acid solution by titration with permanganatein a chloride-pyrophosphate medium a t pH 6-8 with a platinum-silverelectrode system.367 Ascorbic acid has found applications as a reductantand been used in estimating thallium(II1) in the range 60-120 mg.with anaccuracy of &0-6%,368 and gold in a mixture containing platinum and pal-ladium in sulphuric acid.369 The reducing power of iron(=) was markedlyincreased by working in concentrated phosphoric acid solution ; uranium( VI)was quantitatively reduced in this way at room temperature in a mediumof 11~0-13~5~-orthophosphoric acid.370 Thallium(rr1) and antimony(v),produced by oxidation of the lower-valency states with bromine, have beendetermined simultaneously in hydrochloric acid by using vanadium(I1). Thefirst break in the potential was due to thallium, and after addition of strongacid a second break occurred due to Thallium was also deter-mined with hydrazine in sulphuric acid by using a platinum-carbon electrodesystem.The titration was rapid, reversible, and free from interference bys large number of cations and anions. Only halides, molybdate, tungstate,vanadate, and chromate gave difficulties. 372 A high-precision assay ofuranium metal was carried out by dissolution in phosphoric acid to produceuranium(Iv), which was oxidised by excess of dichromate and back-titratedwith standard iron(=) solution ; difEculties from iron, chromium, molyb-denum, and vanadium were avoided by aerial oxidation. The method wastested with standard 99.99% uranium. 373 Several analyses have involvedcomplex formation. Nickel, after separation with dimethylglyoxime, wasdecomposed with nitric-sulphuric acid, the pH adjusted to 10-10-5 withammonia, and the solution titrated with O~O~M-EDTA, a mercury-mercury-EDTA electrode being Thorium has been titrated with the tetra-acetic acid derivatives of 1,2 - di- (2 - aminoet hoxy )ethane and 2 , 2' -diamino-diethyl ether and the methods were used to determine the metal in naturaland artificial monazites.A simplified procedure was worked out for theelement.375 The iron(m)-l ,lo-phenanthroline complex has been used tooxidise cobalt(I1) down to 10-4y0 and the method has been applied to364 U.K.A.E.A. Report, PG 309(W), 1962.365 J. Doleial, S. Rossler, and J. Zfka, CoZZ. Czech. Chem. Cmm., 1962, 27, 1031.366 R. W. Collins and W. H. Nebergall, AnaZyt.Chem., 1962, 34, 1151.367 M. PaleEek, Skcilr'. a. Kerum., 1962, 12, 6.368 R. Bhatnagar and M. L. Bhatnagar, J. Sci. Ind. Res. India, 1962, 21, B, 44.369 N. K. Pshenitsyn, S. I. Ginsburg, and I. V. Prokof'eva, Zhw. analit. Khim.,3 7 0 G. G. Rao and S. R. Sagi, Talunta, 1962, 9, 715.371 S. I. Gusev and L. A. Ketova, Zhur. analit. Khim., 1962, 17, 137.3 7 2 A. Berka and A. I. Bmev, Analyt. Chim. Acta, 1962, 27, 493.373 J. A. Duckitt and G. C. Goode, Analyst, 1962, 87, 121.374 N. M. Silverstone, Metallurgia, 1962, 65, 99.3'5 P. E. Wenger and I. Kapbtanidis, Milcrochim. Acta, 1962, 400.1962, 17, 343CARTWRIGHT, WESTWOOD, AND WILSON 469determination of cobalt in sodium meta1.376 Uranium has been determinedwith this reagent and the efficiency checked c~lorimetrically.~~~ Thio-glycollic acid has been used as a titrant for silver and good end pointswere obtained. Determination of zinc, cadmium, mercury, and leadshowed that 1 : 1 complexes were f0rmed.37~ Other mercapto-acids andthiodiglycol were similarly useful for silver.The stabilities of a number ofmetal complexes were also studied. Chelates of PAN and PAR with man-ganese, cobalt, nickel, and zinc were examined potentiometrically in dioxan-water. All gave metal : ligand ratios of 1 : 2 and the order of stability wasNi > Co > Zn > Mn. Values for the stability constants were workedout. 379 Metal-dye stability constants for Solochrome Violet R with copper,nickel, zinc, lead, magnesium, calcium, and aluminium by combined spectro-photometric procedures were evaluated.380 The sulphosalicylic acid coni-plexes of manganese, cobalt, nickel, and copper have been titrated withsodium hydroxide, a glass electrode being used ; two potential breaks occurredcorresponding to a 1 : 1 and a 1 : 2 metal : complex ratio.Stability constantswere derived for these systems.381 A similar study was made with someazo- and azomethine dyes.382Potassiumhas been determined in silicates by a procedure involving precipit,ation astetraphenylborate. 383 Mercury has been determined with thioacetamide inthe presence of other metals after complex-formation with EDTA. Onlysilver interfered and this had to be allowed for.384Potentiometric acid-base titrations in molten potassium nitrate at 370 Ohave been carried out with potassium dichromate as the acid and potassiumhydroxide as the base.Very large potential changes occurred at the endpoint. An oxygen-platinum and a silver-silver ion electrode were used asthe indicating and reference electr0des.3~-4 potentiometric method for determining bromide-ion concentration hasbeen described utilising a silver-silver bromide electrode which was suitableover the range 10-1 to 1 0 - 4 ~ . The method was applied to the determina-tion of the solubility of lead bromide, and a pBr scale established.3s610 P.p.m. of fluoride was determined by using cerium as titrant in a “ dead-stop ” end-point method.387 Dead-stop methods were also applied to thedetermination of sulphide, polysulphide, and thiosulphate in mixtures.Thesulphide was determined by ammoniacal silver nitrate, thiosulphate withmercuric chloride, and polysulphide by conversion into thiosulphate anda second titration. Results comparable with those obtained by chemicalA few potentiometric precipitation reactions have appeared.376 F. Vydra and R. Psibil, 2. analyt. Chem., 1962, 188, 273.3 7 7 F. Vydra and R. Psibil, Talanta, 1962, 9, 1009.378 A. M. Cabrera and T. S. West, Talanta, 1962, 9, 730.379 A. Corsini, I. Mai-Ling-Yih, Q. Fernando, and H. Freiser, Analyt. Chem., 1962,380 E. Coates and B. Rigg, Trans. Paraday. SOC., 1962, 58, 2058.381 V. S. K. Nair, Talanta, 1962, 9, 27.382 W. J. Geary, G. Nickless, and F. H. Pollard, Analyt. Chim. Acta, 1962, 27, 71.383 M. Huka and Z.Valnj., SklQr‘. a. Keram., 1962, 12, 21.384 M. Piazzi, Ann. Chim. (Italy), 1962, 52, 45.3 8 5 A. M. Shamseldin, Electrochim. Acta, 1962, 7, 285.386 R. T. Pflaum, J. 0. Frohliger, and D. G. Berge, Analyt. Chem., 1962, 34, 1812.387 T. A. O’Donnell and D. F. Stewart, Analyt. Chem., 1962, 34, 1347.34, 1090470 ANALYTICAL CHEMISTRYoxidation methods were obtained.3s8 Nitrite has been determined by titra-tion with lead tetra-acetate. The method was rapid and accurate : 2.35 mg.of NO,- were determined to within &0-17%, and the method was capableof application to 0.1 mg. ; nitrate caused no interference and the method wasapplied to the control of crude Chile salt pet re^.^^^ Traces of oxygen ingases or liquids have been determined by using the aluminium electrode.Purified hydrogen was passed through the solution to constant potential.Water, saturated with the gas or containing the sample to be analysed, wasadded and the potential change was noted.The volume of a standard oxygensolution required to produce a similar change was also recorded and theoriginal oxygen content calculated.390 Hydrazine has been titrated withchloramine-I: and the conditions for satisfactory determination have beenworked out. The presence of iodine monochloride was essential for analytic-ally useful applications. Bromide a t 0 . 1 ~ was found desirable and theconcentrations of hydrochloric acid must be greater than 0*5~.2OlA number of organic systems have been investigated in aqueous solution.Primary alcohols were determined by acetylation and back-titration withsodium hydroxide; to avoid difficulties arising a t the end point the titrationwas carried out to a pH of 7.6.391 A number of acid alcohols, glycol, andglycerol were oxidised quantitatively with an excess of lead tetra-acetate ina dilute acetic acid medium. The excess was then back-titrated with quinol(hydroquinone).Oxidation was in some cases, e.g., citric acid, ratherPyruvic acid has been titrated with vanadium(v) in concentratedsulphuric acid solution; a large change of voltage occurs a t the end point.393A study of an acid-base titration of nitrocellulose in acetone-water solutionshas been made. An optimum condition of 0.5% of nitrocellulose in 99.5%acetone solution was required to avoid difficulties. A higher concentrationof nitrocellulose spoiled the glass electrode and higher water contents causedless satisfactory potential-titre curves.Under the above conditions resultscomparable with more tedious procedures were obtained. 394 Triphenyl-methane dyes have been titrated after conversion into the carbinol baseswith cerium(Iv), and the method was applied successfully to Crystal Violet,Ethyl Violet, and Magenta.Sg5 Thiourea and its organic derivatives havebeen successfully estimated with iodine monochloride in acid solution andchecked with amylose as indicator; an acidity of a t least 3 M was required.396The 2,4-dinitrophenylhydrazones of a large set of ketones have been deter-mined by titrations in sulphuric acid containing a high concentration oftetrahydrofuran by means of sodium nitrite.The results were good unlessthere was a carbonyl or benzyl group or a hydrogen atom adjacent to theC=N group.397S. A. Kiss, 2. analyt. Chem., 1962, 188, 341.3 8 9 A. Morales and J. Zfka, Coll. Czech. Chem. Conam., 1962, 27, 1029.390 E. Scarano, J . Electroanalyt. Chem., 1962, 3, 304, 368.391 J. J. Quattrone and T. Choy, Microchem. J . , 1962, 6, 259.392 A. Berka, V. DvoFBk, and J. Zfka, Mikrochim. Acta, 1962, 541.393 K. S. Panwar and J. N. Gaur, J . Electroanalyt. Chem., 1962, 3, 348.394 L. R. Leake and G. F. Reynolds, Talanta, 1962, 9, 413.395G. G. Rao and N. V. Rao, 2. analyt. Chem., 1962, 188, 89.396 B. Singh, B. C. Verma, and XI. S . Saran, J . Indian Chem. SOC., 1962, 39, 211.S97 J.G. Baldinus and I. Rothberg, Analyt. Chem., 1962, 34, 924CARTWRIGHT, WESTWOOD, AND WILSON 47 1A number of determinations have been carried out in purely non-aqueousmedia. Several of these refer to the titrations of weak acids or bases. Tetra-butylammonium hydroxide has been found to be particularly suitable astitrant for acids,398 and t-butyl alcohol was shown to be especially good forphenols and very weak acids and gave better results than ~ y r i d i n e . ~ ~ Carboxyl groups in polyhexanolactam (polycaprolactam) were determinedin 2,6-xylenol with ethanolic potassium hydroxide at a much lower tempera-ture than in other methods and obviated oxidation diffic~lties.~~O A similardetermination was made for polyamide fibres in propargyl alcohol, tetra-methylammonium hydroxide being used as titrant.401 Ascorbic acid hasbeen accurately determined by ammonium cerinitrate in methyl cyanideby using a glass or antimony indicating electrode. 255 NN'-Disubstitutedp-phenylenediamines have been determined in rubber compounds by oonver-sion into the Wurster salts by oxidation with chloranil. These were strongerbases than the original diamines and were titrated with perchloric acid inacetic acid, methyl cyanide, or acetone to give satisfactory end points.257Acylamides were determined in pyridine with tetrabutylammonium hydrox-ide as the best titrant.402 Substituted phenylureas, which behaved as acidsin butylamine, were determined with the same titrant.403 A number ofheterocyclic N-oxides have been determined in acetic anhydride with per-chloric acid.404 Phenols have been directly titrated in glacial acetic acidby bromine, pyridine being used as a catalyst; a high accuracy wasclaimed.405 Alkylaluminiums were determined in heptane or benzene withpyridine bases by using platinum-silver electrodes ; a change of 250-400 mvoccurred a t the end point.406Differential Electrolstic Potentiometry.-This new technique originatedby Bishop has continued to develop. Argentometric precipitation reactionsfor C1-, Br-, CNS-, and I- and mixtures have been studied in detail.Optimum conditions for current values and ballast resistances have beenevaluated.407 Acid-base titrations have also been studied by using anti-mony electrodes,408 and the interpretation of current, potential, and tempera-ture relationship for antimony in neutral solution has been discussed.409The titration of nanogram amounts of halides has been achieved in variousmedia by use of silver or silver-silver halide electrodes.Full operationaldetails were reported.410 A theoretical discussion on the effect of pH andthe relationship between EA and AI has been given.411398 L. W. Marple and J. S. Fritz, Analyt. Chem., 1962, 34, 796; G. A. Harlow,Analyt. Chem., 1962, 34, 1482, 1487.399 J. S. Fritz and L. W. Marple, AnaZyt. Chem., 1962, 34, 921.400 M. J. Maurice, Analyt. Chim. Acta, 1962, 26, 406.401 S. Wolf and B. Itlobus, 2. analyt. Chem., 1962, 186, 194.402 B. H. Beggs and R. D. Spencer, Analyt. Chem., 1962, 34, 1590.403 M.L. Cluett, Analyt. Chenz.., 1962, 34, 1491.404 D. C. Wimer, Analyt. Chem., 1962, 34, 873; C. W. Muth, R. S. Darlak, W. H.405 C. 0. Huber and J. M. Gilbert, Analyt. Chem., 1962, 34, 247.406 L. Nebbia and B. Pagani, Chimica e Industria, 1962, 44, 383.4 0 7 E. Bishop and R. G. Dhaneshwar, Analyst, 1962, 87, 207.408 E. Bishop and G. D. Short, Analyst, 1962, 87, 467.409 G. D. Short and E. Bishop, Analyst, 1962, 87, 724.410 E. Bishop and R. G. Dhaneshwar, Analyst, 1962, 87, 845.411 G. D. Short and E. Bishop, Analyst, 1962, 87, 860.English, and A. J. Hamner, ibid., p. 1163472 ANALYTICAL CHEMISTRYChronopotentiometw.-Theoretical studies of this technique have beenpublished. A mathematical treatment of a system where the current flowwas a power of time was considered and was applied to reversible and non-reversible processes.412 Application of potential-time process at constant-current to molten salt systems was used with silver nitrate, lead nitrate, leadchloride, and cadmium nitrate in potassium chloride-lithium chloride andsodium nitrate-potassium nitrate melts.413 An apparatus for these studieswas described.A saw-tooth generator producing current pulses has beenapplied to chronopotentiometric analysis. The advantages claimed weremore sharply defined transition times, shorter transition times suit-able for kinetic studies, and the ability to determine several elements simul-taneously. 414The chronopotentiometry of uranium a t platinum electrodes has beeninvestigated, and determinations of uranium based on conversion of uraniuminto uranium(1v) and the oxidation of uranium-(Iv) to -(vI) have been workedout. Iron, iodine, titanium, nitrate, and acetate caused trouble, but not,chromium or vanadium.The medium used was 1.0M-perchloric acid.415Vanadium(v) was reduced at a platinum electrode. The process was re-versible and quantitative provided that the pIatinum had not been strippedof oxides before ~ ~ 8 . ~ 1 ~ A slide rule based on the fundamental equation ofchronopotentiomefry and useful for calculating transition times, concentra-tions, and diffusion coefficients has been described.417High-frequency Potentiometry.-Once again relatively few accounts ofthis technique have appeared. In a review of instrumental methods byStock and Purdy details of cell design, circuitry, and titrations in glacialacetic acid, benzene-ethanol, and o-cresol-chloroform-acetone mixtureshave been discussed.260 A comprehensive review of oscillometry and con-ductometry has shown the close relation between the two techniques.259A new cell design has been reported which is capable of a sensitivity, atapproximately 1 Mc./sec., only attainable by conventional cells a t much higherfrequencies; this consists of two metallic tubes coated on the inside withepoxy-varnish to reduce the reactance of the insulating wall and connectedto a circulating pump and beaker containing the electrolyte.It was success-fully checked with sulphuric acid over the range 0 . 0 0 1 - - 5 ~ .~ ~ ~ A furtherapplication of the Blake zone detector has been carried out to locate theseparated zones when mixtures of sodium fluoride, chloride, bromide, andiodide were subjected to paper chromatography. High-frequency measure-ments of the aqueous extracts from the zones gave a quantitative determina-tion of the amounts of each present.419Macro-amounts of fluoride, particularly in the presence of small amountsof aluminium, have been determined by steam-distillation from an 85%lr12R. W. Murray and C. N. ReilIey, J . Electroanalyt. Chern., 1962, 3, 64.lr13 D. Inman and J. O’Mara Bockris, J. Electroanalyt. Chern., 1962, 3, 126.lrllrH. Hoffmann and W. Jaenicke, 2. anaZyt. Chem., 1962, 186, 93.*15 D. G. Davis, Analyt. Chim. Acta, 1962, 27, 26.lr16 F.C. Anson and D. M. King, Aiaalyt. Chem., 1962, 34, 362.417 A. J. Bard, Analyst, 1962, 87, 911.lr18 A. H. Collins, Analyst, 1962, 87, 733.lrlS J. A. Broomhead and N. A. Gibson, Analyt. Chinz. Acta, 1962, 26, 265C ART WRIGHT , WE S T W 0 0 D , 473phosphoric acid solution. The high-frequency titration was carried out withlanthanum acetate after buffering to pH 4.5. A precision of &O.Ol mg. ofF- was possible. Using perchloric or sulphuric acid in place of phosphoricacid gave poor recoveries.420 Lewis acid-base titrations with an oscillatorat 5 Mc./sec. have been carried out with aluminium chloride in acetonitrileas titrant. Dimethylaniline, diphenylguanidine, tri-n-butylamine, pyridine,quinoline, and p-toluidine gave good end points.The shapes of the titra-tion curves showed that formation of a soluble adduct of the AB type wasfollowed by an insoluble adduct of the AB2 type. The method was rapidand ~ensitive.~21 Samples of natural waters have been analysed for C1-,SO,2-, alkalinity, and total hardness at 5 and 130 Mc./sec. by using con-ventional titrants and EDTA for total hardness.422 Methylglucamine hasbeen proposed as a standard weak base for titrations of acids. It gave verygood end points with hydrochloric, acetic, and oxalic acid at 130 Mc./sec.and was easily obtained pure.423 In the organic field melamine has beentitrated with 0-15y0 cyanuric acid in aqueous solution. Ammeline, ammelide,dicyandiamide, and urea caused no interference. The titration was carriedout equally satisfactorily in the reverse direction.424 Hexaethyl-lead intetraethyl-lead has been determined by a slow titration with permanganatein acetone solution. A calibration curve from known mixtures permittsedready evaluation of the hexaethyl-lead content of test samples.425AN D W IL S 0 N8. DETERMINATION OF ELEMENTS IN ORGANIC COMPOUNDSElemental organic analysis is included in a review of developments inorganic microanalysis by Ma and Gutterson. 426 Specifications for referencesubstances used in organic microanalysis have been published ; the charac-t,eristics of 34 compounds which can be used as standards in element andgroup analysis are described and methods are given for testing each com-pound for Similar specifications for 29 reagents, first publishedten years ago, have been revised 428 and brought into line with manufacturingdifliculties as well as users’ requirements.The efficiency of various catalysts in the combustion of organic com-pounds has been investigated by a number of ~orkers.429-~31 Some novelcombustion procedures have been advocated.Pfab, adapting a macro-method, vaporised the sample in a slow stream of nitrogen and then burned420 R. C. Calkins, Analyt. Chem., 1962, 34, 837.421 E. T. Hitchcock and P. J. Elving, Analyt. Chim. Acta, 1962, 27, 501.4 2 2 L. Erdey, E. Gegus, and M. T. Vhdorffy, Magyar Kim. Lapja, 1962, 17, 277.423 L. BalAzs and E. Pungor, Milcrochim. Acta, 1962, 309.424 I. A. Guriev, L. G. Urusovskays, and V. A. Zarinskii, Zhur. analit.Khim.,425 A. L. Gol’dshtein, N. P. Lapisova, and L. M. Shtifman, Zhur. analit. Khim.,426 T. S. Ma and M. Gutterson, Analyt. Chem., 1962, 34, 111R.427 Microchemistry Group, Analyst, 1962, 87, 304.428 Microchemistry Group, Analyst, 1962, 87, 400.4 2 9 M. K. Zacherl, Chim. analyt., 1961, 43, 535.430 J. HorAEek, V. Pechanec, and J. Korbl, Coll. Czech. Chem. Comm., 1962, 27,431 G. Kainz and H. Horwatitsch, Mikrochim. Acta, 1962, 7.1962, 17, 376.1962, 17, 143.1254474 ANALYTICAL CHEMISTRYit in a fast jet of oxygen; there were difliculties, and a catalyst was re-q ~ i r e d . ~ ~ ~ Another method was to use nitrogen Containing electrolytically-generated oxygen.433 Gleit and Holland 434 used oxygen excited by a radio-frequency discharge, and found that temperatures of less than 100" couldbe used to decompose a wide variety of compounds.The dependence ofcompleteness of oxidation on the proportion of the organic vapour in a gasstream passing through an oxidising tube has been investigated.435Instrumental methods to replace the gravimetric finish in determiningcarbon and hydrogen have attracted considerable attention, and Zacherl 4z9reviews some of them. Greenfield and Smith 436 replace the water-absorptiontube by a conductivity cell containing sulphuric acid, and, beyond a dryingtube, use a smaller conductivity cell containing potassium hydroxide for thedetermination of carbon. Unfortunately, lead dioxide must be used in placeof manganese dioxide for absorbing oxides of nitrogen.A short survey ofmethods for determining water vapour in a continuous gas stream has beenpublished, and Keidel's method receives particular mention. 437 For carbon,absorption of the carbon dioxide in barium hydroxide with measurement ofchange in conductivity has again been advocated.288 Water has been deter-mined by c o u l ~ m e t r y , ~ ~ ~ and by electrolysis (with conversion of carbondioxide also to water by reaction with lithium hydroxide, and further elec-trolysis 439 to determine carbon), and by removal of water vapour andcarbon dioxide in conjunction with measurements on a pair of katharo-met ers. 4OSome modifications of the more conventional methods for carbon andhydrogen have been advocated. VeEefa 441 speeds up equilibration andreplacement of the absorption tubes by placing them permanently inside thebalance room.A fully automatic method for carbon and hydrogen has beendiscussed step by step and described in detai1,442 and the physical and chemi-cal factors affecting removal of oxides of nitrogen by manganese dioxidehave been in~estigated.~~3For the determination of nitrogen a simple but readily controllable cata-lytic generator for oxygen has been described.444 By heating the sample ina closed capillary with oxygen, copper, and potassium hydroxide, andmeasuring the weight of mercury displaced by the resulting nitrogen,Kirsten and Hozumi 445, 446 have evolved a direct method for determiningnitrogen which is applicable on the micro- or ultramicro-scale.432 W. Pfab, 2.analyt. Chem., 1962, 187, 354; 190, 414.433 T. Mitsui, K. Yoshikawa, and C. Furuki, Mikrochim. Acta, 1962, 385.434 C. E. Gleit and W. D. Holland, Analyt. Chem., 1962, 34, 1454.435 G. Kainz and H. Horwatitsch, 2. analyt. Chem., 1962, 187, 87.436 S. Greenfield and R. A. D. Smith, Analyst, 1962, 87, 875.437 Anon., Chern. WeekElad, 1962, 58, 299.438 J. Sodek, Coll. Czech. Chem. Comm., 1962, 27, 1024.4 3 9 H. S. Haber and K. W. Gardner, Microchem. J., 1962, 6, 83.440 P. F. Sommer, W. Sauter, J. T. Clark, and W. Simon, Helv. Chim. Acta, 1962,441 M. VeEeYa, Mikrochim. Acta, 1962, 891.442 W. Simon, P. F. Sommer, and G. H. Lyssy, Microchem. J . , 1962, 6, 239.443 G. Kainz and J. Mayer, Mikrochim. Acta, 1962, 241.4 4 4 R. McGillivray, Analyst, 1962, 87, 833.445 K.Hozumi and W. J. Kirsten, Mikrochim. Acta, 1962, 434.446 W. J. Kirsten and K. Hozumi, Mikrochim. Acta, 1962, 777.45, 595CARTWRIGHT, WESTWOOD, AND WILSON 475Jacobs 447 has modified the indanetrione hydrate method for determiningsmall quantities of nitrogen by carrying out the digestion in sealed tubeswithout a catalyst, and by altering the spectrophotometric determination.These changes make the method more sensitive and more widely applicable.The flask-combustion technique has established itself for determining awide variety of other elements in organic compounds. Complications creepin, such as electrical firing and ja~keting,4~8 but the method generally, what-ever the finishes, remains simple, speedy, and reliable. Mention must,however, be made of a number of methods of determining mercury simul-taneously with carbon and hydrogen, based on adsorption of the mercuryon silver.449, 4509.SPECTROSCOPIC ANALYSISAs in previous Reports this section is divided into emission spectroscopyand absorption spectroscopy, the former including flame photometry, fluori-metry, and X-ray methods, and the latter ultraviolet and visual absorption,atomic absorption, infrared absorption, and nuclear magnetic resonancemet hods.Emission Spectroscopy.-Emission spectroscopic methods for the analysisof solutions have been critically reviewed by Matherny 451 and by Young.452The latter has mentioned many of the advantages to be gained by workingwith solutions, but has pointed out that many of the methods that have beenproposed are of limited application, and that considerable further investiga-tion may be required before these methods can be extended to wider con-centrations of the elements sought, or to other materials.The use of the rotating-disc electrode has been said to result in a ten-foldincrease in sensitivity in the determination of volatile elements in ores.453In the analysis of rocks spectrographic methods have been described for thedetermination of gallium, barium, nickel, cobalt, and and ofsmall amounts of germanium, indium, and thallium.455A rapid method has been described for the determination of smallamounts of vanadium in petroleum, petroleum products, and other organicsubstances.456 The influence of titanium, thorium, and zirconium on theaccuracy of the spectrographic determination of small amounts of uraniumhas been investigated.457Many papers have been published describing modifications of spectro-graphic methods determining trace elements and trace impurities.A con-centration method involving the use of chelating agents such as quinok-8-01,447 S . Jacobs, Analyst, 1962, 87, 53.4 4 8 H . E. 'weir, Microchem. J . , 1962, 6, 109.449 V. Pechanec and J. HorbEek, Coll. Czech. Chern. Comm., 1962, 27, 232.450 A. I. Lebedeva and K. S. Kramer, Izvest. Akad. Nauk S.S.S.R., OtdeE. khim.451 M. Matherny, Chem. Analit., 1962, 7, 7 5 .452 L. G. Yoang, Analyst, 1962, 87, 6.453 I. MihBlka, Acta Chirn. Acad. Sci. Hung., 1962, 30, 359.454 A. SpaEkova, Acta Chirn.Acad. Sci. Hung., 1962, 30, 341.455 L. I. Pavlenko and Z. M. Davydova, Zhur. analit. Khim., 1962, 17, 199.456 P. BunEak, Chem. Analit., 1962, 7 , 269.4 5 7 T. M. Moroshkina, Vestnik. Leningrad. Univ., Ser. Fiz. i Khirn., 1962, 152.NaurE, 1962, 1305476 ANALYTICAL CHEMISTRYtannic acid, and thionalide has been used for the determination of traces ofaluminium, cobalt, chromium, copper, iron, gallium, germanium, manganese,nickel, titanium, vanadium, bismuth, lead, molybdenum, cadmium, zinc,and beryllium in natural water.458 Procedures have been described for thedetermination of up to 60 elements as trace impurities in gra~hite,~59 forthe determination of silicon and other impurities in gallium arsenide,460 andfor the determination of impurities in refined tin.461 A method ha,s beengiven for the preparation of standard samples of lead, and their use in deter-mining impurities in lead has been described.462A hollow light guide constructed from aluminiumtubing has been used for the examination of various regions of flames andis said to improve the signal-to-background ratio of many emission lines andt o double signal ~trength.~63The determination of lithium in water and the effects of the presence ofother ions has been studied;464 small amounts of strontium interfere withthe determination. Rubidium and caesium in micas and other materialscan be determined by using an oxy-hydrogen flame.465 Sodium and potas-sium interfere seriously, but chloride, sulphate, iron, calcium, vanadium, andlithium have little influence.Interference from phosphorus in the determination of calcium can beeliminated when the concentration of phosphate is less than 20 p.p.m.byatomising the solution in the presence of 2% ofI n a study of the flame-photometric determination of lead in lead alloysfrom 4% to 85% of lead has been determined with an accuracy and repro-ducibility of &5y0 of the amount present.467An investigation of the determination of titanium has shown that mostof the elements present in the hydrated oxide precipitate of the group-sepa-ration scheme enhance the titanium emission, as also do magnesium andsodium.468 The method can thus only be applied to relatively pure titaniumsolution in which case better results may be obtained by colorimetricmethods.A study has been made of the emission spectra of arsenic, antimony, andbismuth from acetylene-oxygen flames and it was concluded that the flame-photometric determination of these elements was fea~ible.~69I n a timely review article Parker and Rees have giventhorough attention to the subject of fluorescence spectrometry.47o It is tobe hoped that their plea for the production of instruments that will recordFEame photometry.Fluorimetry.45a W.D. Silvey and R. Brennan, Analyt. Chem., 1962, 34, 784.459 J. A. Goleb, J. R. Faris, and B. H. Meng, Appl. Spectroscopy, 1962, 16, 9.460 J. H. Oldfield and D. L. Mack, Analyst, 1962, 87, 778.461 M. Berecka, Chem. Analit., 1962, 7 , 223.462 S. Witkowska and W. Filasiewicz, Chem.Analit., 1962, 7, 211.463 W. J. Carnes and J. A. Dean, Analyst, 1962, 87, 748.464 M. J. Fishman, J . Amer. Water Works ASSOC., 1962, 54, 228.465 Z . Rez&ii and J. Dvor&k, Acta Chirn. Acad. Xci. Hung., 1962, 30, 375.466 H. B. Heeney, G. M. Ward, and A. F. Wilson, Anaylst, 1962, 87, 49.467 C. L. Chakrabarti, R. J. Magee, W. F. Pickering, and C. L. Wilson, Talanta,468 C. L. Chakrabarti, W. F. Pickering, and C. L. Wilson, Talanta, 1962, 9, 451.469 J. A. Dean and W. J. Carnes, Analyst, 1962, 87, 743.47O C. A. Parker and W. T. Rees, Analyst, 1962, 87, 83.1962, 9, 145C ART W R I G H T , WE S T W 0 0 D , 477directly the true emission and excitation spectra, so that analytical chemistscan readily record and publish data in a form that will be of most value tothemselves and to other workers, will not go unheeded.Parker and Hatchard 4 7 1 have pointed out that the essential differencebetween phosphorescence and fluorescence is in the duration of the emissionafter the exciting light is cut off.They have described modifications to aspectrofluorimeter to measure weak phosphorescence spectra, and haveapplied it to the measurement of simple organic compounds in rigid mediaa t the temperature of liquid nitrogen.Small amounts of aluminium have been determined by measuring thefluorescence of aluminium oxinate solutions 472 and the fluorescence of thechelate compound formed by aluminium with salicylaldehyde formyl-hydrazone. 73The fluorimetric determination of submicrogram quantities of thorium,morin being used in an alkaline solution of diethylenetriaminepenta-aceticacid has been reported.474A study of the luminescence of some piazselenols has shown that 2,3-di-aminonaphthalene is more sensitive and more convenient for the fluorimetricdetermination of selenium than the previously recommended 3,3’-diamino-benzidine.75The use of sodium trimetaphosphate in place of phosphoric acid for thefluorimetric determination of uranium is said to give greater sensitivity.476I n the field of organic analysis a-keto-acids have been determined byconverting them into the corresponding substituted quinoxalines by reactionwith o-phenylenediamine and measurement of their fluorescent properties.477X- Ray methods. Several papers have described the application of X-rayfluorescence methods to the determination of trace metals in various sub-stances.A theoretical study has been made of the determination of heavyelements in which calibration curves for zinc, copper, nickel, chromium, andvanadium have been tested for accuracy by analysing two samples of silicaterock of known composition .478 The determination of traces of severalmetals in organic mineral materials and rocks after extraction has beendescribed,479 and also the determination of uranium, thorium, and lead inzircons. 48*A rapid automatic method has been applied to the determination ofzirconium, zinc, thorium, cerium, neodymium, praseodymium, and lan-thanum in magnesium alloys.481In the biological field X-ray fluorescence methods have been applied toA N D W IL S 0 N471 C.A. Parker and C. G. Hatchard, Analyst, 1962, 87, 664.4 7 2 W. T. Rees, Analyst, 1962, 87, 202.473 Z. Holzbecher and P. Pblkrab, Coll. Czecla. Chenz. Comm., 1962, 27, 1142.474 C. W. Sill and C. P. Willis, Analyt. Chem., 1962, 34, 954.4 7 5 C. A. Parker and L. G. Harvey, Anulyst, 1962, 8’7, 558.476 T. S. Dobrolyubskaya, A. V. Davydov, and A. A. Nemodruk, Zhur. analit.4 7 7 J . E. Spikner and J. C. Tome, Analyt. Chem., 1962, 34, 1468.478Z. H. Kalman and L. Heller, Analyt. Chem., 1962, 34, 946.4 7 g J. Ottemann and G. Friese, Geochim. et Cosmochim. Acta, 1962, 26, 599.480 A. Buchs, Helv. Chim. Acta, 1962, 45, 741.481 G. A. Stoner, Anulyt. Chena., 1962, 34, 123.Khim., 1962, 1’7, 70478 ANALYTICAL CHEMISTRYthe determination of calcium and potassium in plant materials,482 and tothe determination of zinc, copper, and iron in biological tissues.483Other papers of general interest have described the determination of thesix major components of Portland cement by fluorescence X-ray spectro-graphy 484 and the analysis of bauxite by a photographic X-ray method.485Absorption Spectroscopy.-The papers reviewed in this section are con-sidered in the order ultraviolet and visible absorption, atomic absorption,infrared absorption, and nuclear magnetic resonance methods.Ultraviolet and visible absorption.A few papers of general interest havebeen selected from the vast amount of work that has been published in thisfield.Some practical considerations in the search for new reagents for absorptio-metry have been discussed by West,486 and Cheng 487 has discussed themasking action of EDTA with particular reference to its use in the selectivedetermination of copper.A critical comparison has been made of the available methods for thespectrophotometric determination of micro-amounts of copper in textiles 488and the determination of copper in some foodstuffs, by means of 2,9-dimethyl-1 ,lo-phenanthroline, has been de~cribed.~~gMagnesium in uranium has been determined after removal of the uraniumby measurement of the colour given with 8-hydroxyquinoline in the presenceof diethylene glycol monobutyl ether.490An investigation has been made of the boron-curcumin complex in thedetermination of traces of boron.491 Conditions for the formation of thecomplex were studied, including the choice of acid needed for protonationof the curcumin, and the choice of solvent for it.Some evidence was foundfor the existence of a complex having a 1 : 3 ratio of boron to curcumin.A boron oxalate-curcumin complex has been used for the spectrophotometricdetermination of boron in sea water 492 and the boron-curcumin complexhas also been used for the determination of boron in z i r ~ a l o y . ~ ~ ~A method has been developed for the determination of antimony basedon the reaction between chloroantimonate ions and Brilliant Green.494 Maininterference arises from gold and thallium.Determinations have been described of chromium using 1,2-diamino-cyclohexanetetra-acetic acid,495 of molybdenum using alloxantinY4g6 and ofuranium using isopropyltropolone and pyridine.497482 D. F. Ball and D. F. Perkins, Nature, 1962, 194, 1163.483 G. V. Alexander, Analyt. Chem., 1962, 34, 951.484 H. Uchikawa and Y. Inomata, J. Ceram. Assoc. Japan, 1962, 70, 16.485 A. Bezjak, T. Frig-Gabega, V. Uzelac, and I. Arapovi6, Croat. Chem. Actu, 1962,4 8 ~ T . 8. West, Analyst, 1962, 87, 630.487 K. L. Cheng, Analyt. Ckern., 1962, 34, 1392.488 A. G. Kempton, M. Greenberger, and A. M. Kaplan, Textile Res. J., 1962, 32, 128.489 P. D. Jones and E. J. Newman, Analyst, 1962, 87, 637.490 V. T. Athavale, R. L. Bhasin, and B. L. Jangida, Analyst, 1962, 87, 217.4 9 1 M . R. Hayes and J. Metcalfe, Analyst, 1962, 87, 956.492 R.Greenhalgh and J. P. Riley, Analyst, 1962, 87, 970.49s M. Freegarde and J. Cartwright, Analyst, 1962, 87, 214.494 R. E. Stanton and A. J. McDonald, Analyst, 1962, 87, 299.495 A. R. Selmer-Olsen, Analyt. Chim. Actu, 1962, 26, 482.496 Yag Dutt and R. P. Singh, Proc. Indiun Acad. Sci., A , 1962, 55, 195.49'D. Dyrssen and S. Ekberg, Actu Chem. Scand., 1962, 16, 785.34, 51CARTWRIGHT, WESTWOOD, AND WlLSON 479The direct spectrophotometric determination of fluoride can be achievedby means of the lilac-blue complex formed when fluoride reacts with thewine-red chelate of cerium(II1) and alizarin comple~one.*~~ The sensitivityis increased by using a 2% acetonitrile or acetone medium instead ofwater alone. Fluorides may also be determined by means of the bleach-ing effect of the fluoride ion on a thorium-Xylenol Orange complex.499Chlorine and its oxides have been found to give ultraviolet absorptionspectra in carbon tetrachloride which can be used for their determination, 500and iodide ions can be determined by means of the complex formed withthallic ions a t pH 2-S.501Iron can be determined spectrophotometrically by means of the bluecolour formed by the reaction of iron(I1) with quinisatin oxine in a bufferedsolution containing ethyl alcohol and a small amount of dimethylform-amide ; cobalt and nickel interfere.502 Iron has also been determined bymeans of the complex formed with l-hydroxy-9-xanthone in soy0 ethanol.503The applicability and limit'ations of the dithio-oxamide method for thedetermination of cobalt have been investigated.504Spectrophotometric methods have been described for the analysis ofmixtures of ethyltoluene isomers 505 and for the determination of water inorganic solvents other than those containing nitrogen. 506Atmic absorption spectroscopy. Recent work in atomic absorption spec-troscopy has been reviewed 507 and the applications of the technique tochemical analysis have been discussed. 508 Franswa has reviewed the theo-retical background of atomic absorption spectroscopy 509 and has alsodiscussed the determination of a large number of metals. 510I n a study of the factors affecting the determination of strontium inbiological materials and soil extracts it has been found that calcium andphosphate together depress absorption, but neither calcium nor phosphateseparately has serious effect.Interference from aluminium is eliminated bythe presence of an excess of ~alciurn.51~ I n the determination of smallamounts of magnesium in iron, interference by aluminium may be suppressedby the addition of str0ntium,5~~ and in the determination of magnesium inelectronic nickel and nickel alloys interference by aluminium and silicon isovercome by the presence of ni~kel.5~3Heavy metals such as lead, mercury, bismuth, and nickel present in urine498 S. S. Yamamura, M. A. Wade, and J. H. Sikes, Analyt. Chem., 1962, 34, 1308.49@ Z. RezG and J. Ditz, 2. analyt. Chem., 1962, 186, 424.6oo Z. Spurn$, Talanta, 1962, 9, 885.501 D. Betteridge and J.H. Yoe, Analyt. Chim. Acta, 1962, 27, 1.5 0 2 G. H. Ayres and M. K. Roach, Analyt. Chim. Acta, 1962, 26, 332.503 Brahm Dev and B. D. Jain, J . Indian Chem. SOC., 1962, 39, 247.504 R. Bondivenne, G. Beau, N. Busch, and R. Y. Mauvernay, Chim. Analyt., 1962,5 0 5 I. N. Diyarov and M. S. Pevzner, Zhur. analit. Khim., 1962, 17, 102.506 R. C. R. Barreto and H. S. R. Barreto, Analyt.. Chim. Acta, 1962, 26, 494.507 J. E. Allan, Spectrochirn. Acta, 1962, 18, 605.508 G. Milazzo, Chimica e Industria, 1962, 44, 493.509 C. E. M. Franswa, Ghem. Weekblad, 1962, 58, 177.510 C. E. M. Franswa, Chem. Weekblad, 1962, 58, 189.511 D. J. David, Analyst, 1962, 87, 576.512 C. B. Belcher and H. M. Bray, Analyt. Chim. Acta, 1962, 26, 322.513 T. R. Andrew and P.N. R. Nichols, Analyst, 1962, 87, 25.44, 114480 ANALYTICAL CHEMISTRYcan be determined after extraction with ammonium pyrrolidinedithio-carbamate and methyl n-pentyl ketone by vaporising the solutions in theflame of an atomic absorption spectrometer;514 zinc and cadmium can bedetermined by the direct spraying of urine into the flame.Infrared absorption. The use of silicone rubber gaskets in the construc-tion of demountable leak-proof sodium chloride cells has been described,515and details have been given 516 of a low-temperature gas cell capable of beingused for measurements down to -60".The determination of sulphur trioxide has been described, use being madeof a Pyrex-glass cell fitted with '' Irtan 2 " end plates which are only slowlyattacked by the material under te~t.5~7Traces of water may be determined by conversion into acetylene withcalcium carbide.The acetylene is transferred with a dry carrier gas intothe infrared cells and measured in solution in carbon tetrachloride.518In organic analysis, aliphatic formates have been determined by infraredspectrophotometry 519 and the technique has also been applied to the deter-mination of technical hexachlorobenzene.520Nuclear magnetic resonunce. The application of nuclear magnetic reson-ance to analytical chemistry has been reviewed 521 and a new type of spectro-meter having a high differentiation capacity has been de~cribed.5~~A study has been made of the nuclear magnetic resonance spectra ofbutadiene-isoprene copolymers and the method has been applied to theirdetermination.52310. ELECTRICAL METHODSGeneral.-Electrodeposition, polarography, radiochemistry and massspectrometry have been considered in this section. Polarography accountsfor most of the work published on electroanalytical techniques, and this isstill increasing. The review by Wawzonek,52* covering 1960 and 1961, con-tains 860 references to organic systems alone, and comparable developmentshave taken place during 1962. Much which is of interest or even importantmust therefore be omitted in any restricted survey of this field. Cathode-ray polarographic methods are steadily becoming more popular and a numberof applications of the square-wave polarograph have appeared, particularlyin the field of metallurgical analysis.Radiochemical applications have been very prolific and many of thesehave appeared in non-analytical journals as part of wider projects.Only514 5. B. Willis, Analyt. Chem., 1962, 34, 614.515 B. M. Mitzner, Appl. Spectroscopy, 1962, 16, 25.516 H. W. Myers and W. W. Martin, Analyt. Chem., 1962, 34, 1038.517 R. Bent, W. R. Lander, K. S. Pankhurst, and B. D. Waite, Nature, 1962,518 J . W. Forbes, Analyt. Chem., 1962, 34, 1125.519 R. M. Powers, M. T. Tetenbaum, and Han Toi, Analyt. Chenz., 1962, 34, 1132.520 V. I. Kolbasov, S. B. Bardenshhh, and R. V. Dzhagatspanyan, Zawodskaya5 2 1 J. Delmau, Bull. Soc. chim. Frame, 1962, 1.522 J. Dadok and 0. Knessl, Chem. Listy., 1962, 56, 295.523 Hung Yu Chen, Analyt. Chem., 1962, 34, 1134.524 S.Wawzonek, Analyt. Chem., 1962, 34, 182R.193, 62.Lab., 1962, 28, 446CARTWRIGHT, WESTWOOD, AND WILSON 48 1those in which analysis is directly concerned have been considered here. Inradioactivation analysis a greater interest has been shown in short-lived pro-ducts and high-energy neutrons produced by high-voltage generators. Com-binations of techniques have become more widespread, and ion-exchangemethods are frequently used to separate active constituents. The numberof applications of electrodeposition has continued to decline as it is displacedby more rapid and sensitive techniques.Special mention must be made of a new voltammetric method termedcoulostatic analysis. This involves providing a current impulse to an elec-trode which is at a potential corresponding to the base of a polarographicwave.The double layer is thereby charged to a potential at which a faradaicprocess can occur corresponding to the plateau of the wave. Electrochemicaloxidation or reduction then occurs and a faradaic current flows which decayswith time and the voltage falls correspondingly. The decay rate is relatedto the concentration of the electroactive species and the method has beenclaimed to be suitable for determinations in the concentration range10-'M. Publication of the method appeared almost simultaneously byDelahay 525 and R e i n m ~ t h , ~ ~ ~ and a simple apparatus for measuring thevoltage change has been described.5giElectrodeposition. In a review on electroanalysis, details of the progressin controlled potential analyses and applications of internal electrolysisduring 1960-61 have been de~cribed.~05 They were few in number, andcomparatively little new work on electrodeposition methods has been pub-lished during the last year.The analysis of lead- and tin-base alloys has been studied by controlled-potential electrolysis.Details of separation of tin from antimony, and cop-per from lead in tartrate solutions, and methods of avoiding interferencefrom bismuth were described. The methods were applicable to lead-tin-antimony-bismuth alloys. 528 Copper has been determined in aluminiumalloys by deposition from solutions of HN03-HBF, and HN03-HF-HBF,.Tin, if present, forms a complex and dpes not interfere, but bismuth causestrouble and is removed by co-deposition with lead at the an0de.52~ Nickeland molybdenum have been determined when present together.At pH4-4-2, the molybdenum is deposited as 2Mo,o3,13H,0. Copper, if present,is co-deposited with it and must be allowed for. After the solution has beenmade alkaline with ammonia, nickel is deposited.530 The method of internalelectrolysis has been applied to a number of separations. Gold can be sepa-rated from lead, bismuth, antimony, and copper in hydrochloric or nitricacid solution by using a silver anode and sodium chloride as anolyte, andthe method has been applied to the determination of the element in silver-copper-gold alloys. Bismuth was also separated from antimony, lead, and.copper in nitric acid-thiourea solution, by using a zinc or magnesium anode5 2 5 I?.Delahay, Analyt. China. Acta, 1962, 27, 90; Analyt. Chem., 1962, 34, 1267.526 W. H. Reinmuth, Analyt. Chem., 1962, 34, 1272.527 P. Delahay and Y. Ide, Analyt. Chem., 1962, 34, 1580; P. Delahay, Analyt.528 B. Alfonsi, Analyt. Chim. Acta, 1962, 26, 316.629 S. Bertoldi and A. Tartari, Alluminio, 1962, 31, 127.630 G. P. Protsenko and P. M. Kovalenko, Zavodskaya Lab., 1962, 28, 23.Chim. Acta, 1962, 27, 400.482 ANALYTICAL CHEMISTRYin B sulphate anolyte, and antimony has been separated from tin in a fluoridemedium. 531Electrodeposition has also been used as an adjunct in other methods ofanalysis. Iron has been removed and determined by electrolysis of a pyrid-ine-thiocyanate solution at a mercury cathode before determining vanadiumby spectrophotometric means.632Polaromaphy.--With the exception of potentiometry, polarography nowaccounts for more published research than any other electroanalyticalmethod. A general review on recent developments in both classical andoscillographic polarography has appeared.533 Wawzonek has again reviewedorganic applications 524 and so has Z ~ r n a n . ~ ~ ~ Other reviews have coveredinverse polarography, 535 principles and applications of Tast polarography,536non-aqueous media,537 continuous polarographic analy~is,5~~ effects ofadsorption 539 and formate media.S40A new Tast polarograph possessing greater voltage stability and a smallercapacitative current component has been described.541 Portable polaro-graphs suitable for rapid determination of dissolved oxygen have beenreported. In one device a gold cathade is used with the current read ona voltmeter ;w2 in another a wide-bore dropping-mercury electrode main-tained at -1.5 v (vs. Ag-AgC1 electrode) is used.543 A cell suitable forcontinuous measurements uses a rotating indicator electrode with a devicefor depolarising anodically and washing of the electrode in rapid succession.~4An elaborate electrode assembly permitted the simultaneous evaluation ofm, t, h, w, and drop count.645 U-Shaped vibrating mercury capillary elec-trodes have been claimed to be suitable for oscillographic polarography.M6Teflon dropping-mercury electrode capillaries have been tested in mediawhich corrode glass ; it was claimed that such electrodes were satisfactoryand gave greater reproducibility from drop to drop than glass; they wererecommended for general use.547 Rotating-disc electrodes have been foundto be suitable for polarography with solid electrodes.Good results wereobtained with 0.2-1-0 x 10-3~-feryocyanide,548 and anodic oxidation ofMV"'dimethylaniline.649 A simple technique for measuring a current tran-sient a t a known interval after the inception of a drop involved measuring631 P. Deschamps and Y . Bonnaire, Mikrochim. Acta, 1962, 463.632 G. H. Ayres and L. E. Scroggie, Analyt. Chim. Acta, 1962, 26, 470.633 D. N. Hume, Analyt. Chem., 1962, 34, 172R.534 P. Zuman, J . Electroanalyt. Chew., 1962,3, 157; Magyar Kim. Lapja, 1962,17, 8.635 R.Neeb, Angew. Chem., Int. Ed., 1962,1,196; Ya. I. Tur'yan and V. F. Romanov,636 P. 0. Kane, J . Polarog. Soc., 1962, 8, 10.637 G. Schober, V. Gutmann, and E. Nedbalek, 2. analyt. Chem., 1962, 186, 115.638 W. J. Parker, Metal Ind., 1962, 100, 82, 105.63D H. W. Nurnberg and M. von Stackelberg, J . Electroanalyt. Chem., 1962, 4, 1.640 G. S. Deshmukh, J . Sci. Ind. Res. India, 1962, 21, B, 144.542 A. H. Meyling and G. H. Frank, Analyst, 1962, 87, 684.643 R. Briggs and W. H. Mason, Lab. Practice, 1962, 11, 36.644 Y a . I. Tur'yan, Zuvodskaya Lab., 1962, 2.8, 98.645 H. P. Raaen and H. C. Jones, Anulyt. Chem., 1962, 34, 1594.646 J. Horyna and V. JehliEka, Co11. Czech. Chem. Cmrn., 1962, 27, 1326.647 H. P. Raaen, Analyt. Chem., 1962, 34, 1714.648 S.Azim and A. C. Riddiford, Analyt. Chem., 1962, 34, 1023.649 Z. Galus, C. Olson, H. Y. Lee, and R. N. Adams, Analyt. Chem., 1962, 34, 164.Zavodskaya Lab., 1962, 28, 5 ; H. W. Niirnberg, Z . analyt. Chem., 1962, 186, 1.K. Kronenberger and W. Nickels, Z. analyt. Chern., 1962, 186, 79CARTWRIGHT, WESTWOOD, AND WILSON 483oscillographically the potential generated across a series resistance. Themethod was claimed to be suitable for the range 10-5-10-6~.550 Benzyl-triethylammonium chloride has been stated to be especially suitable fordetermining the alkali metals; the hydroxide was also useful for such deter-minations in the presence of heavy-metal ions.551 Normal polarograms wereobtained for lead and a number of nitro-, nitroso-, and azo-compounds, theammoniate of sodium iodide being used as solvent.652A number of metal trace impurities have been determined in alloys.Antimony in cast iron has been measured by a rapid procedure which in-volved dissolution in an oxidising acid and addition of ascorbic acid.Awave for antimony a t -0.11 v (mercury pool) was used for analysis; molyb-denum, titanium, and copper caused no interference, but bismuth and arsenicgave trouble.553 Cadmium was determined in aluminium alloys by deriva-tive polarography. Simple dissolution in hydrochloric acid followed byelectrolysis gave a wave at -0.72 v (s.c.e.). Copper caused some interfer-ence but this was compensated for by deliberate addition of copper. Themethod was suitable for 0.1-0-35% of cadmium.554 Molybdenum in steelswas determined by employing a citric acid base electrolyte a t pH 2, thewaves at -0-27 and -0.65 v (s.c.e.) being used for measurement purposes.666Lead and copper were determined in tellurium and tellurium concentrates ;antimony, if present, was removed by distillation with hydrobromic acid +bromine.The solution was deoxygenated with sulphite, lead was deter-mined at -0.6 V, and copper after addition of tartrate a t -0-33 v ( S . C . ~ . ) . ~ ~ ~A phosphate medium has been found to be suitable for a number of analyses.Uranium has been measured in a tripolyphosphate medium by anodic oxida-tion of the (IV) valency state at -0.19 v (s.c.e.) at pH 9. Only iron(@causes any serious tro~ble.5~' Thallium also has been determined in thismedium; the E, values depend on the pH which had to be >4 to avoid inter-ference from iron(m), bismuth(m), and copper(=); an optimum value ofpH 7 was found. Addition of 0.1% of camphor displaced most interferingions to appreciably more negative values.Thallium was determined at the5 x 1 0 - 5 ~ level in the presence of 400 times as much lead.555" Several deter-minations have used ion-exchange columns to separate reducible speciesbefore analysis. Uranium was separated from thorium and bismuth byusing a Dowex 1-X8 column, eluted with a methanol-nitric acid solution,and determined directly. A mean error of only &l.9% was obtained on10-2000 pg. of urani~m.~5~ A new selective-ion exchange medium basedon a phenylfluorenone derivative was applied to the separation of a numberof metals, and procedures for the selective separation and polarographicdetermination of copper, zinc, cadmium, gallium, indium, tin, arsenic,550 H.B. Mark and C. N. Reilley, J . Electroanalyt. Chem., 1962, 3, 54.551 G. S. Supin, Zhur. analit. Khim., 1962, 17, 258.552 D. E. Sellers and G. W. Leonard, Analyt. Chem., 1962, 34, 1457.553 R. C. Rooney, J . Polarog. Soc., 1962, 8, 20.5c4 R. A. Hine and J. F. Bates, Metallurgia, 1962, 65, 101.555 K. Grasshoff and H. Hahn, 2. analyt. Chem., 1962, 186, 147.556R. G. Pats and T. V. Semochkina, Zavodskaya Lab., 1962, 28, 800.557H. E. Zittel and L. B. Dunlap, Analyt. Chem., 1962, 34, 1757.558 P. S. Shetty, P. R. Subbaraman, and J. Gupta, AnaZyt.Chim. Acta, 1962,27,429.55B J . Korkisch and F. Tera, 2. analyt. Chm., 1962, 186, 290484 ANALYTICAL CHEMISTRYbismuth, uranium, manganese, cobalt , and nickel were given.560 Seleniumwas determined in glass after fusion, removal of silicon with strong acid, andtreatment on an acid exchange resin. The percolate was made ammoniacaland polarographed from -0-6 to 1-0 V, the selenium being determined bystandard addition. 56Complex formation has been applied to several procedures. Gallium hasbeen evaluated by a method based on the displacement of cadmium fromits complex with 1,2-diarninocyclohexane-iVNN’iV’-tetra-acetic acid. Aftera check for free cadmium the mixture was polarographed in an acetate buffer.Interference by aluminium was avoided by addition of fluoride.Othermetals were removed by an extraction procedure and 3 x to 3 x l o - 5 ~ -gallium was determined in this way to &2.570.562 The exchangeability ofthe cobalt(I1) ion with the complexes of the alkaline-earth metals withEDTA has been used to separate them. Barium, strontium, and calciumwere separated by a simple procedure and then made to exchange with thesilver complexonate, thereby liberating silver ions; the change in the con-centration of these, determined polarographically, was a measure of themetal c0ntent.5~~ Manganese and iron give complexes with 2-[di-(2-hydroxypr opyl) aminolet hanol and 2- [ di- (2 - hydroxybutyl) aminolethanol andthe products which were anodically oxidised in sodium hydroxide solution.Manganese gave a wave at a more positive potential than iron, so that bothelements could be determined in the presence of each other ; manganese wasthus determined in a manganese ore and in side rite^.^^^ AluminiGm hasbeen determined in alumino-organo-siloxanes by decomposition with acidfluoride followed by sodium carbonate fusion.The residue was dissolved inan acetate buffer and complexed with Acid Chrome Dark Blue K and thesolution was polarographed over the range 0 to -0.8 v (mercuryTraces of selenium were evaluated in a slightly acid sodium tartrate orlithium citrate solution and the method was adaptable to <I0 , ~ g . / m l . ~ ~ ~T ~ ( I v ) formed pyrogallol complexes giving a two-stage reduction in a per-chloric acid-perchlorate medium; the steps a t -0-28 v and -0.41 v (s.c.e.)were well suited to analytical purposes and the diffusion current was linearwith concentration up to l m ~ .5 ~ ’ Silver gave a wave in a cyanide mediumfrom which the excess of cyanide was removed by nickel ions. None of thecommon cations or anions interfered, except thallium and lead. The latterwas removed by addition of excess of EDTA.56S A study of the complexformed between copper(I1) and mono-, di-, and tri-ethanolamine showedthat the monocomplex Cu(MEA),(OH), was formed above pH 9, the di-complex Cu(DEA),(OH),frompH 9 to l l , and the tricomplex Cu(TEA),(OH),from pH 7 to 11.5. The forma- Details of the media used were given.5695 6 0 J. Seidl, J. Stamberg, and E. HobkovB, J . Appl. Chem., 1962, 12, 500.561 Z.Habermann, SklciP. a. Keram., 1962, 12, 9.562 M. Kopanica and R. Pfibil, Coll. Czech. Chem. Comm., 1962, 27, 17.663 A. Tockstein and V. NovGk, M;krochim. Acta, 1962, 142.664 J. Doleial, V. Petrus, and J. ZJike, J . Electrounalyt. Chem., 1962, 3, 169.m5 E. A. Terent’eva, Zav&kaya Lab., 1962, 28, 807.666 R. Bock and H. Kau, 2. analyt. Chern., 1962, 188, 28.667 A. J. Bard, Analyt. Chem., 1962, 34, 266.568 R. M. Dagnall and T. S. West, Tulanta, 1962, 9, 925.5 6 9 J. F. Fisher and J. L. Hall, Analyt. Chem., 1962, 34, 1094CART WRIGHT , WEST WO 0 D , AND WILSON 485tion of molybdophosphoric acid has been shown to be suitable for determiningsmall amounts of phosphorus. Three waves were given by the complex acid,with E , values dependent on pH and composition of base solution.A pre-liminary separation of the corresponding arsenic complex was necessary. 670Nickel soaps were analysed by forming the pyridine complexes of nickelmyristate and palmitate. Lithium chloride in benzene-methanol andpotassium chloride in ethanediol were used as base solutions.671 Otherstudies of complex formation and stability constants have included cadmiumwith oxine,572 nickel with 4-carboxy-l,2-cyclohexanedione d i ~ x i r n e , ~ ~ ~ andchromium with Solochrome Violet R.574A simple procedure for the determination of arsenic in rocks involveddistillation as arsenic trichloride, after acid decomposition, into an am-monium sulphate-potassium chloride base solution, and polarography overthe range -0.3 to -1.0 v ( s .c . ~ . ) . ~ ' ~ Determination of uranium in monazitesand involved a simple ion-exchange extraction followed by polarographyin a 0-Oh-nitric acid solution. The height of the wave a t -1.05 v wasA direct determination of zinc in foodstuffs involved decom-position with perchloric acid and sodium chloride and addition of hydro-chloric acid; the method was suitable for 10 pg./ml. of the element.s77Copper, zinc, and manganese were determined simultaneously in plantmaterials by low-temperature ashing and dissolution in a base electrolyteof ammonia and ammonium ohloride. No difficulty arose from nickel. Leafsamples from conifers, sunflowers, and fruit trees were examined and pre-liminary experiments indicated that the method was suitable for milk, blood,and other biological materials.578A polarographic study of dissolved oxygen has indicated that the firstwave approximated to a reversible reaction but the second was a definitelyirreversible one. Both were diffusion-controlled and the diffusion currentswere proportional to concentration up to 8 p.p.m. of dissolved oxygen; dif-fusion coefficients were calculated, and the mechanisms involved discussed.679Measurement of the total wave height for oxygen in a 0.05% potassiumchloride solution was made the basis of a production control method for de-termining oxygen when mixed with nitrogen. Tests of standard mixturesshowed the accuracy to be within 1%.580Micro-amounts of chloride ion have been analysed a t a stationary mercurydrop by using a mercury-mercurous sulphate reference electrode.Electro-lysis a t zero volts was carried out for 5 minutes and the potential was thenmade cathodic a t 300 mv per minute. A peak current was obtained and thepeak height was proportional to chloride-ion concentration, the method being570 K. Grasshoff and H. Hahn, 2. analyt. Chem., 1962, 187, 328.571 W. U. Malik and R. Hague, Nature, 1962, 194, 863.5 7 2 R. D. Whealy and B. J. Bland, Talanta, 1962, 9, 823.573 C. V. Banks and J. P. Laplante, Analyt. Chim. Acta, 1962, 27, 101.574 E. Coates and B. Rigg, Trans. Faraday. Soc., 1962, 58, 88.5 7 5 A. I. Kalinin, Zhur. analit. Khim., 1962, 17, 390.676 F. Habashi, Metallurgia, 1962, 65, 255.577 J. Deshusses and J. Vogel, Pharm.Acta Helv., 1962, 37, 401.578 J. C. Sirois, Analyst, 1962, 87, 900.579 V. S. GrSths and M. I. Jackman, Talanta, 1962, 9, 205, 871.580 W. Heimann and K. Wisser, 2. analyt. Chem., 1962, 185, 266486 ANALYTICAL CHEMISTRYapplicable over the range 5 x 10+ to 1.8 x 10-4~.581 Nitrites were deter-mined alone and in the presence of nitrates, nitroparaffins, aldehydes, orketones by reaction with semicarbazide. A wave at -1.2 v (s.c.e.) wassuitable for analysis at pH 1-4. Nitroparaffins must be extracted, butnitrite and acetone can both be determined at pH 3 - 6 4 when the wavesare well separated from that of the semi~arbazone.6~~ The iodine content ofiodised salt was evaluated in a phosphoric acid base electrolyte, a platinumelectrode being used and the currents being measured at -0.2 and -0.6 v(s.c.e.).The difference in current gave a measure of the iodide content, and2.5 p.p.m. of iodine were thus determined.583A very large amount of organic polarography has been described.Acenaphthylene in 92% methyl alcohol containing a quaternary iodide gavea well-defined wave which was useful for analysis in the range 0.2-1.7 MM,and styrene did not interfere with this.584 Aliphatic carbonyl compoundsin low-boiling hydrocarbons were absorbed in an acetate buffer containingsemicarbazide, the resulting semicarbazones giving a wave between -0.95and -1.4 v (s.c.e.) which was used for the determination of total carbonylcontent. 585 a-Amino-acids resulting from protein hydrolysates were deter-mined, after separation by ion exchange, as their copper complexes in anacetate buffer solution.An automatic amino-acid analyser was developedfor this purpose.586 Carbon tetrachloride, chloroform, and dichloromethane,respectively, present in mixtures gave waves at -0.76, -1.75, and -2.65 vin a quaternary ammonium hydroxide solution in 75% ethanol. Themethod was applied to the analysis of hydrochloric acid arising from carbontetrachloride manufacture. 587 Methylpentoses were determined by con-version into acetaldehyde with periodate. A lithium hydroxide base wassuitable for the aldehyde evaluation and other sugars did not interfere.588Aldose oximes and semicarbazones gave single well-defined waves at pH 1.6-4.6 suitable for analysis with a linear relationship between diffusion currentand concentration over the range 2-50 x 10-4~.589 Picric acid has beendetermined in mixtures of nitrobenzenes, nitrophenols, and nitrocyclo-hexane resulting from the nitration of cyclohexane, in a medium of 0 .1 ~ -sodium hydroxide in 40% methanol. The first wave was used in the deter-mination and a preliminary removal of the nitrobenzenes was required. 590The effects of dodecyltrimethylammonium chloride on the half-wave poten-tials of aromatic compounds and the analytical use of the reagent have beendescribed. Suppression of maxima and separation of the reduction wavestook place.591 A full study of the reduction of dimethylglyoxime has been581 Kh. Z. Brainina and E. M. Roizenblat, Zavodskaya Lab., 1962, 28, 21.583 J.Armand and P. Souchay, Chim. Analyt., 1962, 44, 239.683 V. PlGka, P&mysl. Portravin., 1962, 13, 157.m4 V. D. Bezuglyi, V. N. Dmitriev, and T. A. Batovskaya, Zhur. analit. Khim.,586 A. V. Khoroshin, Zavodskaya Lab., 1962, 28, 420.686 M. C. Corfield and A. Robson, Biochem. J., 1962, 84, 146.687M. M. Filimonova, M. I. Levinskii, and Zh. D. Gudzenko, Zavodskaya Lab.,688A. H. Wardi and Z. P. Stary, Analyt. Chem., 1962, 34, 1093.68D J. W. Haas, J. D. Storey, and C. C. Lynch, Analyt. Chem., 1962, 34, 146.liD0 Ya. I. Tur’yan and P. M. Zaitsev, Z h u ~ . analit. Khim., 1962, 17, 231.6D1 D. J. Pietrzyk and L. B. Rogers, Analyt. Chem., 1962, 34, 936.1962, 17, 109.1962, 20, 424CARTWRIGHT, WESTWOOD, AND WILSON 487made. An 8-electron reduction to 2,3-diaminobutane occurred and this WMconfirmed by controlled potential electrolysis.A well-defined wave wasobtained over a range of pH.592 Chloropicrin has been determined in airby &.direct method; a well-defined wave was obtained in a solution of 80%methanol containing 0.08N-nitric acid, and no interference was shown by100 times its weight of carbon tetrachloride, methyl bromide, ethylene di-chloride and dibromide, or chloroform over the potential range +0.2 to-0.8 v (silver chloride ele~trode).5~~ The precision of the method variedfrom &l-1 to 5.0% over the range 4-27 x to 1.22 x 1 0 - 5 ~ . Thepolarographic behaviour of mercaptoalkyl compounds of disubstitutedguanidines, ethylamines, and ethanols and their disulphides have beenstudied for their possible determination in radiation-protection drugs.Overthe range pH 5-4-11.6 the wave corresponded to the formation of RSHg.The disulphides gave a linear relationship with concentration and currentover the range 6-7 x 10-5 to 3-2 x 10-4~.594 2-Mercaptoimidazole hasbeen studied in perchloric and sulphuric acid media. There was a linearcurrent-concentration relationship over the range 8 x to 2 x 10-3~.5g5Several determinations have been carried out in wholly non-aqueouemedia. Ethyl acrylate has been determined in mixtures with casein as partof a study of polymerisation reactions involving them. A wave was obtainedin a dioxan-methanol solution with tetramethylammonium iodide as baseelectrolyte at -1.6 to -1.7 v, which was suitable for analysis.596 1,2,4-Benzothiadiazine and related compounds were examined in anhydrousdimethylformamide.Structural factors and polarographic behaviour werecorrelated with a view to their determination.597 Vinyl cyanide has alsobeen examined in this solvent and gave satisfactory waves at E, = -1.72 v(mercury pool) over the concentration range 5 x to 1 x 1 0 - 4 ~ . Theywere suitable for analytical determinations. 598Procedures for a number of pharmaceuticals have been reported.Analyses for acetazolamide, chlorothiazide, and nitrofurantoin in tabletshave been published.599 Gentisic and homogentisic acid have been deter-mined together in a phosphate or carbonate buffer solution at pH 7-8 bymeans of their anodic waves which were well separated.600 Histamine solu-tions have been standardised by reaction with formaldehyde to give an iminereducible at -1.4 v (s.c.e.).Good results were obtained in the range0.481-1.443 mm601 Quinicine has been evaluated in the presence of athousand-fold excess of quinine in injection and cinchona preparations.After extraction with an alkaline ethanolic solution of m-dinitrobenzene andchloroform, and adjustment to pH 4.4 in acetate buffer, the quinicine was692 M. Spritzer and L. Meites, Analyt. Chim. Acta, 1962, 26, 58.693 B. Berck and J. Solomon, Analyt. Chem., 1962, 34, 574.694 W. Stricks, J. K. Frischmann, and R. G. Mueller, J . Electrochem. SOC., 1962,695 R. A. F. Bullerwell, J . Polarog. Soc., 1962, 8, 2.696 J. G6her and G. V&go, Magyar Kim.Folydirat, 1962, 68, 181.6s7 A. I. Cohen, B. T. Keeler, N. H. Coy, and H. L. Yale, Analyt. Chem., 1962,6eeA. S. Gorokhovskaya and B. E. Geller, Zavodskaya Lab., 1962, 28, 809.Oo0 M. Jirlra, Clinica Chim. Acta, 1962, 7 , 737.Ool D. E. Sellers, K. L. Breenlee, and R. E. van Atta, Analyt. Chem., 1962, 34, 441.109, 518.34, 216.A. F. Summa, J . Pharm. Sci., 1962, 51, 474488 ANALYTICAL CHEMISTRYdetermined polarographically. 602 Purines and pyrimidines and their deriva-tives were examined with a view to their determination, and a number ofprocedures have been recorded for individual determinations.603Alternating-current, Cathode-ray and Other Polarographic Methods.-These new methods have continued to develop. A recent review has sur-veyed the developments in theory and the practical applications to date.533Applications of cathode-ray methods to metallurgical analysis have also beenreviewed. 604 A Leeds and Northrup electrochemograph has been convertedto a recording A.C.polarograph by a small external adjustment in circuitry.This involved injection of a small A.C. and measurement across a seriesresistance shunted by an amplifier and rectifier. 605 The high backgrounddue to charging of the double layer in an A.C. polarograph has been mini-mised by a simple capacity-inductance network, thus giving an improvedcurrent peak and enhanced sensitivity with a narrow band amplifier. Anincreased signal-to-noise ratio was obtained, giving a sensitivity increase of10 to 20 times.606 Lead and cadmium were determined at the 0.1 pg.levelt o within 3% .GO7 A new cell assembly involving identical dropping-mercuryelectrodes has been tested with the differential cathode-ray polarograph.Results have shown that the coefficient of variation can be as low as 0~04~0.608Several determinations involving linear-sweep polarography have beenrecorded. Traces of antimony, copper, and lead have been estimated inferromanganese. Simple procedures for these elements, suitable for routinecontrol purposes, were described.609 Aluminium has been determined inthorium after electrolytic separation of other metals, as the SuperchromeGarnet Y complex a t pH 5.75 in an acetate buffer.610 The lead content ofstandard rocks G.l and W.l has been evaluated oscillographically after re-moval of silica, iron, and fluoride.611 Copper, nickel, arsenic, cobalt, zinc,and cadmium have been determined in uranium-acid-lead solutions afterseparation from each other on an anion-exchange column.Details of thevarious procedures were recorded.612 Zinc was determined in blood by asimple procedure involving preliminary extraction as the dithizone com-plex.613 Azin-phos-methyl residues in fruits and vegetables were deter-mined by cathode-ray polarography after removal of interfering substanceson an exchange column. An accuracy of 0.1 p.p.m. was claimed.614Applications of alternating-current polarography have included deter-minations of cadmium and thallium in products of non-ferrous metallurgy,615602 M.Girard and F. Rousselet, Ann. Pharm. franc., 1962, 20, 109.603 D. L. Smith and P. J. Elving, Analyt. Chem., 1962, 34, 930.604 P. H. Scholes, R & D, 1962, 38.6 0 5 J. W. Hayes and G. H. Aylward, Analyt. Chern., 1962, 34, 1039.606N. G. Lordi, Analyt. Chem., 1962, 34, 1832.6 0 7 R. Neeb, 2. analyt. Chem., 1962, 186, 53.6oo A. G. C. Morris, Analyst, 1962, 87, 478.610 T. M. Florence, Analyt. Chem., 1962, 34, 496.611 V. V. Zhirova, Geokhimiya, 1962, 542.612 L. Jarman and M. Matic, TaZanta, 1962, 9, 219.613 J. Vogel, D. Monnier, and W. Haerdi, J . Electroanalyt. Chem., 1962, 3,614 J. A. R. Bates, Analyst, 1962, 87, 786.61s R. G. Pats, Zavodskaya Lab., 1962, 28, 18.H. I. Shalgosky and J. Watling, Analyt. China. Acta, 1962, 26, 66.321CARTWRIGHT, WESTWOOD, AND WILSON 489the use of Solochrome Violet R for the determination of traces of iron,61sa study of the copper-mannitol complex,617 and the analysis of drugs inanimal feeding stuffs.618Square-wave polarography has been used for several metallurgicalanalyses. Cadmium in silicate rocks has been determined after separationas its dithizone complex, and the method has been applied to standard rocksG.l and W.l, results consistent with other techniques being obtained.61gBismuth, copper, indium, and gallium were determined in gallium arsenidein the 1 p.p.m. range by using 1M-hydrochloric acid as the base electro-lyte.620 Small amounts of uranium, down to 0.5 p.p.m., were determined inhafnium, zirconium, and zircaloy-2. Good agreement with the fluorometricmethod was claimed.621 A series of determinations of copper, lead, molyb-denum, tungsten, and zinc in zirconium and hafnium has also beenreported.622 Niobium was determined in steels in EDTA solution.623Anodic stripping techniques have been used to determine tin and indiumin binary all0ys,~~4 and traces of tin in steels.625Radiochemisb.-With rapid growth of this technique, the Reportersselect examples from diverse fields which are of analytical interest. Uses ofisotopic tracers are very considerable and are still growing but novel andless time-consuming methods have appeared. Activation methods haverapidly increased and several new procedures involving very short irradia-tion times with no chemical separation have simplified determinations.High-energy neutron irradiations from particle accelerators or Van der Graafgenerators have been increasingly applied and have provided rapid and con-venient alternatives to pile irradiations.Reviews have appeared on nucleonics,626 activation analysis for tracemetals in reactor materials,627 general chemistry,628 activation by neutrons,photons, and deuterons and their applications in metallurgy, biochemistry,and medicine,629 isotope dilution analysis in inorganic and trace analysis,630and radiometric titration and ,&reflection methods in analysis.631 A numberof modifications for scintillation counting have been published including theuse of suspensions of finely divided silica, which a t a 4% concentration inthe scintillator gives a transparent gel capable of producing stable suspen-sions of Bal*CO, and a higher counting efficiency than under “infinite616 R.C. Rooney and P. J. McIver, Analyst, 1962, 87, 895.618 A. C. Daftsios and E. D. Schall, J . Assoc. Offic. Agric. Chemists, 1962, 45,610 R. E. Stanton, A. J. MacDonald, and I. Carmichael, Analyst, 1962, 87,620 V. J. Jennings, Analyst, 1962, 87, 548.621 D. F. Wood and R. H. McKenna, Analyt. Chim. Acta, 1962, 27, 446.622 D. F. Wood and R. T. Clark, Analyst, 1962, 87, 342.623 M. H. Cockbill, Analyst, 1962, 87, 611.624 R. D. De Mars, Analyt. Chem., 1962, 34, 259.626 S. L. Phillips and I. Shain, Analyt. Chem., 1962, 34, 262.626 G. W. Leddicotte, Analyt. Chem., 1962, 34, 143R.627 M. RakoviE, Jadernci Energie, 1962, 8, 127.628 R.A. Bailey, U.S. Atom. Energy Comm. Rep., NAS-NS. 3106, 1962.629 J. Hoste, Chem. Weekblud, 1962, 58, 106.6so 5. Ruzidka, Chem. Listy, 1962, 56, 783.631 I. Porubszky and D. Hegedus, Magyar Kim. Lapja, 1962, 17, 90.T. Takahashi and H. Shirai, J . Electroanalyt. Chem., 1962, 3, 330.278.134490 ANALYTICAL CHEMISTRYthickness ” conditions.632 The use of a two-phase system of detergent-anthracene has been claimed to be suitable for a- and p-radiation countingand to have a high efficiency. It was checked on solutions of compounds of35S, 32P, 137Cs, 90Sr, 210Po, 45Ca, ‘Be, and 3H a t the 10-3-10-4~An apparatus for the heterogeneous counting of weak p-emittershas been described in which the sample containing 3H or 14C in solution wasrun through a 1 ml.spiral cell contained in a jacket holding silicone oil andsuspended anthracene crystals. It was claimed to be suitable for biologicalsamples and continuous recording of chromatographic effluents.634 Anotherdevice involved passing the radioactive solution through a glass tube packedwith anthracene crystals and situated between two G.M. tubes in a coin-cidence circuit ; this was claimed to be suitable for continuous-flow record-ing.635 The ring-oven method has been developed for investigations ofsolutions of radioactive materials of the order of nanocuries by a techniqueknown as ring-chronoautoradiography. Details of the apparatiis,636 and itsapplications to 6oCo, 137Cs, Q5Zr, 90Sr, 144Ce, and 106R~,637, 638 have beendescribed. The copper spark method has been applied to the determinationof 1311, 32P, and 35S in solutions down to 0-05 ,ug./ml.leve1.639 Difficultiesarose, however, due to other ions, especially those of alkali metals, and care-ful control of conditions was essential. A radio-respirometer has been devisedby attaching a G.M. tube to the absorption cup of a Warburg apparatus torecord the 14C02 fl0w.640Activation methods have increased considerably in number. Rutheniumhas been determined in platinum, by using the 103Ru isotope for /3-countinga t the 0.83-1.78 p.p.m. leve1,6*1 and arsenic and antimony in platinum byy-counting after separation as metal and s~lphide.6~2 Antimony fromo-03y0 to 1% has been estimated in lead, gold being used as a standard toavoid self-shielding difliculties; the ratio of the heights of the 0.40 Mevand 0.56 Mev y-photopeaks for l98Au and 122Sb, respectively, were used forcalculating the antimony c0ntent.6~3 Similarly, the antimony and cobaltcontent have been determined in magnesium base alloys containing 0.001 to0.1 p.p.m.of these elements;6** tin and uranium tended to interfere with theantimony if present a t more than 2 and 50 p.p.m., respectively, and nickelinterfered with cobalt above 0.03 p.p.m Several applications to tracemetals in steels have been described. Manganese was easily determinedwithout chemical separation by a 3-second irradiation at 4 x 10l2 neutronscm.-2/sec.-1 with measurement of the 840 kev y-photopeaks, and arsenic and632 H.J. Cluley, Analyst, 1962, 87, 170.633 L. S. Myers and A. H. Brush, Analyt. Chern., 1962, 34, 342.m4 E. Schram and R. Lombaert, Ann. Biochem. Ezp. Med. (India), 1962, 3, 68.635 E. Rapkin and J. A. Gibbs, Nature, 1962, 194, 34.6313 L. J. Ottendorfer and H. Weisz, Mikrochim. Acta, 1962, 725.637 H. Weisz arid L. J. Ottendorfer, Mikrochim. Actu, 1962, 818.638 H. Malissa and F. Loley, AnaZyt. Chim. Acta, 1962, 27, 381.639 J. F. Jalkowski and A. Zelle, Acta Chim. Acud. Sci. Hung., 1962, 30, 321.640 J. Goksoyr, Ann. Biochem. Exp. Med. (India), 1962, 3, 439.6 4 1 R. A. Killick and D. F. C. Morris, Tulanta, 1962, 9, 349.642 R. A. Killick and D. F. C. Morris, Talanta, 1962, 9, 879.643 F. Adams and J. Hoste, Tulanta, 1962, 9, 827.644 R. Todd, G.Cuthbert, and R. Dickinson, U.K.A.E.A. Report PG 337(S), 1962CARTWRIGHT, WESTWOOD, AND WILSON 491cobalt could be measured in the same sample after 10 minutes’ and 1 week’sirradiation, respectively, the peaks at 560 kev and 1.33 Mev being used,after chemical ~eparation.6~5 A scheme for the determination of 16 elementsin a nickel-base high-alloy steel after irradiation has been put forward withdetails of the complications and interferences which OCCUF.~*~ Sulphur andphosphorus have also been determined in steels by a double-irradiationmethod involving different fast-to-slow neutron flux ratios, and the methodhas given good results on a range of B.C.S. standard steels.s47 Tantalumwas determined in tungsten, without separation, by measuring the 1.2 MeVy-photopeak for 182Ta after a 3-second irradiati~n.~~g Sodium was deter-mined in rocks and silicate minerals by irradiation for periods of 10 secondst o 1 minute a t 5 x 1012 neutrons cm.-2/sec.-1 and measuring the 24Na photo-peak.To simplify measurement, only y-rays above 2.6 Mev were acceptedby the counter. Gallium and lanthanum interfered only if their contentwas high.G49 Molybdenum, tin, tantalum, and tungsten were determinedby thermal-neutron irradiation followed by solvent extraction of the tan-talum as fluoride with isobutyl methyl ketone. The tin and molybdenumwere converted into sulphides and the tungsten into the benzoin a-oximecomplex; the various elements were then determined byAluminium has been determined in natural diamonds in the range 0.1-20 p.p.m.by irradiation in DIDO at 5 x 10l2 neutrons cm.-2/sec.-l for 10minutes followed by measurement of the 2.27-minute half-life of 28A1.Irradiation in DIDO rather than BEPO avoided the Z8Si( n,p) 28A1 reactionwhich complicates the meth0d.~5l A further method for aluminium in rocksand minerals relied on the 3 MeV beam from a Van der Graaf generator.When this struck a gold target “Bremsstrahlung ” were produced whichinduced the 9Be(y,n)8Be reaction in beryllium. Irradiation for 1 minuteby the neutrons was sufficient to determine O.lyo to 10% of al~minium.~5~A similar sequence was used for the determination of beryllium. In thiscase a tungsten target was used with X-ray generation of fast neutrons.After striking beryllium-containing material, these were moderated tothermal values by polyethylene and were used to irradiate a silver disc.The decay of the lo8Ag was measured by its 2.1 &lev y-photopeak and fromthis the beryllium content was ~alculated.6~~ The activation of silver toproduce lo8Ag can be brought about by “ Bremsstrahlung,” protons, orneutrons and this has been used to determine rapidly the silver content ofsolders in the range 1-667(0.654 Traces of hafnium and zirconium 655 andiridium 656 in meteorites have been determined by irradiation followed byI.J. Graverman and W. A. Henninger, Analyt. Chem., 1962, 34, 1680.645 S. May and G. Pinte, Bull. SOC. chim. France, 1962, 287.647 P. Bouten and J. Hoste, Analyt. Chim. Acta, 1962, 2’9, 315.648 R.Corth, Analyt. Chem., 1962, 34, 1607.649 G. L. Schroeder and J. W. Winchester, Analyt. Chem., 1962, 34, 96.650H. Hamaguchi, R. Kuroda, T. Shimizu, I. Tsukahara, and R. Yamamoto,651 E. C. Lightowlers, Analyt. Chem., 1962, 36, 1398.652 D. F. Rhodes and W. E. Mott, Analyt. Chem., 1962, 34, 1507.653 C. A. Levine and J. P. Suds, Analyt. Chern., 1962, 34, 1614.654 L. I. Bilefield, Analyst, 1962, 87, 504.E 5 5 E. Merz, Qeochim. Cosmochim. Acta, 1962, 26, 347.656 P. R. Rushbrook and W. D. Ehmann, Qeochim. Cosmochim. Ada, 1962, 26, 649.Geochim. Cosmochim. Acta, 1962, 26, 503492 ANALYTICAL CHEMISTRYprecipitation methods and use of y-ray spectrometry; 0.006-0.57 p.p.m.of iridium was determined with high overall chemical yields.A number of metals present in biological materials have been determinedby activation procedures.Molybdenum in the region of 0.9 p.p.m. has beendetermined in clover. Both the 9 0 M ~ and the lolMo isotopes were used,but in the latter case the irradiation time was only 20 minutes.657 Bysolvent extraction, after isotopic dilution, with tri-n-octylamine in kerosene,the molybdenum was obtained in good chemical yield. Sodium and potas-sium were determined in tissues by irradiation and direct measurement ofthe y-photopeak for sodium. Potassium, however, required separation asthe dipicrylamine or tetraphenylborate, with p-counting. Reproduci-bility was claimed to be within 10% and the time for analysis was muchshorter than with any other method.65s Manganese was determined in bio-logical materials in the range 0-14-37.4 pg.per g. by irradiation followed byprecipitation as tetraphenylarsonium permanganate which avoided interfer-ence from chromium.659 Residual bromine, at the 0.05 pg. level, in agri-cultural crops 660 and citrus fruits 661 involved irradiation for 30-60 minutesfollowed by measurement of the activity of the 82Br isotope without anyseparation. Several determinations of oxygen by fast neutrons have beenreported. I n one method 14.5 Mev neutrons were produced by irradiationof a tritiated zirconium target with 250 kev deuterons. Only 10 seconds'irradiation time was necessary for the 160(n,p)16N reaction. The short-lived 16N was measured by counting the pulses from y-photons of energy>36 Mev and a limit of 10 p.p.m.was possible. Only boron and fluorineinterfered.662 A new method of activation involving 3He as the bombardingparticle has been developed. Owing to the low binding energy of the particlethe reactions undergone were usually exoergic and the isotopes produced hadvery high energies. Nuclides up to 48Ca were investigated with short irradia-tion times and the method was non-destructive. It was particularly suitablefor the determination of oxygen down to p.p.b.663Solvent-extraction procedures for separating and determining radio-isotopes have increased in popularity. The extraction of 5lCr a,s chromateinto diphenylcarbazide-isopentyl alcohol mixtures, and 56Mn as the diethyl-dithiocarbamate complex or as tetraphenylarsonium permanganate intochloroform gave excellent recoveries.664 Chromium was isolated from fissionproducts and stainless-steel corrosion products by extraction of the Cr(vI)tetrabutylammonium ion complex into isobutyl methyl ketone. Chemi-cal yield was determined spectrophotometrically, and the 51Cr content ob-tained from the 320 kev y-~hotopeak.~~5 Cerium, after oxidation to thequadrivalent state, was determined in fission products after extraction asc5' B. Van Zanten, D. Decat, and G. Leliaert, Talanta, 1962, 9, 213.G 5 * J. Pijck and J. Hoste, Clinica Chim. Acta, 1962, 7 , 5 .669 H. Smith, Analyt. Chem., 1962, 34, 190.660 V. P. Guinn and J. C. Potter, J . Agric. Food Chem., 1962, 10, 232.661 C. E. Castro and R. A. Schmitt, J . Agric. Food Chem., 1962, 10, 236.s s a R .F. Coleman, Analyst, 1962, 87, 590; E. L. Steele and W. Wayne-Meinke,663 S. S. Markowitz and J. D. Mahony, Analyt. Chem., 1962, 34, 329.864 G. Dinstl and F. Hecht, Mikrochim. Acta, 1962, 321.665 W. J. Mmck, M. E. Kussy, and J. E. Rein, Analyt. Chem., 1962, 34, 1602.Analyt. Chem., 1962, 34, 185; D. J. Neal and C. F. Cook, ibid., p. 178CARTWRIGHT, WESTWOOD, AND WILSON 493the tetra-n-propylammonium nitrocerate complex into nitroethane. Onlyfluoride interfered and this was avoided by the addition of aluminium.666Zirconium and niobium were separated from aqueous solutions by acetyl-acetone-chloroform mixtures. The niobium was extracted a t pH 2-5, andthe zirconium was removed a t pH 5-8.667 Molybdenum was determinedin fission products by extraction as the a-benzoin complex into chloroformfrom acid fluoride solution and /3- or y-counting of the g 9 M ~ .Only tungsteninterfered in the extraction, but not in the Ruthenium wasextracted almost quantitatively from other metals by carbon tetrachloridea t pH 4 in the form of RuO, and was /I- or y-c0unted.66~ A series of solventseparations for metals involved extraction of iron with isopentyl acetate andzinc with dioctylamine in ~ y l e n e . ~ ~ O Cobalt was determined in the presenceof large excesses of mercury, silver, copper, bismuth, lead, or thallium byextraction with diethyldithiocarbamate in chloroform after removal of othermetals by mercury(I1) and cyanide treatment. Cobalt down to 0.1 pg. hasbeen determined.671 Alternatively the cobalt was extracted with a fixedamount of the zinc complex in chloroform. The excess of reagent and com-plexes of foreign metals were removed by exchange with 203Hg(11).The20sHg remaining in the chloroform layer acted as a measure of the cobaltcontent. Lead has been similarly determined after addition of thalliumdiethyldithiocarbamate complex and counting of the residual 204Tl ; 0.06 pg.of lead in the presence of large excess of other metals and anions has beenestimated with accuracy.672 A highly efficient extraction of copper withdithizone in carbon tetrachloride allowed a rapid determination at pH 3.5-5.0 in the presence of thirteen other elements and was applied to the deter-mination of copper in water and urea. A limit of 10-10 g./ml.was ~laimed.~'3Cobalt has been determined in a standard alloy (N.B.S. 157) and in ingot iron(N.B.S. 55e) by using 6oCo as tracer and extracting the 2-nitroso-l-naphtholcomplex in chloroform. A value of 0.006% of cobalt in the latter was inclose agreement with the official value.674A number of chromatographic methods have also been used to separateand determine radioactive species. A rapid and effective separation of 9OSrfrom 'its daughter product on filter-paper impregnated with Amber-lite IR-120 resin from a citrate medium a t pH 3.8, was produced, and theelement was measured by a /I-recording densitometer. Similar separationswere possible with Amberlite IR-4B with water or cellulose phosphate withN - H C ~ . ~ ~ ~ A separation between these elements was also effected by ananion-exchange resin by forming the rhodizonates.Yttrium was retainedbut strontium was Tervalent iron was strongly held on a cation-666 S. F. Marsh, W. J. Maeck, G. L. Booman, and J. E. Rein, Analyt. Chem., 1962,34, 1406.6 6 7 N. Suzuki and T. Umori, Bull. Chem. SOC. Japan, 1962, 35, 595.668 L. Wish, Analyt. Chem., 1962, 34, 625.669 J. W. T. Meadows and G. M. Matlack, Analyt. Chem., 1962, 34, 89.671 P. C. van Erkelens, Analyt. Chim. Acta, 1962, 26, 46.6 7 2 P. C. van Erkelens, Analyt. Chim. Acta, 1962, 26, 32.6 7 3 J. RhZibka and J. Starj., Talanta, 1962, 9, 617.674 W. D. Ralph, T. R. Sweet, and I. Mencis, Anulyt. Chem., 1962, 34, 92.676 P. C. Stein, Analyt. Chem., 1962, 34, 352.676 A.A. K. Al-Mahdi and T. Schonfeld, Mikrochim. Acta, 1962, 254.J. Pijck, J. Hoste, and J. Gillis, Mikrochim. Actu, 1962, 76494 ANALYTICAL CHEMISTRYexchange resin and only slowly eluted by a buffered citrate solution atpH 2-9-32, thus giving a good separation from most other metals. Theefficiency of the method was checked with 59Fe.677 Zinc was determinedin effluent waters, after removal of the lead by co-precipitation with stron-tium sulphate, by passing the water through a column of cellulose acetateimpregnated with dithizone at pH 4.5.67s Several separations of fission pro-ducts have been made. The rare earths have been separated and deter-mined by using cation-exchange columns. After scavenging with zirconiumphosphate and barium sulphate and finally elution with a-hydroxybutyratesolutions of pH 4.2 and 3.4, individual rare earths could be determined.679Descending paper chromatography was used to separate plutonium andamericium with butanol-nitric acid mixtures.It was possible to separatePu(m) from Pu(r~).llO Separation of iodide ions by means of 1311 on anAmberlite IR-400 resin, followed by elution with 4~-ammonium chloride andp-counting, was found to be suitable for low-level detection and determina-tion. 680 The separation of 1311-labelled thyroxine and tri-iodothyroninefrom blood serum was effected on ion-exchange resin, an acetic acid-formicacid medium being used. Separation from other components of the serumwas efficient and more rapid than extraction methods hitherto used.681Similar separations have been possible by paper chromatography in aphosphate buffer at pH 8.5 6S2 and a trichloroacetic acid medium.683 By useof a column of alumina it was possible to separate and determine labelledsulphur, tetramethylthiuram disulphide, and dimorpholinyl disulphide in atoluene extract of vulcanisates.Liquid scintillation counting of the eluatewas possible in spite of some quenching.684 Tritium assay by proportionalcounting after gas- chromatography has advantages over other methodsand the difficulties arising from coincidence losses a t high count ratesand interferences from other peaks have been s t ~ d i e d . ~ ~ 5 The separation ofoctadecane, phenanthrene, and similar compounds labelled with 14C wasefficiently carried out on an alumina column.When applied to their deter-mination in asphaltic bitumens and marine sediments some difficulties arosefrom other components of high molecular weight and separation washarder.686 Paper Chromatography has been applied to several biochemicalassays by using 14C-labelled materials. The methyl esters of 14C-labelledbile acids have been effectively separated by descending chromatography onpaper impregnated with aluminium hydroxide, the solvents being petroleum-methanol and petroleum-benzene-methanol. Cholic, deoxycholic, andlithocholic acid were determined in the range 0.6-3.0 pg.687 Pyridoxal6 i i D. A. Knyazev and A. I. Mikhailichenko, Zhur. priklad. Kh,im., 1962, 35, 66.6'8 B. A. Loveridge and A. F. Owens, A.E.R.E.Report AERE-R 3945, 1962.6 i 9 K. Wolfsberg, Analyt. Chem., 1962, 34, 518.680 M. Lesigang and F. Hecht, Mikrochim. Acta, 1962, 327.681 K. Muller, H. Skrube, and H. Spitzy, Mikrochim. Acta, 1962, 1144.6 8 a A. Taurog, Biochim. Biophys. Acta, 1962, 60, 197.683 S. Lissitzky, J. Torresani, A. Pinchera, and M. Andreoli, Clinica Chim. Acta,685 J. K. Lee, E. K. C. Lee, B. Musgrave, Yi-Noo Tang, J. W. Root, and F. S.686 P. Hamway, M. Cefola, and B. Nagy, Analyt. Chern., 1962, 34, 43.68' B. P. Smirnov, R. A. Popova, G. P. Danilova, and R. A. Niskanen, Biokhimiya,1962, 7, 13. 684 H. I;. Pedersen, Acta Chem. Xcand., 1962, 16, 870.Rowland, Analyt. Chern., 1962, 34, 741.1962, 27, 197CARTWRIQHT, WESTWOOD, AND WILSON 495phosphate in blood has also been estimated after separation of plasma andconversion by enzyme into tyramine.688 An automatic scanning method wasused for measuring the activity.Gas-liquid chromatography has been usedto determine 14C-labelled lipids. The effluents from the column were con-densed directly into cartridges filled with anthracene crystals and silicone oil,and the activity measured directly by scintillation counting. OSgA considerable number of papers have been published on isotopic tracerand carrier methods involving precipitation of active species. Sodium hasbeen determined in sea water by scavenging with lanthanum hydroxidefollowed by precipitation of sodium chloride by hydrogen chloride and fol-lowed by 4n proportional counting of 24Na. Sulphur has also been deter-mined by precipitation as barium sulphate with a low-background !-counterto determine the 3%.Full details of interferences and their treatment wereworked out. 090 Strontium was determined in bone after addition of carrierby ashing and y-counting after removal of the daughter product andprecipitation as nitrate.691 -A rapid procedure for the determination ofcobalt in fission products involved separation of the hydroxide and conver-sion into Co[Hg( SCN)*] ; separation from other products was almost coni-plete.692 Other fission products determined by precipitation methods in-cluded silver as iodide after scavenging and repreci~itation,~~~ calcium asoxalate after removal of strontium as nitrate and scavenging with ferrichydr0xide,~94 yttrium and promethium as iodates after preliminary purifi-cation stages,695 and antimony as meta1.696 The use of thionalid for co-crystallisation of ultramicroscopic quantities of elements has been appliedto 27 elements.Of these, 16 showed very high recoveries and the methodwas applied to the determination of silver in sea water by using lloAg astra~er.6~' A rapid method for determining small concentra.tions of iodineinvolved addition of sodium iodide, liberation of iodine, and precipitation assilver iodide.698 Radio-assay of methanethiol containing 35S or 14C waseffected by precipitation of the mercuric salt from a mercuricyanide solution.The /?-radiation was measured by a thin-window gas-flow counter ; goodreproducibility was obtained after correction for self-absorpti0n.6~~A number of novel procedures have been reported.Manganese has beenisolated by distillation as permanganic acid from a solution of concentratedsulphuric and nitric acids and iodate, 54Mn being used as tracer. Recoverywas excellent and the method was applied to the determination of the ele-ment in iron cyclotron targets. ' 0 ° A method for determining radon in waters6 8 8 A. Hamfelt, Clinica Chirn. Acta, 1962, 7 , 746.689 A. Ksrmen, L. Giuffrida, and R. L. Bowman, J . Lipid Res., 1962, 3, 44.690 D. L. Love and D. Sam, Analyt. Chem., 1962, 34, 336.691 H. Foreman and M. B. Roberts, Talanta, 1962, 9, 559.6 9 2 S. F. Marsh and W. J. Maeck, Talanta, 1962, 9, 285.693 G. J. Hunter, G. F. Marshall, and M. Perkins, A.E.R.E.Report AERE-AM 89,694 U.K.A.E.A. Report PG 311(W), 1962.6Q6 M. E. Pruitt, R. R. Rickard, and E. I. Wyatt, Analyt. Chem., 1962, 34, 283.696 J. W. Arden, G. J. Hunter, and M. PeIkins, A.E.R.E. Report AERE-AM 87,1962.697 M. G. Lai and H. V. Weiss, Analyt. Chem., 1962, 34, 1012.698 U.K.A.E.A. Report PG 334(W), 1962.' 0 ° J. Pijck and J. Hoste, Analyt. China. Acta, 1962, 26, 501.1962.R. H. Herber, Analyt. Chern., 1962, 34, 340496 ANALYTICAL CHEMISTRYwas based on the equilibrium between 214Bi and its parent radon. By use ofan inert carrier, the bismuth was precipitated as bismuth n-propyl gallatewhich was B-counted in the usual way. A limit of 20 picocuries/l. wasclaimed.701 A rapid method for determining active indium involved anamalgam-exchange reaction in hydrobromic acid solution.After acquiringactivity, the amalgam was back-extracted with inert indium solution andthe activity of the aqueous solution was measured. The possible interferenceof 19 other elements was tested but contamination was < O-l%.702 Dis-solved oxygen has been determined in pure and natural waters by its quanti-tative oxidation of 204Tl deposited on copper turnings. The water contain-ing dissolved oxygen was passed through a column containing the turningsand the TI+ liberated was detected by a G.M. tube; the method was claimedto be suitable for the range 0.2-3 p.p.m. on use of a linear calibrationcurve.7o3 A simple method for determining the isotope effect on reactionrate has been applied to D-glucose by double labelling.By following the rateof oxidation of a- or ~-[6-~~C,l-~H]glucose and a- or ~-[l-~*C,6-~H]glucose,information on the importance and position of the isotope in the moleculewas obtained. Since the ratio of activities only was required, separation ofthe individual species was not necessary. 704MMS Spectrometry.-A recent comprehensive review has described thedevelopments in methodology and analytical applications which haveoccurred during the years 1960 and 1961, particularly in the United Statesof America, and the U.S.S.R.705 I n another review of methods for determin-ing interstitial elements in metals, mass spectrometry was claimed to behighly successful for oxygen, giving a possible precision of &O.OOOl% on a 1 g.sample.706 New instruments reported include the SMU 50OY7O7 a modifiedinstrument including a battery-operated emission regulator, which is par-ticularly suitable for isotope ratio analyses and has been successfully appliedto 13C/12C ratios;708 and a time-of-flight instrument with two collectors, oneof which collects the total ion current and the other records the mass spec-trum.709 A modified filament arrangement has been described in whichthe centre filament is vertical and parallel to the side filaments, permittingsimultaneous analysis of two samples and the measurement of abundancedifferences smaller than is possible with the normal filament arrangement. 710A modified radio-frequency spark-source has been applied to determinationof amino-acids and their ~alts.7~1 Other devices include an all-glass heatedinlet for injecting samples into the stream feeding the spectrometer,712 an701 J.R. W. Kerr, D. I. Coomber, and D. T. Lewis, Analyst, 1962, 87, 944.70a R. R. Ruch, J. R. De Voe, and W. W. Meinke, Talanta, 1962, 9, 33.705 H. G. Richter and A. S. Gillespie, Analyt. Chem., 1962, 34, 1116.7 0 4 H. S. Isbell, L. T. Sniegoski, and H. L. Frush, Analyt. Chem., 1962, 34,705 R. M. Reese, Analyt. Chem., 1962, 34, 243R.' 0 6 M. W. Mallett, Talanta, 1962, 9 133.707 D. Charles, Chim. analyt., 1962, 44, 49.?OsA. 0. Nier, W. R. Eckelmann, and R. A. Lupton, Analyt. Ckmn., 1962, 34,709 R. S . Gohlke, Analyt. Chem., 1962, 34, 1332.'11 W. L. Baun and D. W. Fischer, Analyt. Chem., 1962, 34, 294.'la L.Peterson, Analyt. Chem., 1962. 34, 1850.982.1368.H. Patterson and H. W. Wilson, J . Sci. Instr., 1962, 39, 84CARTWRIGHT, WESTWOOD, AND WILSON 497inlet for injecting samples directly from a gas-chromatography column, 713and a molecular-sieve device for separating volatile compounds from largeexcesses of carbon dioxide and water, with subsequent removal of adsorbedmaterials for analysis.714The plutonium-uranium ratio in feed solutions for reactor separationplants has been determined by using an MS 5 spectrometer. The concentra-tions of 235U, 238U, and 239U were determined by using 233U as a tracer, andthose of 24OPu, 248Pu, and 244Pu by using 242Pu as tracer.'15 A check bymass spectrometry on the effectiveness of chemical precipitation of rubidiumand strontium showed that separation of strontium as sulphate after removalof traces of iron and aluminium is more rapid and efficient than by ion-exchange techniques,716 though the latter can be shown to give productswhich are pure enough for mass-spectrometric analysis.717 Analysis of anumber of ferrocenes has shown that little or no fragmentation occurs at lowvoltages, and the peak intensities of the spectra are quantitative measuresof the quantity of material.7ls Silver has been determined in meteorites bya wet method followed by chromatography and precipitation as sulphidewhich was examined on a tantalum filament in a mass spe~trometer.~lg ThelSO content of sugars and glycogen has been determined by oxidising themin the presence of mercuric cyanide to yield carbon dioxide, followed by mass-spectrographic analysis of the latter.720Most applications have, of course, been associated with organic materials,especially in the petroleum industry.Analyses of gasolines and other motorfuels have produced calibration data for 13 aromatic, 2 olefin, and 4 satur-ated hydrocarbon types in the c6412 range with a reproducibility of 0.2%.The aromatics included alkylated benzenes, indanes, and naphthalenes. 721Similar analyses of light catalytic cycle stocks (b.p. range 622-625"~),within the formula range CnHBne16 and CnH2n-18, showed that the formerrange was largely alkylfluorenes and the latter contained a high percentageof phenanthrenes and anthracenes, 722 and compounds of the CnH2n--14 typewere tetrahydroant hracenes, tetrahydrophenanthrenes, and benzindanes.Catalytically cracked furnace oils have shown the presence of paraffins, con-densed and uncondensed polycycloalkanes, alkylbenzenes, indanes, tetra-lins, indenes, naphthalenes, acenaphthylenes, fluorenes, and acenaphthenes.Infrared data and elution methods were used to assist the interpretations. 724The ratio of branched to normal hydrocarbons up to C,, has been determined713 V.A. Cirillo, D. J. Skahan, B. Hollis, and H. Morgan, Analyt. Chem., 1962,34, 1353; C. BrunnBe, L. Jencld, and K. Kronenberger, 2. analyt. Chem., 1962. 189, 50.?14 M. L. Bazinet and C. Merritt, Analyt. Chern., 1962, 34, 1143.716 U.K.A.E.A. Report PG 340(W), 1962.716 W. G. Deuser, Geochim. Cosmochim. Acta, 1962, 26, 515.717 P. W. Gast, Geochim. Cosmochim. Acta, 1962, 26, 927.'18 D. J. Clancy and I. J. Spilners, Analyt. Chem., 1962, 34, 1839.719 V. R. Murthy, Geochim. Cosmochim. Acta, 1962, 26, 481.720 J. S. Lee, Analyt. Chem., 1962, 34, 835.721 D. M. G. Lawrey and J. F. Paulson, Analyt. Chem., 1962, 34, 538.7 2 2 K. W. Bartz, T. Aczel, H. E. Lumpkin, and F. C. Stehling, Analyt. Chem.,733 T. Aczel, K. W. Bartz, H. E. Lumpkin, and F. C. Stehling, Analyt. Chem.., 1962,724 M. E. Fitzgerald, V. A. Cirillo, andF. J. Galbraith, AnaZyt. Chcm., 1962,34,1276.1962, 34, 1814.34, 1821498 ANALYTICAL CHEMISTRYin Fischer-Tropsch products by ushg a molecular-sieve technique.725Nitrites have been identified in petroleum products after removal of thenitrogen bases with hydrochloric and perchloric acid and separation byformation of complexes with ferric chloride and zinc chloride. Dicyano-benzene, cyanoindene, cyanohexane, cyanonaphthalene, and cyanobiphenylderivatives were identified. 726A number of papers have been published on correlations for classes ofcompounds : 103 monohalogenated aliphatic compounds have been investi-gated and degradation paths shown t o be characteristic of the electronega-tivities of the halogen atom. The cleavage mainly occurs in the carbon-halogen bond and, as expected, the ease of breakdown follows the orderI > Br > C1 > B'. There is some tendency for iodine and bromine atomst o form, but with the other halogen compounds only hydrogen chloride andfluoride are found. If the carbon bond adjacent to the halogen is branchedthen the cleavage follows the order C1 > Br > I.727 When aromatic com-pounds were tested, the major ion degradation paths were shown to be acombination of effects found previously for aromatic hydrocarbons and ali-phatic halogenated compounds, with the former predominating for the aro-matic fluorides and the latter for the aromatic iodides. Poor ring halogencompounds, other than fluorides, the loss of halogen gave a major ion, butwhen the halogen was on a side chain cleavage of the bond ,9 to the groupcontaining the halogen atom was highly favoured : 88 compounds in all weretested. 728 Aliphatic nitriles gave significant amounts of the molecular ionin their mass spectra and cleavage of the a-bond to the functional group wasquite insignificant. /?-Bond cleavage with rearrangement gave the base peakup to C,, but became less important a t higher molecular weights or withchain-branched compounds. The ion of mass M + 1, however, was signifi-cant and useful for molecular-weight identification in many cases. 729 Withamines the molecular ion peak decreased rapidly as the molecular weightincreased. Those compounds which were not substituted on the a-carbonatom underwent /?-bond cleavage to produce the most abundant ion. Witha-substitution an a-p rearrangement of groups took place to form the mostabundant ion.730 The mass spectra of a number of methyl and beiizylsubstituted benzoate also gave useful data for analytical purposes. 731Deuterium has been determined in organic compounds by combustion fol-lowed by reduction of the H,O and D,O to H, and D, and analysis of theresultant gases. With the use of small-scale built-in apparatus the methodwas rapid and reliable.732By low-temperature ionisation the parent peaks of 30 steroids have beenobtained and have provided a method for their molecular-weight determina-' s 6 A. G. Sharkey, J. L. Schultz, and R. A. Friedel, Anulyt. Chem., 1962, 34,726 G. K. Hartung and D. M. Jewell, Analyt. Chi,m. Actu, 1962, 27, 219.727 F. W. McLafferty, Analyt. Chern., 1962, 34, 2.728 F. W. McLafferty, Analyt. Chem., 1962, 34, 16.720 F . W. McLafferty, Analyt. Chem., 1962, 34, 26.730 R. S. Gohlke and F. W. McLafferty, Alzalyt. Chem., 1962, 34, 1281.7 3 1 T. Aczel and H. E. Lumpkin, Analyt. Chem., 1962, 34, 33.732 N . Tamiya, Bull. Chem. Soc. Japan, 1962, 35, 863.826CART W RIG H T , WE ST WO 0 D , 499The method is claimed t o be rapid. Highly substituted pregnanesAND W IL S 0 Ntion.733and pregnenes gave similar results.73411. THERIAL METHODSEarly work from 1893 to 1940 on thermogravimetric analysis has beenreviewed by Duva1,735 and more recent developments by B&rta.736 Theimportance of close attention to conditions of operation and state of thesample in obtaining reproducible results continues t o be stressed. Berlinand Robinson 737 have derived a relation between final decomposition tem-perature, the size and physical condition of the sample, and the rate ofheating, which was in agreement with published data on the decompositionof a number of compounds, and in reasonable agreement with apparent acti-vation energies calculated for the decompositions. From e.m.f. valuesobtained in thermogravimetry, Soulen 738 has used an electronic digital com-puter to calculate temperature, weight, loss of weight, and rate of loss ofweight.A number of papers have described modifications to or refinements ofthermogravimetric apparatus, including automatic temperature control andregistration of temperature and change of ~eight,~39 a new method of tem-perature regulation with a transistorised thermobalance,740 an automaticthermobalance for use with a vacuum,741 and modifications to allow safeoperation in a hydrogen atmosphere. 742A useful review of differential thermal analysis by Mackenzie andMitchell 743 lists 297 references. I n addition to an account of the historicaldevelopment, principles, and technique of the method, it describes the grow-ing applications, not only to clays and minerals, where much of the develop-ment work was done, but also to a much wider field of inorganic, organic,and organometallic compounds. Barrall and Rogers 744 discuss the appli-cations to organic compounds, and the merits of employing a diluent, whichmay, for some analytical work, advantageously react with the sample.Other work has been concerned with chelates of the oxines,745 melting andboiling points and other phase transitions in organic andmaterials with components of high vapour pressure in an apparatus whichpermits rapid cycling over a small temperature range.747The combination of results from thermogravimetric and differentiali 3 3 L. Peterson, Chem. and Ind., 1962, 264.734 L. Peterson, Analyt. Chem., 1962, 34, 1781.735 C. Duval, China. analyt., 1962, 44, 191.i 3 6 R. Barta, Silikcity, 1962, 6, 125.7 3 7 A. Berlin and R. J. Robinson, Analyt. Chirn.. Acta, 1962, 27, 50.i 3 8 J. R. Soulen, Analyt. Chern., 1962, 34, 136.739 P. Imrig, Silikdty, 1962, 6, 91.7 4 0 Z. Formanek and J. Dykast, Silikcity, 1962, 6, 113.5 4 1 0. brnjr, Silikcity, 1962, 6, 81.7 4 2 H. J. Isensee, 2. analyt. Chem., 1962, 186, 357.743 A. C. Mackenzie and B. D. Mitchell, Analyst, 1962, 87, 420.7 4 4 E. M. Barrall I1 and L. B. Rogers, Analyt. Chem., 1962, 34, 1101.745 W. W. Wendlandt and G. R. Horton, Analyt. Chern., 1962, 34, 1098.746 D. A. Vassallo and J. C. Harden, Analyt. Chem., 1962, 34, 132.747 D. B. Gasson, J. A!& Instr., 1962, 39, 78500 ANALYTICAL CHEMISTRYthermal analyses has shown advantage in work on phosphor raw materials,74sand there have been more investigations 7 4 9 9 750 into the practice andadvantages of simultaneously registering both sets of results.P. F. S. CARTWRIGHT.J. V. WESTWOOD.D. W. WILSON.748 R. C. Ropp and M. A. Aia, Analyt. Chem., 1962, 34, 1288.7 4 9 L. Erdey, G. Liptay, G. Svehla, and F. Paulik, Talanta, 1962, 9, 489.750 A. Blaiek and J. Halousek, Silikhty, 1962, 6, 100

ISSN:0365-6217    

DOI:10.1039/AR9625900436

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

CRYSTALLOGRAPHY1. GENERALTHIS Report is concerned with papers on crystal-structure analysis andallied topics which were published in 1962. A few papers from earlieryeam, whose inclusion now seems appropriate, are also mentioned, but asusual the reader may find that something of importance has been overlooked,probably one of his own publications in fact! Because of indisposition ofa contributor the section on inorganic structures has been held over untilnext year. 1962 was the 50th anniversary of the discovery of X-ray diffrac-tion by von Laue, Friedrich, and Knipping, and the occasion was celebratedby a meeting in Munich in July. This took the form of a commemorativesession, lectures describing the development of the subject, and a symposiumon " Recent Advances in Experimental and Theoretical Methods of CrystalStructure Research" during which some 65 papers were presented.Theyear has also been marked by the award of two Nobel prizes, in Chemistryand in Medicine, to five research workers who are (among other things)X-ray crystallographers: M. F. Perutz, J. C. Kendrew, F. H. Crick, J. D.Watson, and M. H. Wilkins. Recent spectacular progress in protein crystal-lography and biomolecular structures was reviewed in these Reports twoyears ago, and, although 1962 might seem the occasion, it was felt thatthe time was not yet ripe for another review. There has been no diminutionin the number of papers dealing with (relatively!) simple crystal structures ;indeed, the X-Ray Analysis Group of the Institute of Physics has thoughtit worth while to produce a list of crystal-structure investigations in progress,to prevent duplication of effort.Experimental Techniques.-A metal cryostat of simple construction,which can be oscillated or rotated, and was designed for the study of singlecrystals or powders at temperatures down to 4" K, has been described.lStreib and Lipscomb have described their equipment for crystal growthand investigation a t temperatures in the helium-nitrogen range.Apparatusfor making X-ray investigations at high pressures is coming into use in anumber of laboratories, and a simple device capable of producing a quasi-hydrostatic pressure of 150 kbar has been described.3 A suggestion formodelling a counter diffractometer on a Seeman-Bohlin focusing camerahas been p~blished.~ Other improvements in diffractometer design includea simplified three-circle X-ray goniometer.5 X-ray image intensifiers andsecondary electron image intensifiers can be used for direct observation andrecording of diffraction patterns; in fact the signal strength can be madesuch that cinefilm running at standard speed can record the changing patternK.L. Chopra, Cryogenics, 1962, 2, 167.E. R. Pike, J . Sci. Instr., 1962, 38, 205.* W. E. Streib and W. N. Lipscomb, Proc. Nat. Acad. Sci., Wash., 1962, 48, 911. * J. C. Jamieson and A. W. Lawson, J. AppZ. Phys., 1962, 33, 776.ti R. W. H. Small and S . Travers, J . Sci. Instr., 1961, 38, 205502 CRYSTALLOGRAPHYfrom a rotating crystal.6 Polaroid film promises to be particularly usefulin recording neutron diffraction patterns.Most of us will regard as belatedthe discovery 8 that a counter and scaler can be used to measure integratedintensity.It is perhaps not inappropriate to mention under this heading the pro-gress that has been made in accurate measurement of lattice parameters,Knowles reports new diffraction measurements bearing on the factor forconversion of X-units into Angstroms, and gives this factor as 1.002049 -+ 0.000036. A single-crystal method has been used to give the unit celldimensions for seven pure materials to six significant figures,l0 while a newanalysis l1 of data published by Bond l2 has given the unit cell dimensionof silicon to about the same accuracy. Otte l3 has discussed the effectof specimen condition on the precise determination of lattice para-meters.Theory and Practice of Structure An&&.-Progress in the last ten yearsor so in the field of X-ray and electron diffraction by molecules and crystalshas been reviewed.14 An interesting paper l5 discusses the possibilities fordirect structure analysis by a computer when stereochemical informationcan be utilised.Users of crystallographic computers may find a recentconference report l6 of interest. Crystallographers have long speculated onwhether it might not be possible to circumvent the phase problem by ex-perimental measurement of the relative phases of diffracted X-ray beams.Such a measurement has now been reported,17 in which a highly perfectcrystal of germanium is used, but it is likely to remain merely an interestingdemonstration.Steady progress continues in the theory of structureanalysis; methods may still be roughly classified as “ Patterson function ”or “direct.” New methods for locating the replaceable atoms in a pairof isomorphous crystals have been described. l8 The number of structurallyidentical units within a cell may exceed the number of general positions.The angular relation between two such units unrelated by space-group sym-metry may in principle be found by a Patterson-function method. Applica-tions in protein crystallography are being made.lg The possibility ofimproving the resolution in electron-density maps of protein crystals bymaking use of phase relations between structure factors has been investi-gated.20 Vector sets, related to the Patterson function, may be generalisedt o give so-called image sets which are related to the result of convolutingG. W.Goetze and A. Taylor, Rev. Sci. Instr., 1962, 33, 353.H. G. Smith, Rev. Sci. Instr., 1962, 33, 128.8 Y. Z. Nozik and I. I. Yamzin, KristallograJiya, 1962, 7, 123.J. W. Knowles, Canad. J. Phys., 1962, 40, 257.lo A. S. Cooper, Acta Cryst., 1962, 15, 578:IIK. E, Beu, F. J. Musil, and D. R. Whitney, Acta Cryst., 1962, 15, 1292.12 W. L. Bond, Acta Cryst., 1960, 13, 814.13H. M. Otte, J. Appl. Phys., 1961, 32, 1536.l4 M. Roux and M. Cornille, Cahiers de Phys., 1962, 16, 45.I5 H. J. Milledge, Proc. Roy. SOC., 1962, A., 207, 566.V. G. Petrov, KristallograJya, 1962, 7, 163.l7 M.Hart and A. R. Lang, Phys. Rev. Letters, 1961, 7, 120. lev. R. Sarma and R. Srinivasan, Acta Cryst., 1962, 15, 457; S. Raman andW. N. Lipscomb, 2. Krist., 1961, 116, 314.19 M. G. Rossmann and D. M. Blow, Acta Cryst., 1962, 15, 24.2O W. Hoppe, Acta Cryst., 1962, 15, 13COCHRAN: GENERAL 503two different functions ; these sets may have crystallographic applications.21Possible improvements have been suggested22 in the use of Buerger’sminimum function. An investigation of the symmetries of vector super-position diagram8 has been made.23 Examples of structure determinationsmade by such methods are those for thiamine hydrochloride (vitamin B,)and for the synthetic peptide tosyl-~-prolyl-~-hydroxyproline.~~ Theauthors of the latter investigation have made an interesting comparisonof a number of related methods.26 A connexion between Patterson-functionand direct methods has been discussed by Hauptman and Karle.26 Theconversion of these authors to this point of view is welcomed! A generaltheory of ineq~alities,~’ based on earlier work by Karle and Hauptman,28has been worked out.Successful applications of direct methods have beenmade in determining the structures of deoxyanisoin, ( + )-S-methyl-L-cysteinesulphoxide, and rubrofusarin. 29 The last named (Cl5HI2O5) is probably thelargest molecule whose structure has been determined by the use of signrelations between structure factors. An interesting feature of the analysisis that an incorrect set of signs gave a plausible structure which could notbe refined despite the fact that atoms differed from their correct positionsby only 0.25A on average.30 It is becoming almost standard practice todetermine the absolute configuration of organic molecules containing bromineor iodine by making use of the phenomenon of anomalous dispersion.Recentexamples include the investigations of himbacine hydrobromide, N-methyl-gelsemicine hydriodide, and codeine hydr~bromide.~l Bijvoet 32 has in-vestigated the effect on the theory of the method of having in the unitcell several atoms which scatter anomalously.Some interesting developments have taken place in optical analoguemethods for structure determination. Harburn and Taylor 33 have shownhow three-dimensional Fourier transforms can be derived optically, anda similar experimental technique has been used to obtain non-centrosym-metric Fourier projections. The structure determination 34 of 9,lO-anthra-quinol dibenzoate provides a good example of the use of optical methods.Accurate Structure Anslysis.-A useful survey of the accuracy obtainablein intensity measurements, when a three-circle counter dsractometer is used,has been published.35 Sources of error in intensity measurements, to which21 M.J. Buerger, 2. Krist., 1961, 116, 430.22 S. Raman, Acta Cryst., 1962, 15, 283.23 E. Subramanian, 2. Krist., 1961, 116, 182.2 4 J. Kraut and H. J. Reed, Acta Cryst., 1962, 15, 747; J. Fridrichsons and A.25 J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962, 15, 1065.26 H.Hauptman and J. Karle, Acta Cryst., 1962, 15, 547.27 S. Naya, Acta Cryst., 1962, 15, 69.28 J. Karle and H. Hauptman, Acta Cryst., 1950, 3, 181.29 H. G. Norment and I. Karle, Acta Cryst., 1962, 15, 873; R. Hine, ibid., p. 635;30 G. H. Stout and L. H. Jensen, Acta Cryst., 1962, 15, 1060.31 J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962,15,119; M. Przybylska,32 J. M. Bijvoet, Acta Cryst., 1962, 15, 620.33 G. Harburn and C. A. Taylor, Proc. Roy. SOC., 1961, A, 264, 339; G. Harburn34 J. Iball and K. J. H. Mackay, Acta Cryst., 1962, 15, 148.35 L. E. Alexander and G. S. Smith, Acta Cryst., 1962, 15, 983.McL. Mathieson, ibid., p. 569.G. H. Stout and L. H. Jensen, ibid., p. 451.ibid., p. 301; G. Kartha, F. R. Ahmed, and W. H.Barnes, ibid., p. 326.and C. A. Taylor, Nature, 1962, 194, 764504 CRYSTALLOGRAPHYvery little attention has been paid, include simultaneous diffraction (Um-weganregung) and the contribution of thermally-scattered radiation closeto the Bragg peak. The possible importance of simultaneous diffraction isstrikingly demonstrated by recent measurements on germanium, and thefact that it is prone to occur when equi-inclination geometry is used hasbeen pointed 0 ~ t . ~ 6 A means of correcting for the effect of thermal scatter-ing has been worked and is claimed to be of general application.Accurate determinations of the electron distribution and of thermal para-meters in lithium hydride 3s and in a-quartz 39 have been reported. Organicmolecules for which structure determinations have been made with con-siderable accuracy (standard deviations of bond lengths about 0.005 8)include monofluoroacetamide and N-a~etylglycine.~~ Jensen 41 has re-examined the problem of systematic deviations in bond lengths, involvinghydrogen atoms, as determined by X-ray diffraction, and suggests thatsystematic errors are more likely to be in the refinement procedure thanin the experimental data.The electron distribution in diamond has beencalculated by the Thomas-Fermi method and by the method of ortho-gonalised plane waves.42 Both methods give results in fairly good agree-ment with X-ray mewurements. A theoretical estimate of the magnitudesof aspherical contributions to the atomic scattering factors of certain atoms,particularly in relation to the accuracy of experimental measurements andscaling procedures, has been made by D a ~ s o n .~ ~Thermal Effeds in Crystals.-Lonsdale 44 has given a survey of the topicsof atomic movements in crystals, phase changes, and solid-state reactions.Methods of measuring the Debye-O and results for cubic crystals have beenreviewed by Herbsteim4s The allegedly anisotropic temperature factors ofcertain cubic crystals have not been confirmed by a careful re-in~estigation.~~The influence of anharmonic effects on the temperature factor has beenworked out, and may be appreciable in certain circumstance^.^^ Such effectsare, however, unlikely ever to assume importance in structure analysis. TheDebye temperatures of germanium, as determined from X-ray or from spe-cific-heat data, differ by as much as 20%, but this is to be expected fromthe frequency distribution of the modes of thermal vibration.48 Measure-ments of the temperature factors of perfect crystals have given results which36 H.Cole, F. W. Chambers, and H. M. Dunn, Acta Cryst., 1962, 15, 138; H. L.37 S. Annaka, J . Phys. SOC. Japan, 1962, 17, 846.23 R. S. Calder, W. Cochran, D. GIifEths, and R. D. Lowde, J . Phys. und Chem.39 R. A. Young and B. Post, Acta Cryst., 1962, 15, 337.40 D. 0. Hughes and R. W. H. Small, Acta Cryst., 1962, 15, 933; J. Donohue andR. E. Marsh, ibid., p. 941.41 L. H. Jensen, Acta Cryst., 1962, 15, 433.4 2 H. C. Bolton and J. W. Heaton, Proc. Phys. SOC., 1961, A, 72,239; L.Kleinmanand J. C. Phillips, Phys. Rev., 1962, 125, 819.4 3 B. Dawson, Actu Cryst., 1961, 14, 1271.4 4 K. Lonsdale, Nature, 1962, 194, 5.4 5 F. H. Herbstein, Adv. Phys. (Phil. Mag. Supplement), 1961, 10, 313.4 6 R. W. Cahn and R. Feder, Acta Cryst., 1962, 15, 322.4 7 M. A. Krivoglaz and E. A. Tekhonova, Kristallografya, 1961, 6, 496.4 8 B. W. Batterman and D. R. Chipman, Phys. Rev., 1962, 127, 690.Yokel and I. Fankuchen, ibid., p. 1188.Solids, 1962, 23, 621COCHRAN: GENERAL 505are not entirely in accord with the theory.49 A one-dimensional modelfor the lattice vibrations of molecular crystals has been in~estigated.~~ Aneutron diffraction study of ferrous fluorosilicate hexahydrate has shownthat the thermal motion can be accurately described in terms of rigid-bodytranslations and librations.51 As already reported,S2 the coherent inelasticscattering of neutrons by a single crystal can be analysed to give informationabout lattice vibrations. The inelastic scattering of neutrons by hydrogenousmaterials is mainly incoherent, and neutron studies of powder specimens oforganic materials may yet develop into a new spectroscopic technique; anexample is provided by an investigation of hexamethylenetetramine. 63 Anumber of similar studies are described in a conference report.54S m e b and Geometrical Crystallography.-Papers dealing with thesetopics are not likely to attract more than passing attention from structuralcrystallographers. Quite often, however, the ideas reported in them even-tually turn out to have practical applications. For example, the questionof how simple mosaics representing plane groups can be fitted on to thesurfaces of polyhedra 55 may have importance for virus structures, since theprotein layer surrounding the ribonucleic acid centre is made up of identicalunits packed in a symmetrical way.The symmetry of irregular polyhedrain a non-lattice array has applications to the theory of liquid crystals.56Many papers in the Russian literature also deal with " black and white "and " colour " symmetry. The subject has been reviewed by Neronova andBe10v.~' I n a later paper the same authors discuss colour antisymmetrymosaics,58 and other papers in KristuZZograJiyu deal with allied topics suchas symmetry and antisymmetry groups of finite strips, infinite black andwhite ribbon groups,59 and the two-dimensional Shubnikov groups.6o Thesubject has not been neglected in the German literature.It has beenshown 61 how two-sided two-coloured band groups can be described byHermann-Manguin type symbols. The concept of point-group symmetryhas been generalised 62 by attributing a variable quality to the points ofa point group. The 32 crystallographic point groups thus give rise to 139cryptosymmetry or colour symmetry point groups for which symbols havebeen devised.*3 The problem of the general classification of groups involv-ing change of side, sign, or colour has been treated from a strictly geometrical4 9 B. W. Batterman, Phys. Rev., 1962, 126, 1461; 127, 686.5 0 E.Sandor, Acta Cryst., 1962, 15, 463.51 W. C. Hamilton, Acta Cryst., 1962, 15, 353.5 2 Ann. Reports, 1960, 57, 470.53 L. N. Becka, J . Chem. Phys., 1962, 37, 431.5 4 " Symposium on the inelastic scattering of neutrons in solids and liquids,"International Atomic Energy Agency, Vienna, 1963.6 5 G. S. Pawley, Acta Cryst., 1962, 15, 49.5 6 G. S. Pawley, 8. Krist., 1961, 116, 1.5 7 N. N. Neronova and N. F. Lelov, Kristallografiya, 1961, 6, 3 ; see also Ann.5 8 N. N. Neronova and N. V. Belov, Kristallqrafiya, 1961, 6, 831.6o A. M. Zamorzaev and A. F. Palistrant, Kristallografiya, 1961, 6, 163.61 A. Pabst, 2. Krist., 1962, 117, 128.6 2 A. Niggli and H. Wondratschek, 2. Krist., 1950, 114, 215; H. WondratschekReports, 1960, 57, 466.A.V. Shubnikov, Kristallografiya, 1962, 7 , 3, 186.and A. Niggli, ibid., 1961, 115, 1.63 0. Wittke, 8. Krist., 1962, 117, 153606 CRYSTALLOGRAPHYpoint of view.64 Finally, we may note that even the equivalent in recipro-cal (or Fourier) space of coloured or otherwise complex groups in crystalapace has been considered. 65 The combination of results of morphologicalmeasurements with knowledge of the space-group can give informationabout the arrangement of bonds in the structure, as has been shown by anexample.66 Kitaigorodski's work has been &ended 67 by the developmentof a graphical method of determining close-packed two-dimensional arraysof identical figures, with special reference to the structures of organic crystals.Loeb has published a further paper 68 on a modular algebra for the descriptionof the location and environment of crystal elements which is suitable forstorage in computers and may provide a useful system of classification.2.ORGANIC STRUCTURESw. c.Acyclic Compounds.-Molecules containing conjugated double- bondsystems may be non-planar as a result of steric hindrance. An electrondiffraction study has shown that, whereas methylglyoxal (Me-COCHO) isplanar, a-chloroacraldehyde [CH,:CCl*CHO] is n ~ n - p l a n a r . ~ ~ I n the latter,the rotation angle of the C=O and C=C bonds from the trans- and cis-con-figuratim is 57" and 41" for the two rotational isomers, which are in theratio 2 : 1.The chain configurations in poly( ethylene adipate) and poly( ethylenesuberate) are similar, and their packing and the angle B are determinedby interaction between the C=O dipoles and neighbouring chains.70In a new study of sodium bi~arbonate,'~ the C-0 distances are 1-346,1.264 and 1.263AY and the hydrogen bond between adjacent bicarbonateions is 2.595A.Each sodium is surrounded by six oxygen atoms a t anaverage distance of 2.438 Lf in a slightly distorted octahedral arrangement.All the atoms, apart from the hydrogens, in monofluoroacetamide(CH,F*CO*NH,) are closely planar. 72 Of the molecular dimensions, theC-C bond of 1.533 & 0.006 if is longer than expected for sp3 and sp2hybridised atoms, but L(0-CN) = 124", which is consistent with valuesin other amides of known structure. The two N-He-0 bonds [d(N-.O)= 2.955 and 2.878 Lf] are non-linear, with L(H-N-0) = 11" and 26".The fluorine atom does not participate in intermolecular hydrogen bondsbut may bond intramolecularly with the amide nitrogen or hydrogen atom.Average dimensions in the CC chain of NN'-hexamethylenebispropion-amide (Et*CO*NH-[CH,],-NH*CO*Et} 73 are d(C-C) = 1.529 -j= 0-002 A,L(C-C-C) = 112.8 0.7", and L(H-C-H) = 109 & 1".W.T. Holser, Acta Cryst., 1961, 14, 1236.66 A. Bienenstock and P. P. Ewald, Acta Cryst., 1962, 15, 1253.66 J. D. H. Donnay and G. Donnay, KristaUograJiya, 1961, 6, 840.67 A. I. Kitaigorodski, Kr&stallograJya, 1957, 2, 456; P. M. Zorkii and M. A. P o d -68 A. L. Loeb, Acta Cryet., 1962, 15, 219.6 0 P. A. Akishin, L. V. Vilkov, and N. I. Mochalova, Zhur.strztlct. Khim., 1961,7OA. Turner-Jones and C. W. Bunn, Acta Cryst., 1962, 15, 105.71 R. L. Sass and R. F. Scheuerman, Acta Cryst., 1962, 15, 77.72 D. 0. Hughes and R. W. H. Small, Acta Cryst., 1962, 15, 933.73 L. H. Jensen, Acta Cryst., 1962, 15, 433.Koshits, ibid., 1961, 6, 655.2, 545SUTOR: ORGANIC STRUCTURES 507The SC:(NH,), group in thiourea dioxide [(NHs;)zC:S0,],74 the low-temperature form of thiourea,75 studied by electron diffraction, and inS-methylisothiourea sulphate ([MeS:C(NH,),], + SO,,-} 76 is planar or verynearly so. Thiourea dioxide has a pyramidal arrangement of carbon andoxygen atoms about the sulphur atom, and the length of the C-S bond(1.85 -+ 0.02 8, cf. 1.79 and 1.74 both & 0.01 8 in S-methylisothioureasulphate) accounts for the ease with which it is broken.Each moleculeforms eight hydrogen bonds with neighbouring molecules. In thiourea,weak N-H--S hydrogen bonds have dimensions d(N-S) = 3-45, and3.38 8, and d(H-S) = 2-20 and 2.39 8. There is a preliminary report ofthe structure of the compound Me,N*SO,*NMe,. 5 7 Triethyl~carpane,~~formed by the addition of carbon disulphide to triethylphosphine, is a zwit-terion of a quaternary phosphonium derivative of dithioformate, Et,P +CS,-.The phosphorus atom forms four nearly tetrahedral bonds of average lengthd(P-C) = 1-80 A. Other dimensions are: d(C-S) = 1.69 & 0.03 8 andL(S-C-S) = 128 &- 2". In potassium 00-dimethyl phosphorodithioate 79[KS,P(OMe),], each potassium ion is surrounded by six sulphur and twooxygen atoms, forming a distorted tetragonal anti-pyramid.The P-0 dis-tance of 1-64 8 is comparable with the single-bond value in metaphosphates.Aromatic and Other Cyclic Molecules.-As in o-chlorobenzoic acid, molecu-lar overcrowding in o-bromobenzoic acid 80 is reduced by a twist (18O) ofthe carboxyl group out of the aromatic plane, and by a sideways and out-of-plane displacement of exocyclic carbon and bromine atoms away fromeach other. There are in-plane displacements of exocyclic C-C and (341bonds away from each other in 2-chloro-5-nitrobenzoic acid.*l Buttressingof the hydrogen atom at position-6 by the nitro-group (which is twistedonly 7" out of the aromatic plane) may cause a relayed steric effect resultingin the somewhat larger rotation (23") of the carboxyl group.Both acidsoccur in centrosymmetrical dimers linked by hydrogen bonds of length 2.64and 2.61 8, respectively. In the potassium salt of o-nitrophenol hemi-hydrate,82 the anion is planar with a short non-bonded intramolecular dis-tance of 2.64A between the nitro- and phenol groups. Each potassiumion is co-ordinated by seven oxygen atoms at distances of 2.69-2.94 8, butthe system has no apparent symmetry. In the structure of m-bromonitro-benzene,s3 each bromine atom forms two charge-transfer bonds, withd ( B r 4 ) = 3-38 8. The chain of nitrogen atoms in the p-dibromo-derivative of diazoaminobenzene (BrC,H,*N:N*NH *C,H,Br) is non-hear . *The apparent equality of the two N-H bonds (1.23 and 1.25 8) may resultfrom a true or statistical transfer of the hydrogen atom.Molecules are7 4 R. A. L. Sullivan and A. Hargreaves, Acta Cryst., 1962, 15, 675.76 V. F. Dvoryankin and B. K. Vainshtein, Kristallografiya, 1961, 6, 949.76 C. H. Stam, Acta Cryst., 1962, 15, 317.7 7 T. Jordan, W. Smith, and W. N. Lipscomb, Tetrahedron Letters, 1962, 37.78 T. N. Margulis and D. H. Templeton, J. Chem. Phys., 1962, 36, 2311.7 0 Ph. Coppens, C. H. MacGillavry, S. G. Hovenkamp, and H. Douwes, Acta Cryst.,81 G. Ferguson and G. A. Sim, J . , 1962, 1767.8a J. P. G. Richards, 2. KriSt., 1961, 116, 468.84 Yu. D. Kondrashev, Kristallograjiya, 1961, 6, 515.1962, 15, 765.G. Ferguson and G. A. Sim, Acta C y s t . , 1962, 15, 346.T. L. Charlton and J. Trotter, Proc. Chem.Soc., 1962, 221508 CRYSTALLOGRAPHYlinked in infinite spirals by hydrogen bonds between nitrogen atome. Ortho-rhombic aniline hydrobromide 85 crystallises in a distorted cesium chloride-type structure consisting of bromine and anilinium ions. I n di-(p-chloro-pheny1)amine 86 the valency angle of the nitrogen atom is 134". Moleculesof tetrachloroquinol are almost planar, and ring dimensions are inter-mediate between those for a benzenoid and a quinonoid structure. Theposition of the hydrogen atom suggests that the two intermolecular dis-tances [d(O.-O) = 2-92, d(O-C1) = 3.29 81 constitute a bifurcated hydrogen-bond system. A three-dimensional analysis of chloranil (tetrachloro-p-benzoquinone), the molecules of which adopt the quinonoid form and arevery nearly planar, has been published.88The structure of bis-m-bromobenzoylmethane 89 (1) has been accuratelydetermined by using three-dimensional scintillation-counter data.Symmetryrequires equivalence of the two C-0 groups [d(C-0) = 1.306 & 0-015 81and the intervening C-C bonds [d(C-C) = 1.393 0.015 81 of the enol formin which these /I-diketones primarily exist, and thermal parameters supportBr Br0 C O * c H 2 * C O 0 M e 0 0 C H 2 * C O a O M e('1 (2)the interpretation that this equivalence is real rather than statistical. Themolecule has a short intramolecular hydrogen-bond distance, withd(0-0) = 2.464 Strong repulsion between the oxygen atoms,possible if the hydrogen bond is bent, may result in displacement of theseatoms from the molecular plane and account for the high thermal parametersnormal to the ring.The determination of the structure of deoxyanisoin (2),and a refinement of that of 4,4'-dimethoxybenzophenone, show that mole-cular dimensions are closely similar.90 In the former, carbonyl and methoxy-groups are coplanar with adjacent benzene rings, and planes through therings are inclined a t 62" to each other. I n the latter, methoxy-groups arealso coplanar with adjacent benzene rings. The carbonyl group is notcentrally located between the planes of the adjacent benzene rings whichare inclined a t about 55".I n chloro- and bromo-diphenylar~ine,~~ rotation of both phenyl ringsfrom their ideal positions is such that only one ring can interact with thearsenic lone-pair.Pentaphenylantimony 92 has a square-pyramidal struc-ture with the antimony atom lying in the pyramid about 0.5 A above thebase, and a two-fold axis coinciding with the axial Sb-Ph bond.The oxygen atoms deviate from the plane of the anthracene ring in9,lO-anthraquinol dibenz0ate.3~ The planes of the benzoate groups are0.015 8.s 5 I. Nitta, T. WatanabB, and I. Taguchi, J . Chem. SOC. Japun, 1961, 34, 1405.86 K. Plieth and G. Ruban, 2. Krist., 1961, 116, 161.87 T. Sakurai, Acta Cryst., 1962, 15, 443.88 S. S. C. Chu, G. A. Jeffrey, and T. Sakurai, Acta Cryst., 1962, 15, 661.a0 D. E. Williams, 147. L. Dumke, and R. E. Rundle, Actu Cryst., 1962, 15, 627.S O H . G. Norment and I. L. Karle, Acta Cryst., 1962, 15, 873.0 1 J. Trotter, Can&.J . Chern., 1962, 40, 1590; J . , 1962, 2567.J. Wheatley and G. Wittig, Proc. Chem. SOC., 1962, 251SUTOR: ORGANIC STRUCTURES 509inclined to this plane at 110". In 1,5-dichloro- and 1,5-dibromo-anthra-quinone,93 the anthraquinone nucleus has a " chair "-like shape. Only thetwo aromatic rings and the atoms attached directly to them are coplanarin rubrofusarin (3).94 There is a preliminary report of the structure of~elebixanthone,~~ and a two-dimensional refinement of that of biphenylene, 96The aromatic rings in 1,2-~yclopentenophenanthrene (4) are slightly twisted,(5). H2cocH2F F . .I IPh-C-C -C-C- PhI1 I I I1Ph-C-f:-$-C-PhI ,Ph Ph (6)and the five-membered ring is non-planar, the two atoms attached to thearomatic nucleus lying below the mean plane and the third lying above.97Molecular strain in 4,12-dimethyl-(2,2)metacyclophane (5) is relieved bya lengthening of the CH2-CH, bonds [d(C-C) = 1.573 & 0.003 A] and bya step-wise displacement of the two benzene rings and their distortion toa " boat ''-shape.9* Rotation of the methyl groups which appear stationarymay be strongly hindered.In the dimer of fluorotriphenylcyclobutadiene (6),the angles between the plane of the cyclobutane ring and the planes of thecyclobutene rings are about 112 & 2", with a trans-configuration about thecyclobutane ring.99 The fluorine atoms are also trans with regard to thesame ring.Full details of the structure of azulene are now available,loO and a three-dimensional refinement of that of 2,3-dihydro-2,3-methylene- 1,4-naphtha-quinone has produced changes in molecular dimensions.lol There is apreliminary report of the work on cyclotetradecaheptaene which is shownto correspond to a distorted pyrene structure.lO2Heterocyclic Compounds.-Three-dimensional refinements of the struc-tures of furan-, thiophen-, and selenophen-2-carboxylic acid (7), and a low-temperature study of the thiophen acid, are reported.103 The increase in93 L. A.Chetkina, G. A. Gol'der, and G. S. Khdanov, Kristallografiya, 1961, 6, 628.94 G. H. Stout and L. H. Jensen, Acta Cryst., 1962, 15, 451.9 5 G. H. Stout, V. F. Stout, M. J. Welsh, and L. H. Jensen, Tetrahedron Letters,96 T. C. W. Mak and J. Trotter, J., 1962, 1.9 7 R. F. Entwistle and J.Iball, 2. Krist., 1961, 116, 251.9 8 A. W. Hanson, Acta Cryst., 1962, 15, 956.D9 C. Fritchie and E. W. Hughes, J. Amer. Chem. SOC., 1962, 84, 2257.1962, 541.loo J. M. Robertson, H. M. M. Shearer, G. A. Sim, and D. G. Watson, Acta Cryst.,lol W. K. Grant and J. C. Speakman, Acta Cryst., 1962, 15, 292.loa J. Bregman, Nature, 1962, 194, 679.lo3 P. Hudson, Acta cry&., 1962, 15, 919; M. Nardelli, G. Fava, and G. Giraldi,1962, 15, 1.ibid., p. 737; P. Hudson and J. H. Robertson, ibid., p. 913510 CRYSTALLOGRAPHYsize of the heavy atom causes larger displacements from the molecular plane(0, 0.03, 0.06A for 0, S, and Se) and a decrease in the angle centred onthis atom (log", 92", and 87"), but apparently does not modify the ringC-C distances.In 2-furoic acid, the carboxyl OH group is trans with respect(8) CH2.CH2Meto the hetero-atom, as compared with the &-arrangement in the other two,but reversal of the relative sizes of angles C-C-0 probably still permitssome attraction between the carboxyl group and ring oxygen atom. Theexocyclic C-C bond of 1.41 A in 2-furoic acid is remarkably short ; correspond-ing values for the sulphur and selenium compounds are 1-48 and 1-44A.According to an accurate structure analysis, molecules of maleic anhydride l o 4are non-planar, the ring hetero-atom lying 0.03 A from the molecular plane.Exocyclic C-C bonds average 1.21 8 (corrected for thermal motion); otheraverage distances, d(C=C) = 1.303 and d(C-0) = 1.388, both & 0.005 8,are shorter than the double-bond and the single-bond value respectively.In N-p-bromophenylsuccinimide 105 and N-methylpyrrole, the nitrogenatom forms three coplanar bonds.The five-membered ring of pyrazolinehydrochloride lo7 lies in a mirror plane with d(C=N) = 1.255 & 0*009,d(N-N) = 1.468 & 0.007, d(C-N) = 1.498 &- 0.008, and d(C-C) = 1.473,1.472 (both 0.010 A), and molecules are linked by hydrogen bonds withd(N-H.41) = 3-092 & 0.005 8. Similar bonds occur in pyridine hydro-chloride lo* [d(N-H-Cl) = 2.95 81 and in the substituted triazolopyri-midine lo9 (8) where d(N-H.-Cl) = 3.18 and 3-30 A. The latter moleculeis planar and has two structural features reminiscent of purines, namelyshort C-C and C-N bonds in the pyrimidine ring, and molecular dimensionsinexplicable in terms of simple resonance theory.In 5-carboxymethyl-cytosine (9), exocyclic atoms deviate significantly from the plane of thepyrimidine ring.110 A feature of the crystal structure is a transfer of theAH02C. [CHJ 3-N-N.[CH2] COzHcarboxyl proton to a pyrimidine nitrogen atom in half the molecules (whichtherefore correspond to zwitterions). As a result, a proton is shared bya pair of nitrogen atoms related by a centre of symmetry, and anotherproton is similarly shared by a pair of oxygen atoms. The hydrogen bondsI04 R. E. Marsh, E. Ubell, and H. E. Wilcox, Acta Cryst., 1962, 15, 35.Io6 J. Barassin, G. Tsoucarb, and H. Lumbroso, Compt. rend., 1961, 253, 2546.lo6 L. V. Vilkov, P. A. Akishin, and V. M. Presnyakovs, Zhur.Ptrukt. Khim., 1962,3, 5.M. Nardelli and G. Fava, Acta Cryst., 1962, 15, 214.C. RBrat, Acta Cryst., 1962, 15, 427.lo9 P. G. Owston and J. M. Rowe, Ada Cryst., 1962, 15, 231.I1o R. E. Marsh, R. Bierstedt, and E. L. Eichhorn, Acta Cryst., 1962, 15, 310SUTOR: ORGANIC STRUCTURES 511formed are only statistically symmetrical since the protons appear ran-domly distributed between sites closer to one or other atom in each pair.Unusual hydrogen bonding in piperazine-l,4-dibutyric acid (10) linkshydroxyl oxygen atoms to ring nitrogen atoms of adjacent molecules withd(0-H-N) = 2.60 & 0.01 (cf. that in meso-l,4-diaziridin-l'-ylbutane-2,3-diol l12). There is a preliminary report of the structure of isoquinolinechlorohydrate,113 and two independent investigations show that benzo-furoxan 114 has the benzofurazan 1 -oxide structure (1 1 ).In 9,10-dihydro-9-hydroxy-9 -phosphaphenanthrene 9-oxide ( 12) ,115 thetwo benzene rings are not conjugated [d(C-C) = 1.57 0.05 a].The twoOHP-C bonds are 1.79 and 1-80 8. C-S bondsin2-methylthiobenzothiazole (13)are 1.73, 1.77, 1.78, and 14328, the last corresponding to the S-Me dis-tance.116 In merocyanine (14), the two cyclic sulphur atoms are in thetrans-position.117 The rhodanine ring is planar but the two methylenecarbon atoms deviate from the plane of the other ring.Methyl metadithiophosphonate (15) is a dimer of crystallographic sym-metry 2/m.llS The P-S distances, 2-14&0-02 for a cyclic and 1.94&0.02 8for an exocyclic bond, correspond to the single and the double bond valuerespectively. In tetramethyl-NN'-bistrimethylsilylcyclodisilazane,119 thereis no significant difference between cyclic and exocyclic Si-N bonds, whichaverage 1.719 8.A puckered eight-membered ring of alternate phosphorusand nitrogen atoms occurs in tetrameric phosphonitrilic dimethylamide 120and metastable phosphonitrilic chloride;121 d(P-N) = 1-58 and 1.57 Arespectively. In the former compound exocyclic P-N bonds of 1.67 and1.69 A are considerably shorter than the single bond value.Addition Compounds.-In the 1 : 3 addition compounds formed by iodo-ll1 R. Potter, Nature, 1962, 193, 673.112 Ann. Reports, 1961, 58, 475.11* D. Britton and W. E. Noland, Chem. and Ind., 1962, 563; R. Hulme, ibid., p.42.l15P. J. Wheatley, J . , 1962, 3733.11* P. J. Wheatley, J., 1962, 3636.11' G. Germah., P . Piret, M. van Meerssche, and J. de Kerf, Acta Cryst., 1962, 15,11* P. J. Wheatley, J., 1962, 300.l l * P . J. Wheatley, J., 1962, 1721.l * O G. J. Bullen, J., 1962, 3193.121 R. Hazekamp, T. Migchelsen, and A. Vos, Acta Cryst., 1962, 15, 539.F. Genet, Compt. rend., 1962, 254, 2389.373512 CRYSTALLOGRAPHYform with sulphur 122 (CH13,3S,) and with quinoline 123 each iodine atomis linked to a sulphur atom and to a quinoline nitrogen atom by charge-transfer bonds of length 3-50 and 3.05 & 0.03 8, respectively. The valuesof ,/(C-I-X), 178" and 177", where X = S and N, indicate a linear arrange-ment of these atoms. The sulphur and selenium atoms in the iodine complexof 1,4-selenothian (C4H,SSe,21,) are disordered, 124 each site being filled by3Se + is.As the iodine atoms in the iodine complexes of 1,4-dithian andlY4-diselenan are bonded to the sulphur and to the selenium atoms of thesix-membered ring in the equatorial and axial positions, respectively, thereare several possibilities for the present compound. The arrangement adoptedis the equatorial one.A refinement of the chloranil-hexamethylbenzene complex 125 indicatesa coplanar structure for the two molecules, instead of the puckering andnon-planarity observed previously but thought not to be significant.The complex of cupric chloride and 1,2,4-triazole 126 consists of a dis-torted octahedral co-ordination group of two nitrogen atoms a t 1.98 8, twochlorine atoms at 2.34 8, and two chlorine atoms at 2.77 8 about eachcopper atom.The infinite chains of octahedral groups joined by sharingedges are linked by triazole molecules.Natural Products and Related Compounds.-Again this year, this sectioncontains a high proportion of the organic molecules studied. A refinementof the structure of codeine hydrobromide dihydrate, using three-dimensionaldata, and the absolute configuration of the molecule are re~0rted.l~' Com-plete structure analyses of ( - )-N-methylgelsemicine hydriodide 128 andcalycanthine 129 are now available. I n the latter paper, an intermoleculardistance with d(C-0) = 3-18 8 is compared with similar values in otheralkaloids. X-Ray work on chimonanthine,130 an isomer of calycanthine,has shown which of two chemically feasible structures is correct.Likecalycanthine, the molecule adopts the cis-configuration (16). In casimiro-edine 131 (17) the nitrogen atom attached equatorially to the ,&glucose ringMe H122 T. Bjorvatten, Acta Chem. Scand., 1962, 16, 749.lZ3 T. Bjorvatten and 0. Hassel, Acta Chem.. Scand., 1962, 16, 249.124 H. Hope and J. D. McCullough, Acta Cryst., 1962, 15, 806.125 N. D. Jones and R. E. Marsh, Actu Cryst., 1962, 15, 809.126 J. A. J. Jarvis, Acta Cryst., 1962, 15, 964.127 G. Kartha, F. R. Ahmed, and W. H. Barnes, Acta Cryst., 1962, 15, 326.li8 M. Przybylska, Acta Cryst., 1962, 15, 301.lZQ T. A. Hamor and J. M. Robertson, J., 1962, 194.130 I. J. Grant, T. A. Hamor, J.M. Robertson, and G. A. Sim, Proc. Chem. SOC.,13l S . Raman, J. Reddy, W. N. Lipscomb, A. L. Kapoor, and C. Djerassi, Tetrahedron1962, 148.Letters, 1962, 357SUTOR: ORGANIC STRUCTURES 513forms three coplanar bonds and in the dichloride studied is not protonated.The CH,*CH,*NHMe chain is somewhat extended.There are preliminary reports of work on isophotosantonic lactone, 132hunterburnine,l33 hetisine hydrobromide, and gedunin. 135 The positionsof the substituents in hetisine hydrobromide differ from those suggestedfrom chemical evidence. The structure deduced for gedunin by analogywith limonin and the structures of al-bromopicrotoxinin 136 and bromo-geigerin acetate 137 are confirmed. Samandarine,138 one of the salamanderalkaloids, the only genuine alkaloids so far known in animals, has a sterolskeleton like that of EiB-androstane, with the same cis-trans-trans-junctionbetween the four rings.From the empirical formula, the structure of himbacine hydrobromidea t -150" has been defermi11ed.1~9 The planarity of the lactone group andthe shortening of the C-0 bond adjacent to the keto-group, observed inM ethe dibromolactone from jacobine,lgO have been demonstrated in this com-pound and in shellolic bromolactone hydrate lgl (lactone plane not calcu-lated), and in iridomyrmecin (18) and its epimer isoiridomyrmecin ( 19).142The difference in biological activity of the last two may be related to theirdifferent stereochemistry.I n iridomyrmecin, the cyclopentanoid ring isendo, in the epimer it is exo to the six-membered ring.A preliminary report of a-D-glucose monohydrate lg3 has shown that thepyranose ring is " chair "-shaped with molecular dimensions fairly similarto those in a-D-glucose.In the crystal, there is a very short intermoleculardistance, with d(C-0) = 2.61 8. The pyranose ring in methyl-3,4,6-tri-O-acetyl-2 - chloromercuri-2 -deoxy-b-~ -glucopyranoside 44 is also " chair "-shaped with substituents attached equatorially.In an accurate three-dimensional analysis of E-lysine monohydro-chloride dihydrate,145 the following average distances have been found :d(C-NH3+) = 1.482 & 0.004, d(C-C) = 1.524 & 0.003 A, L(C-C-C) = 111.7"132 J. D. M. Asher and G. A. Sim, Proc. Chern. SOC., 1962, 111.133 J.D. M. Asher, J. M. Robertson, G. A. Sim, M. F. Bartlett, R. Sklar, and134 M. Przybylska, Canad. J . Chem., 1962, 40, 566.135 S. A. Sutherland, G. A. Sim, and J. M. Robertson, Proc. Chsm. $oc., 1962, 222.136 B. M. Craven, Acta Cryst., 1962, 15, 387.13' J. A. Hamilton, A. T. McPhail, and G. A. Sim, J., 1962, 708.G. Weitz and E. Wolfel, Acta Cryst., 1962, 15, 484.139 J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962, 15, 119.140 Ann. Reports, 1961, 58, 478.141 E. J. Gabe, Acta Cryst., 1962, 15, 759.142 J. F. McConnell, A. McL. Mathieson, and B. P. Schoeborn, Tetrahedron Letters,14s R. C . G. Killean, W. G. Ferrier, and D. W. Young, Acta Cryrt., 1962, 15, 911.144 H. W. W. Ehrlich, J., 1962, 509.145 D. A. Wright and R. E. Marsh, Acta Cryst., 1962, 15, 54.W.I. Taylor, Proc. Chem. SOC., 1962, 72.1962, 445; B. P. Schoeborn and J. F. McConnell, Acta Cryst., 1962, 15, 779.514 CRYSTALLOGRAPHY(cf. those in NN'-hexamethylenebispropionamide p. 506). All hydrogenatoms belonging to nitrogen atoms and water molecules participate inhydrogen bonds and one proton a.ttached to a nitrogen atom forms a bifur-cated bond. N-acetylglycine 146 has also been refined in three dimensions,and bond lengths and angles are very similar to those reported earlier.The determination of the absolute configuration a t the asymmetric sulphuratom in ( +)-8-methyl-L-cysteine sulphoxide may represent the first of itskind.147 The crystal structure consists of pairs of sheets of molecules heldtogether by hydrogen bonds between the nitrogen atom of one moleculeand surrounding oxygen atoms of different molecules. Di( histidino)zinc(n)pentahydrate 148 and di-(L-histidino)zinc(II) dihydrate 149 consist of zincatoms approximately tetrahedrally co-ordinated by two or-amino- and bytwo imidazole-nitrogen atoms. Two carbonyl oxygens can also be con-sidered loosely co-ordinated. A small twist of the peptide group betweenthe prolyl and hydroxyproline groups, and a flexibility in the proline ringobserved in the synthetic peptide t oluene-p - sulphonyl-L-prolyl-L- hydroxy-proline m ~ n o h y d r a t e , ~ ~ ~ may be of importance in the construction of mole-cular models of peptides and proteins.I n vitamin B, (thiamine hydrochloride) (20) 151 the planes of the thia-zolium and pyrimidine rings make a dihedral angle of 76" and are twistedso that the amino-group in the latter ring and the CH-group in the formerring are close. Parts 111, IV, and V of the structure of vitamin B,, describethe work in Oxford and Princeton on the vitamin.152 Parameters for ninety-three atoms of the molecule, fifteen water molecules, and seven less welldefined water molecules are given. The latest difference maps have smallmaxima which confirm the identification of the various single-atom sub-stituents in the nucleus as methyl groups.D. J. S.W. COCHRAN.D. J. SITTOR.146 J. Donohue and R. E. Marsh, Acta Cryst., 1962, 15, 941.1 4 ' R. Hine, Acta Cryst., 1962, 15, 635.14* M. M. Harding and S. J. Cole, Proc. Chern. SOC., 1962, 178.149 R. H. Kretsinger, R. F. Bryan, and F. A. Cotton, Proc. Chem. Soc., 1962, 177.lSo J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962, 15, 569.15l J. Kraut and H. J. Reed, Acta Cryst., 1962, 15, 747.152 J. G. White, Proc. Roy. SOC., 1962, A , 266, 440; D. C. Hodgkin, J. Lindsey,M. Mackay, and K. N. Trueblood, ibid., p. 475; D. C. Hodgkin, J. Lindsey, R. A.Sparks, K. N. Trueblood, and J. G. White, ibid., p. 494

ISSN:0365-6217    

DOI:10.1039/AR9625900501

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

INDEXAb, G., 455.Abel, E. W., 142, 145.Abeles, R. H., 403, 408,Abell, P. L., 49.Abraham, D. J., 322.Abraham, M. H., 143.Abraham, R. J., 201, 202,Abrahamson, E. W., 452.Abrahamsson, S., 276, 284.Abramovitch, R. A., 336.Abrams, R., 374.Abramsky, T., 393, 403.Acheson, R. M., 319, 324,Ackerman, M., 119, 120.Acquista, A., 121.Aczel, T., 199, 497, 498.Adam, G., 356.Adams, D. M., 173.Adams, F., 490.Adams, G. A., 370.Adams, J. Q., 49.Adams, K. A. H., 336.Adams, R. N., 48, 52, 482.Adams, R. W., 60.Adams, W. S., 445.Adamson, A. W., 171.Addison, C. C., 178.Adema, E. H., 47.Adityachaudury, N., 347,Adrian, F. J., 48, 57, 58,Ae Im, Y., 175.Affrossman, S., 254.Affsprung, H. E., 95.Agar, J., 382.Agarwala, V. S., 461.Agirbiceanu, I., 120.Agosta, W.C., 272.Ahearn, A. J., 120.Ahmad, M., 357.Ahmed, F. R., 512, 533.Ahuja, H. S., 145.Aia, M. A., 500.Aikens, D. A., 455.Aizenshtat, E. L., 361.Akerlind, L., 106, 127.Akhren, A. A., 197.Akhtar, M., 305, 483.Akishin, P. A., 506, 510.Akiyama, S., 269.Akiyoshi, S., 299.Ahbran, D. M., 258.Alberty, R. A., 244.Alcock, N. W., 151.Alder, B., 65.409, 420.364.325, 338.352.205.OF AUTHORS’ NAMESAlder, B. J., 97.Alderman, P. R. H., 178.Aldrich, R. A., 393.Alekseeva, D. P., 165.Alexander, C. A., 153.Alexander, G. V., 478.Alexander, L. E., 503.Alfonsi, B., 481.Alfredsson, B., 448.Alicino, J., 332.Alimarin, I. P., 450.Alivastatos, S. G. A., 416.Alivisatos, S. G. A., 417.Allan, J.E., 479.Allardt, H. D., 161.Allegra, G., 151.Allen, A. D., 164.Allen, E., 159.Allen, E. R., 37.Allen, F. W., 376.Allen, G., 225.Allen, J. C., 226, 265.Allen, S. H., 403, 405.Allen, W. F., 283.Allendorf, H. D., 37.Alleston, D. L., 143.Alley, S. K., 84.Allfrey, V. G., 380.Allinger, A. L., 196.Allinger, N., 317.Allinger, N. L., 198, 286.Allison, M. J., 274.Allner, K., 328.Allred, A. L., 66.Al-Madhi, A. A. K., 493.Almenningen, A., 190.Alonso, C., 434.Alpert, D., 8, 9.Alsop, D. J., 310.Altaner, C., 447.Altman, K. T., 398.Altshuller, A. P., 449, 465.Amai, R. L. S., 353.Amaya, K., 95, 96.Amberger, E., 145, 147.Amdur, I., 88, 89.Amelunxen, R., 425.Amiel, Y., 198, 307, 316.Amin, El. S., 365.Amma, E.L., 166, 169.Ammann, R., 463.Amschler, H., 314.Amster, R. L., 137.Ananchenko, S. N., 306.Anand, V. D., 460.Anantaraman, A. V., 96.Andersen, B., 359.Andersen, J. R., 202.Anderson, A. G., 414.515Anderson, B., 417.Anderson, B. C., 281.Anderson, B. M., 247, 416.Anderson, C. D., 135, 375.Anderson, D. L., 84.Anderson, D. M. W., 370,Anderson, D. R., 237.Anderson, J. C., 253.Anderson, J. D., 361.Anderson, J. H., 54.Andersen, J. R., 327.Anderson, L., 361.Anderson, M. M., 66.Anderson, N. G., 445.Anderson, P. S., 335.Anderson, R., 76, 83, 84.Anderson, R. S., 53, 109,Anderson, S., 170.Andersson, L. H., 448.Andreades, S., 280.Andreev, N. S., 190.Andreoli, M., 494.Andresen, H. G., 46.Andrew, T. R., 479.Andrews, H., 337.Andrews, L.J., 82, 217,220, 226, 233.Andrews, P., 361.Andrianov, K. A., 141.Anet, E. F. L. J., 327, 363.Anet, F. A. L., 192, 286,Anet, R., 282.Angelici, R. J., 177.Anger, V., 442.Angers, M., 434.Angier, R. B., 283.Angus, W. R., 125.Angyal, S. J., 362, 363, 365.Anisonyan, A. A., 27.Anliker, R., 428, 429.Annaka, S., 504.Annan, W. D., 370.Anner, G., 305.Anneser, E., 332.Anselme, J.-P., 330.Anson, F. C., 472.Antipova-Karataeva, I. I.,Antkowiak, W., 296.Antonaccio, L. D., 204, 352,Antonakis, K., 362.Antonescu, R., 314.Antoniades, H. N., 427.Apirina, R. M., 451.Aposhian, H. V., 374.Appel, H. H., 344.205.357.154.35351 6 INDEX OF AUTHORS' NAMESAppel, R., 145, 148, 241,Appella, E., 419.Aprahamian, N.S., 232.ApSimon, J., 358.ApSimon, J. W., 243, 296.Arai, S., 51.Arakawa, H., 291.Arapovid, I., 478.Archer, A. P. G., 353.Archer, D. A., 338.Arden, J. W., 495.Ardon, M., 158, 178.Arellano, R., 336.Arens, J. F., 270.Argoudelis, A. D., 341.Arigoni, D., 299, 305.Ariyoshi, U., 368.Arm, H., 95.Armand, J., 486.Arnason, B., 260.Arnaud, P., 276.Arndt, C., 271.Arnett, E. M., 308.Arnold, N., 319.Arnstein, H. R. V., 376,Arojan, A., 344.Aroney, M., 192.Aroney, M. J., 190, 191.Arotsky, J., 150, 151.Arsonault, G. P., 391.Arthur, J. C., jun., 369.Arthur, J. R., 12.Arya, V. P., 295, 297.Asaba, T., 20.Asatiani, Ya. V., 131.Ascherl, A., 332.Ashby, E. C., 133, 137,256.Asher, J. D. M., 291, 294,Ashmore, P.G., 24.Ashworth, A. J., 91.Asinger, F., 320.Aslanov, G. A., 453.Asperger, S., 223.Aspinall, G. O., 370.Asprey, L. B., 154.Asthana, 0. P., 460.Astle, M. J., 319.Astraclian, L., 379.Asundi, R. K., 128.Aszalos, A., 364.Athavale, V. T., 444, 478.Atherton, N. M., 51, 59.Atkim, P. W., 54, 55, 56.Atkinson, M. R., 417.Atsuyoshi, O., 230.Aubrey, D. W., 133, 136.Augl, J. M., 176.August, J. T., 431.Aurell, B., 447,Avidor, Y., 418.Avram, M., 309.Avramerko, L. I., 21, 42,258, 280, 323.381, 406.351, 513.43, 44.Axelrod, B., 331, 358.Axelrod, L. R., 430.Axford, D. W. E., 27.Ayer, W. A., 337, 357.Ayers, W. A., 406.Aylward, F., 257.Aylward, G. H., 488.Ayres, G. H., 479, 482.Ayrey, G., 224.Ayscough, P.B., 53.Azarnooth, A., 98.Azatyan, V. V., 25.Azim, S., 482.Azizov, U., 369.Azizyan, T. A., 230.Bazcrchers, W. H., 297.Babaeva, A. V., 165.Babel, D., 164.Babko, A. K., 437.Bacharach, A. L., 427.Bachman, G. L., 241.Baciocehi, E., 231.Backeberg, 0. G., 262.Bacon, R. G. R., 234, 258.Baddeley, G., 217, 246.Badding, V. G., 256.Badger, G. M., 308.Baeckmann, A. V., 444.Baer, H. H., 366.Bafus, D. A., 130, 206.Bag, S. P., 451.Bagdasarian, M., 388.Bagnall, K. W., 153.Baikov, V. I., 128.Bailar, 5. C., jun., 165, 171.Bailey, A. J., 361.Bailey, N., 47.Bailey, R. A., 489.Bailey, R. W., 367.Bailey, S. W., 447.Bailey, W. J., 273, 285, 307.Bain, P. J., 235.Bains, M. S., 156.Baird, J. C., 53, 54.Baird, R., 219.Baird, S.L., 62.Baiulescu, G., 450.Bak, B. 195 199 202, 327,Baker, A. E., 157.Baker, A. J., 295.Baker, B. R., 365, 366, 375,Baker, C. H., 99.Baker, E. B., 132.Baker, F. W., 232.Baker, J. A., 336.Baker, R., 232.Baker, R. H., jun., 418,421.Baker, W., 309.Baker, W. A., 154.Balaban, A. T., 307, 314.Balandina, M. A., 459.Balhzs, L., 473.Baldeschwieler, J. B., 144.329.424.Baldinus, J. G., 470.Baldwin, J. E., 286.Baldwin, M. E., 194.Baldwin, R. R., 22, 23, 24,Ball, D. F., 478.Ball, D. H., 365.Ball, J. J., 121.Ballard, R. E., 169.Balthausen, C. J., 45, 46,Baltazzi, E., 324, 389.Baltchefsky, H., 418.Bamford, C., 246.Bamford, C. H., 49.Ban, Y., 348, 350.Bandi, L., 431.Banick, W. M., jun., 457.Banister, A.J., 148.Banks, B. E. C., 244, 246.Banks, C. V., 170, 485.Banthorpe, D. V., 238.Barabanova, A. S., 157.Baranova, L. I., 165.Barassin, J., 510.Barber, M., 32.Barbier, M., 278.Barbieri, P., 412.Barchielli, R., 411.Barclay, G. A., 163.Barclay, L. R. C., 253.Bard, A. J., 462, 463, 464,Bardenstein, S. B., 480.Bardsley, W. G., 349.Barendrecht, E., 462, 463.Barford, R. A., 275.Barger, R. L., 102.Barker, H. A., 400, 401,402, 403, 413.Barker, J. A., 89, 95.Barker, R., 362.Barker, S. A., 277, 361, 364,Barltrop, J. A., 294, 299,Barnard, J. A., 37.Barner, R., 237.Barnes, C. S., 200, 292.Barnes, W. H., 503, 512.Barnett, B. H., 410.Barnett, L., 380.Barney, J. E., 467.Barnum, D. W., 169.Barr, J. K., 448.Barrall, E.M., 11, 499.Barrens, J., 194.Barreto, R. C. R., 479.Barrett, J., 396.Barrett, J. M., 411.Barron, D. N., 420.Barrow, R. F., 101, 102,106, 107, 119, 121, 124,126, 127, 128.Barry, G. W., 233.BBrta, R., 499.25.128, 157.472, 484.368.302INDEX O F AUTHORS’ NAMES 517Bartelink, H. J. M., 47.Bartell, L. S., 189.Bartels, H., 150.Barth-Wehrenalp, G., 170.Bartkus, E. A., 310, 331.Bartky, I. R., 128.Bartlett, M. F., 351, 353,Bartlett, N., 130, 161, 165.Bartlett, R. K., 134.Bartley, W. J., 312.Bartnik-Kurzawinska, J.,Bartocha, B., 137.Barton, D. H. R., 243, 260,263, 267, 286, 293, 294,296, 300, 305, 306, 343.513.465.Barton, J. W., 309, 338.Bartos, J., 442.Bartosinski, B., 412, 413.Bartz, K.W., 497.Bartz, Q. R., 365.Barua, A. K., 301.Bashilova, N. I., 450.Basilio, C., 381.Basolo, F., 163, 175, 177.Bass, A. M., 102, 127.Bassett, J. Y., 234.Bassilios, H. F., 262.Bastiansen, O., 190.Bastien, B. N., 219.Bate, R., 448.Bateman, L. C., 218.Bates, J. A. R., 488.Rates, J. F., 483.Bates, R. B., 200, 275, 292,Bates, R. G., 439.Batorewicz, W., 222.Batovskaya, T. A., 486.Battersby, A. R., 343, 354.Batterman, B. W., 504,505.Battiste, M. A., 314.Battle, A. M. del C., 394.Bauer, H., 324.Bauer, L., 202.Bauer, R., 131, 182.Bauer, V. J., 196.Baulieu, E. E., 433.Baumgardner, C. L., 308.Baumgarter, F., 183, 184.Baun, W. L., 496.Bautz, E., 976.Bautz, E. K. F., 350.Baxter, J. N., 359.Baxter, R. M., 343.Bayard, R.T , 8.Bayer, O., 279.Bayer, R. P., 242.Baylis, E. K., 217.Baylouny, R. A., 285, 307.Bazinet, M. L., 497.Beachell, H. C., 132.Beak, P., 353.Beard, C., 197..Beam, A. G., 419, 420.303.Bearse, A. E., 334.Beaton, J. M., 267, 305.Beattie, I. R., 138, 141,142, 155.Beau, G., 479.Beaudet, R. H., 195.Beaven, G. H., 233.Bbcart, M., 112.Beck, F., 252.Beck, W. S., 410.Becka, L. N., 505.Becke-Goehring, M., 145,Beckel, C. L., 114.Beckel, C., 115.Beclser, E., 411, 412.Becker, E. D., 329.Becker, J. A., 12.Beckers, H. G., 146.Beckmann, S., 287.Beckwith, A. L. J., 236.Bedford, A. F., 330, 333.Bedford, C. T., 276, 288,Bedford, G. G., 192.Beech, J. A,, 32.Beenakker, J. J. M., 86, 87.Beer, L., 395.Beers, R.F., 371.Beg, M. A. A., 143.Begbie, R., 370.Begemann, P. H., 275.Beggs, B. H., 471.Behrens, H., 149, 177.Behun, J. D., 442.Beider, S. Ya., 27.Beilby, A. L., 463.Belardini, M., 295.Belcher, C. B., 479.Beletskaya, I. P., 230.Bel’gorskii, I. M., 31.Belil, G., 270.Bell, C. L., 202.Bell, E. A., 194.Bell, H. M., 210.Bell, J. A., 241.Bell, J. L., 420.Bell, K. M., 43.Bell, R. A., 298.Bell, R. P., 246.Bell, S. C., 339.Bell, T. N., 147.Bellar, T., 449.Bellasio, E., 323.Bellemans, A., 95.Bellig, E., 163.Bellin, J. S., 320.Bello, L. J., 374.Belohlav, L. R., 231.Belousov, V. P., 97.Belov, N. V., 505.Belova, V. I., 165.Ben Aim., R, 37, 38.Bender, M. L., 225, 246,247, 248, 249, 250, 252.Bendich, A., 375.146, 148.319.Ben-Efraim, D.A., 198,307.Benesi, H. A., 82.Benik, I., 356.Benington, F., 273, 348.Benitez, A., 375.Benjamin, B. M., 212.Benjamin, L., 97.Benkeser, R. A., 333.Benkovic, P., 247.Bennett, H., 455.Bennett, M. J., 185.Bennett, R., 201.Bennett, R. G., 110.Bennett, R. P., 233.Benson, A., 390, 394.Benson, G. C., 97.Benson, M., 219.Benson, R. E., 52.Benson, S. W., 228.Bent, R., 480.Bentrude, W. G., 253.Benz, R., 153.Benzer, S., 382.Berck, B., 487.Berecka, M., 476.Berends, W., 371.Berezowsky, J. A., 357.Berg, P., 379, 382.Berg, R. A., 127.Berge, D. G., 469.Bergeim, F. Ip., 342.Bergelson, L. D., 260.Berger, A., 253.Berger, J. G., 197.Rergman, I., 458.Eergman, J., 317.Bergson, G., 333.Bergstrom, X., 276, 284.Berka, A., 452, 453, 467,Berkelhammer, G., 414.Berkman, J. I., 403.Berlin, A., 499.Berlin, A.J., 196, 282.Berlin, A. M., 155.Berliner, D. L., 429.Berliner, E., 233.Berlinguet, L., 265.Bernal, I., 47, 51, 163, 175,Bernard, R. E., 332.Bernasek, E., 295.Bernhard, C., 316.Bernhard, S. A., 253.Bernhauer, K., 375, 402,Bernheim, R. A., 66.Bernstein, H. J., 64.Bernstein, J., 342.Beroza, M., 278, 329, 447.Berson, J. A., 211, 227, 228,Bertoldi, S., 481.Bertrand, R. R., 89.Bessman, M. J., 374.Bestian, H., 185.468, 470.178.411, 412, 413.229, 230, 253518 INDEX OF AUTHORS’ NAMESBestman, H. J., 260, 261.Bestmann, H. J., 274.Bethea, T. W., 258.Betrand, M., 272.Betteridge, D., 479.Beu, K.E., 502.Beukers, R., 371.Beutner, H., 177.Bevan, C. W. L., 329.Bews, A. M., 370.Beyermann, K.: 438.Bezjak, A., 478.Bezuglyi, V. D., 486.Bhatnager, M. L., 461, 468.Bhatnagar, R., 461, 468.Bhasin, R. L., 444, 478.Bhattacharaya, A., 354.Bhattacharaya, P. K., 355.Bhattacharyya, S. C., 290.Bhattacharyya, S . N., 96.Bheernasankara Rao, C.,Bibber, M. J. V., 374.Bickel, A. F., 307, 313, 314,Bickelhaupt, F., 358.Bieber, R. E., 416.Bieber, T. I., 261.Biellmann, J.-F., 303.Bielstein, H. O., 135.Biemann, K., 194,204, 352,Bienenstock, A., 506.Bierderbick, K., 330.Bierstedt, R., 510.Bigley, D. B., 294.Bigorajski, G., 38.Bijvoet, J. M., 503.Bilefield, L. I., 491.Billig, E., 175.Billman, J. H., 256.Bills, D.G., 102.Bines, B. J., 370.Bingel, W. A., 114.Binkowski, B. B., 138.Binks, R., 343.Biordi, J., 217.Birch, A. J., 266, 290, 294,306, 314, 319, 329, 360.Bird, C. W., 339.Bird, R. B., 88.Birkeland, S. P., 267.Birkhimer, C. A., 332.Birkofer, L., 328, 376.Birnie, G. D., 409.Birnkraut, W., 144.Birtwistle, J. S., 296.Bishop, C. T., 246,359,362,Bishop, E., 453, 467, 471.Bishop, E. O., 64.Bisht, C. D., 453.Biswas, B. B., 374.Bittler, K., 183.Bittrich, H. J., 95, 96.Bjerrum, J., 174.450.315.353.366.Bjork, R. G., 461.Bjorvatten, T., 512.Black, W. A. P., 364.Blackadder, D. A., 238.Blackburn, G. M., 318, 341.Blackie, M. S., 66, 67.Blackman, E. J., 235.Blades, A. T., 223.Blaha, K., 344.Blake, A. R., 40.Blake, C.A., jun., 447.Bland, B. J., 485.Blankenstein, G., 320.Blanks, R. F., 92.Blatter, H. M., 198.Blay, N. J., 131.Blaiek, A., 500.Blight, M. M., 172.Block, B. P., 170.Blodgett, K. B., 15.Bloembergen, N., 66.Bloemendal, H., 383.Blom, J., 359, 361.Blomberg, C., 266.Blomquist, A. T., 183, 269,Bloomer, J. L., 233, 286.Bloomfield, J. J., 262.Blount, W., 338.Blow, D. M., 502.Blumberg, E. A., 39.Blundell, A., 35.Bly, R. K., 279.Blyholder, G., 14.Boase, D. G., 456.Boaz, H. E., 355.Bobbitt, J. M., 204, 344.Bock, H., 143, 144, 177.Bock, R., 484.Bockris, J. O’M., 167.Bodanszky, M., 332.Bode, H., 151.Boden, N., 145.Bogri, T., 349.Bohm, R., 364.Bohme, D., 99.Boenicke, H., 140.Boesman, E., 55.Boeters, H., 145, 147.Boettcher, F.-P., 235, 335.Boettcher, R.R., 337.Bogdanova, A. A., 141.Bogorad, L., 385, 391, 392,Bogoyavlenskaya, M. L.,Bohlmann, F., 271, 329,Bojesen, E., 431.Bolinder, A., 410.Boling, W. H., 445.Bolte, E., 432.Bolton, C. H., 366.Bolton, H. C., 504.Bolton, J. R., 50, 51,52, 58,281, 308.393, 395.26.345.60, 206.Bond, H. E., 445.Bond, W. L., 502.Bondivenne, R., 479.Bonelli, R. A., 235.Bonet, J. J., 303.Bonham, R. A., 192.Bonitz, R. E., 459.Bonnaire, Y., 482.Bonner, T. G., 221, 362.Bonner, W. A., 212, 367.Bonnet, R., 411.Bonnichsen, R., 418.Boocock, G., 44.Boomer, G. L., 493.Booman, K. A., 54.Boone, J. L., 135.Boord, C. E., 32.Booth, D., 25.Booth, G., 173, 178.Booth, H., 338.Bor, G., 177.BorEib, S., 209.Borden, G. W., 285.Bordwell, F.G., 223.Borek, E., 374.Boretti, G., 411, 412.Borisov, A. E., 147.Bork, V. A., 462.Bornowski, H., 271, 329.Borodin, P. M., 69.Borowitz, I. J., 201.Bos, H., 47.Bosch, J., 270.Bosch, L., 383.Bose, 5. L., 367.Bose, P. K., 301.Bose, S., 453.Boser, H., 420.Boss, C. R., 46.Boston, J. L., 181.Bothner-By, A. A., 192,Bott, R. W., 254.Bottei, R. S., 170.Bottini, A. T., 193, 231,Bottomley, G. A., 91.Bouben, N. Ya., 52.Boulton, A. J., 332.Bouquet, G., 176.Bourne, E. J., 221, 362.Bourns, A. N., 219, 224.Bouten, P., 491.Bowers, A., 305.Bowers, V. A., 48, 56, 57,Bowman, R. L., 495.Boyer, J. P., 300.Braddock, L. I., 449.Bradford, J. L., 134.Bradley, D.C., 131, 156,157, 168, 170.Bradley, J. N., 19.Bradley, M. J., 153.Bradlow, M. L., 431.Bradlow, H. L., 433.198, 300, 307, 342.320.58, 205INDEX OF AUTHORS’ NAMES 519Bradshaw, J. S., 230.Bradsher, C. K., 347.Brady, D., 142.Brady, R. O., 402, 413.Braendlin, H. P., 229, 231,Bragg, D. R., 327.Brahm, Dev., 479.Bminina, E. M., 156.Brainina, Kh. Z., 486.Bramley, R., 199.Brand, L., 421.Brandon, N. E., 247.Brandon, R. W., 60.Brandsma, L., 270, 340.Brantner, H., 454.Brasch, J., 324.Brasseur, L., 273.Bratten, D., 22.Braunling, H., 262.Brauer, G., 161.Bray, H. M., 479.Bray, R., 411.Bredereck, H., 367.Breenlee, K. L., 487.Bregman, J., 509.Breig, E. L., 195.Breiter, J. J., 258, 322.Bremond, M., 128.Brenet, J., 161.Brennan, G.L., 132.Brennan, R., 476.Brenner, S., 379, 380.Breslow, D. S., 176.Breslow, R., 210, 281, 286,Bretscher, M. S., 381.Breuer, H., 433.Brewer, F. M., 138.Brewer, H. W., 348, 354.Brewer, L., 100, 127, 128.Brey, W. S., jun., 196.Brickman, M., 232.Brieger, G., 285.Briegleb, G., 82.Brieux, J. A., 235.Briggs, R., 482.Bright, A., 344.Brignell, P. J., 337.Brigorghe, M., 176.Brimacombe, J. S., 364,Bringi, N. V., 353.Brinkman, A. A. A.M., 441.Brisdon, B. J., 159.Britton, D., 511.Brivati, J. A., 51, 55, 56.Brochmann-Haussen, E.,Brocklehurst, K., 246.Brocklehurst, P., 199.Brodskaya, V. M., 454.Brody, J. K., 101, 128.Briill, H., 442.Broida, H. P., 102,107, 116,288.307, 314.368.448.127.Bromels, E., 132.Bromley, D.A., 101.Brook, M., 125.Brooker, A. C., 320.Brookes, P., 373.Brooks, C. T., 24.Brooks, R. V., 432.Broomhead, J. A., 472.Broschard, R. W., 366.Brossi, A., 347.Brotherton, R. J., 135.Brown, A. C., 97.Brown, B. R., 310.Brown, C. A., 132, 254.Brown, D., 153.Brown, D. A., 185.Brown, D. H., 160.Brown, D. J., 319.Brown, D. M., 375, 376.Brown, G. B., 373, 377.Brown, G. L., 378.Brown, G. M., 98.Brown, H. C., 132,207,210,219, 227, 232, 254, 255,262, 336.Brown, H. W., 51.Brown, I., 95, 330.Brown, J. B., 433, 434.Brown, K. B., 447.Brown, M., 210.Brown, M. R., 46.Brown, P. J., 263.Brown, R. D., 165, 337.Brown, T. H., 66.Brown, T. L., 130, 206.Brown, T. M., 158.Brown, W.B., 84, 88, 99.Brown, W. H., 277.Brown, W. I., 440.Brownstein, A. M., 408,Brownstein, S., 197.Bruce, J. M., 309.Bruckenstein, S., 456.Brugel, W., 202, 334.Briimmer, W., 330.Bruer, S. W., 343.Bruice, T. C., 244, 246, 247,249, 250.Bruin, F., 51.Bruin, M., 51.Brunnhe, C., 497.Bruno, J. J., 247, 249.Bruns, K., 294.Brush, A. H., 490.Brush, S. G., 94.Brushmiller, J. G., 169.Bryan, R. F., 372, 514.Bryce-Smith, D., 313.Bryson, M. J., 427, 429.Brzostowski, W., 93.Bubeva-Ivanova, L., 349.Bubnov, Yu. N., 135.Buc, H., 65.Buchanan, J. M., 406, 407.Buchi, G., 269, 350.409.Buchner, W., 148, 280.Buchs, A., 477.Buchta, E., 276.Buchwald, H., 146.Buck, K. R., 233.Buckingham, A. D., 133,Budd, A. L., 463.Budde, W.L., 230.Budge, A. H., 83.Budb, A., 118.Budzikiewicz, H., 200, 201,204, 205, 303, 306, 352,353, 354.185.Budzikiewicz, M., 351.Buchi, G., 292, 293, 294.Buchner, O., 241, 323.Buchner, W., 258.Biihler, R. E., 236.Buell, G. R., 227.Buerger, M. J., 503.Buffagni, S., 162.Buhl, F., 454.Bukun, N. G., 129.Bullen, G. J., 511.Bullerwell, R. A. F., 487.Bullock, E., 314, 329, 337,Bu’ Lock, J. D., 271, 276.Bumgardner, C. L., 262,BunEa.k, P., 475.Buncel, E., 224, 234.Bunn, C. W., 506.Bunnenberg, E., 197, 306.Bunnett, J. F., 219, 222,223, 234, 235, 251, 252.Bunton, C. A., 247, 252.Bunyar, P. J., 244,258,266,Burastero, J. J., 460.Burch, J. E., 206.Burdon, J., 310.Burg, A. B., 144.Burger, T. F., 185.Burgess, A. R., 39.Burgmaster, J., 262.Burgstahler, A.W., 297.Burkhalter, J. H., 109.Burkhardt, F., 347.Burlaka, V. P., 462.Burlingame, A. L., 204, 352.Burlitch, J. M., 243.Burn, D., 306.Burn, I., 86.Burnell, R. H., 357.Burnham, B. F., 387.Burriel-Marti, F., 452.Burrows, E. P., 279, 334.Burrows, W. D., 334.Burstein, S., 427.Burton, F. G., 460.Burton, J. S., 360.Burton, R. M., 414, 416.Buscarhs, F., 449.Busev, A. I., 455, 468.389, 391, 396.320.310520 INDEX OF AUTHORS' NAMESBusch, D. H., 173, 174,Busch, N., 479.Buss, H., 168, 422.Butcher, S., 195.Butenandt, A., 278.Butler, A. R., 246, 248.Butler, C. G., 277.Butler, K., 288, 318.Butterfield, D., 246.Buyske, D. A., 432.Buzas, A., 267.BUZ&S, I., 440.Bycroft, B.W., 341.Byers, R. G., 219.Byham, G., 152.Cabana, A., 203.Cabannes, F., 31.Cabezas, M. E., 305.Cabib, E., 360.Cadist, P., 269, 272.Cabrera, A. M., 469.Cadoff, B. C., 287.Cadogan, J. I. G., 226, 227,244, 258, 265, 266, 267,325.Cady, G. H., 150.Caglioti, L., 255, 301, 302.Cahn, R. D., 419.Cahn, R. W., 504.Cahn, W. R., 296.Cainelli, G., 255, 301, 302.Cains, T. L., 52.Cairns, J., 379.Cairns, T. L., 323.Calder, R. S., 504.Calderazzo, F., 176.Caldin, E. F., 254.Caldow, G. L., 127.Calkins, R. C., 473.Calloman, J. H., 100.Callow, R. K., 277.Calov, U., 147.Calpin, J. A., 463.Calvert, B. J., 345.Calvert, J. G., 33, 40, 43.Calvin, M., 62.Cama, H. R., 274.Cambie, R. C., 297.Cambio, R., 76, 84.Cameron, D.D., 306.Cameron-Wood, M., 244,Campaigne, E., 204, 341.Campbell, I. G. M., 333.Campbell, N., 308.Campbell, R. D., 245.Campbell, R. T., 461.Campbell, T. W., 267.Canellakis, E. S., 371.Canill, P., 195.Canjar, L. N., 95.Canning, R. E., 445.Cannon, J. R., 411.Cannon, P. L., 465.175.258, 325.Cantoni, G. L., 378.Capeller, I,., 332.Capizzi, F. M., 456.Caplow, M., 248.Capon, B., 246, 362, 363.Carasino, F. P., 162.Cargill, R. L., 282, 288.Carleton, N. P., 102, 110,Carlin, R. B., 240.Carlin, R. L., 169.Carlon, F. E., 267.Carlsmith, L. A., 311.Carlson, A. A., 334.Carlson, R. D., 253.Carlstrom, A., 418.Carman, R. M., 295.Carmichael, I., 489.Carmichael, J. L., 97.Carnell, P. J. H., 157.Carnes, W.J., 476.Carnighan, R. H., 200, 303.Carpenter, A. T., 392.Carpenter, R. D., 349, 389.Carrington, A., 47, 49, 50,51, 58, 59, 60, 68.Carrington, K., 206.Carrington, T., 110.Carroll, A. P., 145.Carroll, P. K., 101, 107, 121,Carroll, T., 103.Carruthers, W., 294.Carson, R. C., 167.Carter, A. C., 432.Carter, D. G., 156.Carter, J. H., 253.Cartledge, J., 35.Cartwright, G. E., 395, 396.Cartwright, J., 478.Cartwright, P. F. S., 451.Casassas, E., 449.Case, D. E., 296.Case, J. R., 149, 150.Caserio, M. C., 208.Casnati, G., 327.Cason, J., 275, 318.Caspi, E., 204.Cass, R. C., 136.Cassady, D. R., 270.Cassimatis, D., 155.Cassmar, O., 434.Castanera, E. G., 413.Castells, J.,' 270.Castellucci, N. T., 339.Castro, C.E., 492.Cathon, R. E., 406.Cattanach, J., 185.Catterall, R., 63.Caughey, W. S., 396.Causey, R. L., 452.Cava, M. P., 296, 303.Cavalca, L., 164.Cavalieri, L. F., 371.Cave, A., 355.Cavell, R. G., 157.112.123.Cazes, J., 236.Ceder, 0. J., 279.Cefola, M., 445, 494CermBk, V., 123.Cernf, o., 499.Cerny, V., 303.Cerrai, E., 444.Gervinka, O., 346.Chacraborti, S. K., 301.Chadwick, J. R., 138.Chaikoff, I. L., 427.Chakrabarti, C. L., 476.Chakravarti, K. K., 290,Chamberlain, M., 379.Chamberlain, N. F., 204,Chamberlin, T. C., 222.Chambers, D. L., 277.Chambers, F. W., 504.Chambers, R. D., 185.Chambers, W., 375.Chamboux, J., 38.Chance, B., 418, 421.Chandler, B. V., 340.Chandler, J. A., 155.Chang, C.T., 218.Chang, E., 434.Chang, H. W., 307, 314.Chantry, G. W., 55, 56.Chao-Hwa Yang, 446.Chapeville, F., 382.Chaplain, R. A., 415.Chapman, D., 148, 277.Chapman, J. H., 347.Chapman, N. B., 233, 253,Chapman, 0. L., 198, 285,Chappelenr, P. S., 98.Chappell, S. F., tert., 282.Chargaff, E., 381.Charles, D., 496.Charles, K. R., 233.Charlot, G., 459.Charlton, T. L., 507.Charman, H. B., 269.Charney, E., 289, 297.Chastain, B. H., 365.Chatt, J., 160,162, 164, 171,178, 179, 185, 186.Chatterjee, A., 347, 352,354, 381.Chatterjee, S., 338.Chaudhury, D. K., 233,Chaykin, S., 414.Chaykovsky, M., 265, 281,Cheaney, D. E., 27.Cheek, C. H., 449.Cheese, I. A. F. L., 368.Cheeseman, G. W., 339.Chen, A., 245, 269.Cheng, C.C., 339, 374.Cheng, K. L., 478.329.341.336.314.336.321INDEX OF AUTHORS’ NAMES 52 1Cheng, P., 380.Cheng, T., 378.Cheng Wu-Chieh, 103.Chernyaev, I. I., 153, 154.Chernyak, N. Ya., 22.Chesick, J. P., 220.Chesnut, D. B., 61, 70.Chetkina, L. A., 509.Cheung, H. T., 296.Cheuychit, P., 308.Chia-Tsun Liu, 96.Chiang, Y., 233.Chibber, S. S., 210.Chien, J. C. W., 46.Childress, S. J., 339.Chipman, D. R., 504.Chiriboga, J., 445.Chirnside, R. C., 438, 459.Chisholm, M. J., 275.Chiswell, B., 172.Chiurdoglu, G., 195, 196,Chkheidze, I. I., 52.Chodkiewicz, VI., 272.Chopard-Dit-Jean, L., 274.Chopra, K. L., 436.Chortyk, U. T., 219.Chow, W. Z., 292.Choy, T., 470.Chr&ien-Bessi&re, Y., 255.Christ, H.A., 202, 332.Christen, M., 232.Christensen, B., 331.Christensen, D., 195, 199,Christensen, G. M., 364,Christenson, S . H., 62.Christian, S. D., 95.Christiansen, J., 195.Christiansen, J. A., 359.Christy, M. E., 322.Chu, K.-Y., 97.Chu, S.-H., 336.Chu, S . S. C., 508.Chumachenko, M. N., 462.Chumaerskii, N. A., 206.Chun, C. Lin., 195.Church, M. G., 218.Church, R. F., 302.Churchill, J. A., 427.Ciaccio, L. L., 233.Ciampolini, M., 162, 164,Ciganek, E., 224, 279.Cilento, G., 416.Ciotti, M. M., 415, 416, 417.Cipollini, E., 206.Cirillo, V. A., 497.Claassen, H. H., 130.Clancy, D. J., 497.Clanet, F., 446.Clark, D. E., 347, 348.Clark, H. C., 142, 143, 157,Clark, J. C., 267, 308, 474.198.202, 327, 329.442, 445.233.165.Clark, R.F., 282.Clark, R. T., 489.Clarke, C., 348.Clarke, E., 128.Clarke, E. A., 346.Clarke, G. A., 218.Clarke, R. L., 201.Clarke, W. G., jun., 197.Clark-Lewis, J. W., 340.Class, E., 150.Clauss, K., 185.Clayson, K. J., 415.Clayton, C. J . , 360.Clement, R. A., 338.Clementi, E., 111.Clemons, C. A., 449.Clezy, P. S., 396.Cline, M. J., 382.Clin6, R. E., 374.Clinton, W. L., 114.Clippinger, E., 214.Cloney, R. D., 114.Closs, G. E., 241.Closs, G. L., 60, 242, 280.Closs, L. E., 241.Clovis, J. S., 239.Cluceru, D., 450.Cluett, M. L., 471.Cluley, H. J., 490.Clutter, R., 261, 323.Coates, E., 469, 485.Coates, G. E., 130, 162, 165,Coates, M. E., 405.Cobb, G. C., 120.Cockbill, M. H., 437, 489.Cochran, E.L., 48, 56, 57,Cochran, W., 504.Cockerell, L., 170.Cockett, M. A., 338.Codington, A., 373.Codington, J. F., 375.Coe, P. L., 311.Coeffier, G., 161.Coffer, J. L., 226.Coffey, C. E., 181.Coffey, R. S., 241.Coffman, D. D., 201.Cohen, A. I., 487.Cohen, B., 149.Cohen, D., 154.Cohen, E. G. D., 94.Cohen, L. A., 252.Cohen, P., 418.Cohen, S., 282.Cohen, T., 250.Cohen-Bazire, G., 274.Cohn, G. L., 427.Cohn, W. E., 376, 377.Colburn, C. B., 144.Colburn, C. F., 54.Cole, H., 504.Cole, J. E., 306.Cole, S. J., 514.Cole, T., 54, 55, 56.182, 185.58, 205.Coleman, C. F., 447.Coleman, M. H., 440.Coleman, R. F., 492.Coleman, W. E., 282.Coles, B. A., 46.Colin, R., 124, 127.Coller, B. A. W., 337.Collins, A.H., 472.Collins, C. J., 212.Collins, D. J., 294.Collis, M. J., 245.Collins, R. W., 468.Collman, J. P., 170, 173.Colowick, S. P., 417.Colter, A. K., 223.Cone, N. J., 355.Conley, R. T., 311.Connelly, J., 396.Connick, R. E., 67, 68, 69,Connolly, D. J., 281.Connolly, J. F., 91, 97.Connolly, J. W., 140.Connors, K. A., 225.Connors, W. J., 378.Conover, L. H., 288, 318.Conreur, C., 356.Conrow, K., 342.Cook, C. D., 164.Cook, C. F., 492.Cook, D., 194.Cook, J. W., 294.Cook, N. J., 375.Cook, R. E., 359.Cook, R. J., 53.Cooke, D. W., 174, 175.Cooke, G. A., 253.Cookson, G. H., 389.Cookson, R. C., 197, 267,270, 285, 289, 294, 308,309, 331, 333.70.Coombe, R. G., 366.Coomber, D. I., 496.Coombs, T. L., 422.Cooper, A.S., 502.Cooper, C. D., 120.Cooper, F. P., 246, 362.Cooper, G. D., 266.Cooper, J. E., 233, 277.Cooper, M. K., 160.Cooper, R. D. G., 273.Coopes, I. H., 91.Cope, A. C., 210, 224, 279,Coppens, G., 224.Coppens, Ph., 507.Coppinger, G. M., 83.Corbett, J. D., 147, 167.Corbett, J. F., 338.Corbin, J. L., 221.Corcoran, J. W., 411.Cordes, E. H., 245, 247.Corey, E. J., 230, 258, 265,281, 291, 309, 321.Corfield, M. C., 486.Corkins, J. T., 452.286522Corney, N. S., 24.Cornforth, J. W., 419.Cornille, M., 502.Cornwell, C. D., 195.Corpel, J., 454.Corral, R. A., 354.Correia, J. S., 318.Corriez, P., 359.Corse, J., 207,Corset, J., 63.Corsini, A., 469.Corss, R. J., 185.Corth, R., 491.Corwin, A. H., 336, 391Costa, B., 448.Costain, C.C., 193.Cosulich. D. B.. 366.Cotton, *F. A.; 129, 160,161, 162, 163, 172, 176,514.Coulson, C. A., 115, 127.Coulter, A. W., 304.Courtney-Pratt, J. S., 101.Courtois, J. E., 368.Cowe, D. W., 25.Cowen, J. A., 55.Cowie, J. M. G., 97.Cox, D. A., 309.Cox, E. F., 208.Cox, E. V., 405.Cox, G. F., 130.Cox, P. F., 66.Cox, R. A., 381.Coy, N. H., 487.Crabtree, A., 331.Craig, A. D., 139.Craig, L. C., 333.Crain, D. L., 231.Crain, R. D., 231.Cram, D. J., 190,230, 258.Cramer, F., 376.Cramer, R., 179.Cramer, R. M. R., 60, 148.Crandall, J. K., 283.Cranwell, P. A., 349.Craven, B. M., 513.Crawford, T. H., 191.Crayton, P. H., 156.Crick, F. H. C., 380.Criddle, W. J., 361.Crispin, D.J., 306.Cristol, S. J., 219, 224, 253.Croll, I. M., 81.Crombie, L., 200, 277, 329.Cromwell, N. H., 223, 224.Croon, I., 369.Crosbie, G. W., 409.Crosby, D. G., 265.Cross, A. D., 296.Cross, B. E., 298.Cross, F. J., 337.Cross, M. J., 409.Crossweimer, L. I., 62.Crosswhite, H. M., 101.Crouch, E. A. C., 166.Crowley, H. C., 345.INDEX OF AUTHORS’ NAMESCrowley, K. J., 281, 289,Cruickshank, A. M., 168.Cruickshank, A. J. B., 73.Cruickshank, D. W. J., 138.Csicsery, S. M., 240.Culbertson, J. B., 246.Cullis, C. F., 32, 36, 39.Culvenor, C. C. J., 345, 346.Cummings, F. E., 136.Cummings, W., 235.Cumper, C. W. N., 203.Cunningham, J., 55.Cunningham, L. W., jun.,Curcumelli-Rodostamo, M.,Curl, R. F., 191.Curphey, T. J., 303.Curran, C., 164.Curran, J.F., 425.Currie, R. B., 337.Curtin, D. Y., 196,220,264.Curtis, G. G., 303.Curtis, N. F., 172.Curtiss, C. F., 88.Cusachs, L. C., 114.Cusin, F., 26.Custer, J., 467.Cuthbert, G., 490.Cuthbert, J., 32.Cvetanovid, R. J., 21, 43,Cymcrman Craig, J., 268.Dadok, J., 480.Dalme, W., 130.Daftsios, A. C., 489.Dagnall, R. M., 484.Dahl, L. F., 138, 181.Dahlbom, R., 194.Dahlgard, M., 365.Dahne, W., 161.Daiber, J. W., 111.Dailey, B. P., 195.Dalby, F. W., 110.Dalgarno, A., 89.Dalziel, K., 414, 415, 420,Damany-Astoin, N., 123.Dams, R., 451, 452.Danby, C. J., 131.Dance, J., 270.Dancewicz, A. M., 388.Daniel, H., 224.Danieli, N., 289, 305, 327.Daniels, R., 335.aanilov, S. N., 369.3anilova, A.V., 346.Danilovs, G. P., 494.Danishefsky, S., 243, 287.Dankleff, M., 168.Danon, F., 89.Danyluk, S. S., 200, 316.lao, T. L., 434.larby, A. C., 283.302.417.357.44, 241.421.Darlak, R. S., 471.Darling, J. J., 424.Darling, S. D., 306, 355.Darooge, M. A., 198.Darwent, B. de B., 42.Darwish, D., 223.Das, J., 451.da Silva, J. J. R. F., 170.Dathe, C., 147.Datta, S. K., 456.Dauben, W. G., 282, 288,291, 299, 303, 304.Daughaday, W. H., 427.Daum, G., 328.Dave, K. G., 341, 349.Davenport, A. J., 99.Daves, D., 339.David, D. J., 479.Davidson, A. J., 310.Davidson, E. R., 114.Davies, A. G., 143.Davies, D., 153.Davies, D. A., 27.Davies, D. I., 224.Davis, A,, 27.Davis, D. G., 472.Davis, F., 445.Davis, G.L., 138.Davis, G. T., 223.Davis, M., 342.Davis, R. E., 132.Davis, S. J., 334.Davis, S. P., 100, 101, 119.Davison, A., 176.Davydov, A. V., 477.Davydova, Z. M., 475.Dawson, B., 504.Dawson, C. R., 462.Dawson, J. W., 133.Dawson, R. F., 342.Dayagi, S., 231.De, A. K., 443.Deacon, G. B., 168.Dean, G. A., 439.Dean, J. A., 476.Deane, A. M., 153.Dear, R. E. A., 240.Dearman, H. H., 46.Deb, A., 354.Debo, A., 146.le Boer, E., 51.Decat, D., 492.Degmi, J., 329.Deghenghi, R., 265, 266.Degn, H., 359, 431.le Graaf, W., 88.Deguchi, Y., 57.3e Ita, 0. S., 458.3e Jongh, D. C., 253.ie Kerf, J., 511.Dekker, C. A., 361, 372,le Kloet, S. R., 380.IeKluiver, H., 120.ie Koch, W. T., 300.lelahay, P., 481.375INDEX OF AUTHORS’ NAMES 523de la Mare, P.B. D., 224,Delbruck, M., 372.Della Porta, P., 13.Dellweg, H., 372, 411.Delmas, G., 99.Delmau, J., 189, 480.de Mars, G. A., 46.De Mars, R. D., 489.de Mayo, P., 284, 294, 300,de Miquel, M., 434.Demint, R. J., 369.Demole, E., 278.den Boef, G., 437.den Hertog, H. J., 235, 335,Denney, D. B., 261.Deno, N. C., 209, 285.Denot, E., 305.De Puy, C. H., 222.Derevitskaya, V. A., 369.Dersin, H.-J., 148.Derwish, G. A. W., 206.Desai, N. B., 261.Desai, R. B., 300.Desbarres, J., 463.Deschamps, P., 482.Descoins, C., 274.Deshmukh, G. S., 460, 482.Deshusses, J., 485.Dessy, R. E., 230, 245, 269.do Stevens, G., 320.Deulofeu, V., 347, 358, 366.Deuser, W. G., 497.Deutsch, E. W., 127.Deutsch, J.L., 101, 107,Deutschman, A. J., jun.,Dev, B., 450.Dev, V., 320.Devanathan, M. A. V., 463.Devaux, G., 362.De Voe, J. R., 496.de Vries, G., 441.de Vries, M., 383.Dewar, E. T., 364.Dewar, J., (Sir), 307.Dewar, J. H., 339.Dewar, M. J. S., 83, 207,226, 240, 342.De Witt, E. J., 255.De Wolfe, R. H., 253.Deyrup, J. A., 373.Dhaneshwar, R. G., 471.Dharmatti, S. S., 203.Diamentis, A. A. D., 244.Diaz-Peiia, M., 94.Dickens, B., 181.Dickerhorf, D. W., 130,206.Dickerman, S. C., 236.Dickinson, C. L., 323.Dickinson, R., 490.Dickson, R. S., 155.Dickstein, J. I., 231.232, 233.324, 337.336.124.364.Diczfalusy, E., 427, 434.Dieckmann, M., 382.Diehl, H., 439.Diehl, P., 202, 332.Dieke, G. H., 101, 107, 109,Dikshitulu, L.S. A., 454,Dillard, R. D., 270.Dilling, W. L., 288.Diluzio, J. W., 178.Di Marco, A., 411, 412.Din, F., 86.Dinning, J. S., 406, 408,Dinstl, G., 492.Dinulescu, I. G., 309.Dion, H. W., 203, 365, 366.Diorio, A. F., 130.Dirscherl, A., 439, 441.Discher, C. A., 465.Ditchburn, R. W., 107, 111.Ditsch, L. T., 222.Dittmar, B., 230.Dittmer, D. C., 322.Ditz, J., 479.Dixon, R. N., 101, 118.Dixon, W. B., 199, 202, 327.Diyarov, I. N., 479.Djerassi, C., 190, 197, 199,200, 201, 204, 205, 300,303, 306, 347, 348, 351,352, 353, 354, 512.Dmitriev, V. N., 486.Doadrio, A., 442.Dobrolyubskaya, T. S., 477.Dobrott, R. D., 131.Dobrynin, V. N., 289, 318.Dobson, G. R., 175, 176.Dobson, X. A., 269.Dobson, T.A., 341.Dobychin, S. L., 465.Dobyns, V., 201, 321.Dodgen, H. W., 68.Dodson, R. M., 286.Doehaerd, T., 195.Doerffel, K., 440.Doering, W. von E., 200,238, 289.Doerr, I., 375.Doherty, D. G., 425.Doherty, M. D., 418.Dokoupil, 2, 79, 92, 98.Dolan, E., 63.Dolej3, L., 292.Doleial, J., 467, 468, 484.Dolin, M. I., 415.Domange, L., 136.Dominguez, J., 328.Don, G., 356.Donaldson, E., 442.Donaldson, K. O., 407.Donoghue, J. T., 168.Donohue, J., 504, 514.Donnay, G., 506.Donnay, J. D. H., 506.127.467.409.Donninger, C., 419.Doornbos, D. A., 455.Doornekemp, J. G. F., 463.Dorain, P. B., 46.Doran, B. M., 406.Doran, P., 22, 23.Dorfman, L. M.,Dorfman, R. I., 427, 429,Dorokhov, V. A., 133, 136.Doran, V. F., 171.dos Santos-Veiga, J., 50,51, 52, 206.Doty P., 378.Dougall, D.K., 396.Douglas, A. E., 101, 107,Douglas, B. E., 169.Douglass, J. R., 253.Douglass, R. M., 153.Douwes, H., 507.Dowell, J. T., 103.Dowgialls, A., 362.Dowling, J. M., 193.Downing, D. F., 320.Downing, D. T., 274.Downing, M., 409.DOWS, D. A., 173.Doyle, F. P., 322.Doyle, W. T., 62.Drttgo, R. S., 107, 155.Drake, J. E., 139, 141.Dravnieks, F., 49, 50, 68.Dreger, L. H., 196.Dreiding, A. S., 327.Dreizler, H. D., 195.Drenchko, P., 324.Drenth, W., 269.Dreschler, D., 336.Dresel, E. I. B., 394.Dressler, R. L., 260.Drever, D. F., 40.Drews, B., 449.Drey, C. N. C., 332.Driesel, E. I. B., 394.Driessen, H.-E., 265.Drillat, J., 37.Droege, J.W., 21.Drowart, J., 100, 119, 120,Drummond, D. W., 370.Drummond, J. L., 456.Druyan, R., 420.Drye, D. J., 157.Dubbs, C. A., 445.Dubeck, M., 232.Dubovitskii, V. A., 155.Duc Dohkac Manh, 205.Duckitt, J. A., 468.Duckworth, M. W., 156,Duclaux, A. D., 423.Dudani, P. G., 139.Duell, E. G., 227.During, G., 95, 96.Duffy, C., 143.430.109, 118, 127.124, 128.157524 INDEX OF AUTHORS’ NAMESDuggan, E. L., 379.Duhart, P., 131.Duhne, C., 458.Duling, I. N., 335.Dulova, V. G., 322.Dumke, W. I., 508.Dunathan, K., 338.Duncan, A. B. F., 100.Duncan, F. J., 241.Dunford, H. B., 107.Dunitz, J. D., 287, 328.Dunlap, L. B., 464, 483.Dunlap, R. D., 92, 97.Dunn, D. B., 374.Dunn, H. M., 504.Dunn, T. M., 162, 163.Dunnavant, W.R., 264.Dunne, T. G., 172.Dunstan, I., 132.Dupont, J. A., 131, 132.Durand, M. H., 270.Durham, L., 203, 366.Durham, L. J., 204, 205,348, 352, 353, 354.Durie, R. A., 101, 108.Durrant, B., 129.Durrant, P. J., 129.Dutler, H., 305.Duts, M., 195.Dutta, N. L., 347.Dutta, P. C., 296.Dutton, G. G. S., 364, 370.Dutz, R., 376.Duval, C., 198, 439, 499.Dvoritk, J., 476.DvoPQk, V., 470.Dvoryankin, V. F., 507.Dyatkina, M. E., 153.Dybczyliski, R., 448.Dybvig, D. H., 220, 264.Dykast, J., 499.Dyke, D. E. L., 81.Dymova, T. N., 130.Dyrssen, D., 478.Dzhagatspanyan, R. V.,Dzierzynski, M., 30, 31, 34.Eaborn, C., 232, 254.Eade, R. A., 300.Eardley, R. P., 455.Eargle, D. H., 59.Eason, R., 382.Eastham, J. F., 233.Eastman, J.W., 62.Easton, N. R., 270.Easty, D. B., 361.Eaton, D. R., 52.Eaton, P. E., 284.Ebel, H. F., 311.Eberhardt, M., 236.Eberhardt, W. H., 103.Ebert, M., 446.Ebsworth, E. A. V., 140,Ecke, H., 146.480.150.Eckelmann, W. R., 496.Eckert, J. M., 201, 203.Eckfeldt, E. L., 463.Edgell, W. F., 206.Edmonds, M., 374,Edmondston, P. B., 330.Edwards, A. J., 15%Edwards, B. E., 204, 341.Edwards, D. A., 159.Edwards, J. A., 305.Edwards, J. O., 168, 254.Edwards, J. W., 464.Edwards, 0. E., 243, 296,297, 318, 347, 358.Efremov, V. Y., 33.Egerton, A. C. (Sir), 28.Eggerer, H., 404.Eglinton, G., 269, 277, 282,Egnell, C., 267.Ehmann, W. D., 491.Ehrlich, G., 11, 12, 13, 14.Ehrlich, H. W. W., 513.Ehrlich, P., 155.Eichenberger, W., 274.Eichhorn, E.L., 510.Eichler, S., 179, 181.Eickermann, R., 157.Eigen, M., 246.Eisch, J. J., 138, 266, 334,Eisenbraun, E. J., 344.Eisenhauer, G., 148.Eisenthal, R., 250.Eisinger, J., 12, 13.Eisman, E. H., 261.Eisner, U., 337.Eistert, B., 317.Eiter, K., 277, 278.Ekberg, S., 478.Ekert, B., 372.Elad, D., 263, 273.Elias, D. H. D., 233.Elias, H., 136.Elias, L., 21.Eliel, E. E., 196.Eliel, E. L., 207, 223, 236,256, 257, 284.Eliseev, S. S., 159.Elisesva, N. G., 130.Ellert, G. V., 154.Ellestsd, G. A., 292.Elliot, D., 452.Elliott, B., 182.Elliott, I. W., 338.Elliott, T., 197.Ellis, B., 306.Ellis, R. B., 132.Ellison, F. O., 108.Elmore, N. F., 347.Elodi, P., 424.Els, H., 327.El Sayed, M.F. A., 175.Elvidge, J. A., 334.EIving, P. J., 473, 488.Emanuel, N. M., 39.295.337.EmelBus, H. J., 138, 146,Emerson, T. R., 336.Emmons, W. D., 259.Emons, H.-H., 140.Emovon, E. U., 224.Emsley, J. W., 145.Engel, C. R., 256.Engel, L. L., 427.Engel, W., 155.Engelbrecht, A., 150.Engelhardt, V. A., 323.Engelsma, G., 62.Engelsman, J. J., 462.England, D. C., 131.England, S., 425.Englehard, N., 341.Englert, G., 332.English, W. H., 471.Enikolopyan, N. S., 28, 29,Enslin, P. R., 300.Entwistle, R. F., 509.Enzell, C., 292.Erao, P., 358.Erb, R., 341.Ercoli, A., 256.Erdey, L., 440, 454, 473,Erdos, E., 95.Erdtman, H., 296, 296.Erickson, C. E., 133.Erkovich, S. P., 111.Erne, F., 439.Ernst, B., 365.Erpelding, J.J., 235.Erpelding, T. J., 269.Ertel, K., 261, 446.Eskananzi, It., 172.Estabrook, P., 418.Essen, L. N., 165.Ettinger, R., 71, 131.Eugster, C. H., 328.Evans, A. G., 182, 226.Evans, D., 263, 276.Evans, F. J., 326.Evans, H. J., 403.Evans, J. C., 233.Evans, R. F., 336.Evans, R. J. D., 272.Evans, W. H., 446.Everard, A. F., 235.Everett, D. H., 73, 91.Evers, E. C., 129.Everse, J., 421.Ewald, P. P., 506.Ewart, G., 145.Ewing, G. J., 161.Eyring, H., 17.Eyton, W. B., 318.Faber, G., 367.Faber, J. S., 455.Fabricand, B. P., 65.Fabrichnyi, B. P., 276.Fackler, J. P., 165.150, 177.30, 31, 32.500INDEX OF AUTHORS' NAMES 525Fahey, R. C., 226, 232.Faigle, H., 273.Failes, R. L., 224.Fainberg, A. H., 229.Fairbrother, F., 157.Falconer, J.W., 22, 32.Falconer, W. E., 21, 35.Fales, H. M., 343, 348.Falk, J. E., 394.Fallon, R. J., 113, 114.Fan, C. Y., 101.Fankuchen, I., 504.Farber, M., 135.Faris, J. P., 448, 476.Farmer, J. B., 56, 60.Farrell, P. G., 286.Fateley, W. G., 195.Fathy, I., 321.Faulhaber, G., 177.Faulkner, J. E., 121.Fava, G., 164, 509, 510.Favin, S., 20.Fawcett, C. P., 415, 417.Fay, R. C., 169.Feakins, D., 145.Feather, M. S., 360.Feather, P., 306.Fechtig, O., 290.Feder, R., 504.Fsdorak, N. A., 267.Fedorova, A. V., 272.Feeney, J., 143, 145.Feigl, F., 442.Felauer, E. E., 277.Feller, K. L., 279.Fellman, W., 183.Fels, I. G., 414.Feltham, R. D., 46.Fender, B. E. F., 88.Feniak, G., 297, 318.Fenimore, C.P., 20, 21.Fensham, P. J., 146.Fenske, M. R., 37.Fenske, R. F., 171.Ferguson, G., 286, 297, 507.Ferguson, H. I. S., 101.Ferguson, R. E.,' 32.Fergusson, J. E., 160, 161.Fernandez, M., 425.Fernandez, V. P., 421.Fernando, Q., 166, 463, 465,Ferrari, C., 347.Ferreira, J. M., 204, 354.Ferrier, F. J., 359.Ferrier, R. J., 359, 364.Ferrier, W. G., 513.Ferris, L. M., 153.Ferrus, R., 152.Fetter, E. J., 330.Fetter, N., 137.Fetzer, U., 252.Fessenden, R. W., 48, 51.Feuer, H., 258.Fiarman, I. D., 246.Fichtel, K., 183.469.Field, B. O., 155.Fields, D. L., 280.Fields, E. K., 243, 308.Fierce, W. L., 144.Fiers, W., 379.Fife, T. H., 247, 250.Fife, W. K., 236.Figgins, P. E., 173.Figgis, B. N., 143, 171.Filasiewicz, W., 476.Filimonova, M.M., 486.Filippova, L. F., 26, 27.Finan, P. A., 263.Finch, A., 135, 206.Finch, N., 204, 351, 354.Findlay, T. J. V., 96.Fine, D. A., 162.Finegold, H., 197.Fink, K., 374.Fink, R. M., 374.Fink, W., 140.Finkbeiner, H. L., 266.Finkelstein, M., 220.Finn, E. J., 114.Finn, R. T., 224.Firestone, R. A., 337.Firsching, F. H., 451.Firth, W. C., 253.Fischer, A., 240, 288.Fischer, D. W., 496.Fiecher,E. O., 180,183, 184.Fischer, G., 442.Fiecher, H., 52, 219, 272,Fischer, J., 143.Fischer, J. F., 484.Fischer, R., 327.Fischl, J., 447.Fish, A., 32, 36, 39.Fisher, H. F., 425, 426.Fisher, I. P. 31.Fisher, M. E., 94.Fishman, J., 433, 434.Fishman, M. J., 476.Fitzgerald, M. E., 497.Fitzsimmons, B.W., 145.Flahaut, J., 136.Flaschka, H., 456.Flavin, M., 404, 405.Fleck, G. M., 244.Fleissner, E., 374.Fleming, I., 268.Fleming, J. S., 312.Fleming, M. A., 135.Fletcher, A. N., 154.Fletcher, H. G., jun., 362.Flock, F. H., 332.Flood, C., 430.Flood, S. H., 232, 233, 268.Florence, T. M., 488.Flores, S. E., 204.Florini, J. R., 432.Floyd, K. W., 408.Fluck, E., 145, 146, 149.Fluendy, M. A. D., 94.Flygare, W. H., 192.395.Fock, W., 95.Fodor, G., 260.Forster, T., 100.Foex, M., 153.Fog, J., 456.Foldi, V. S., 267.Folt, V. L., 192.Foner, S. N., 35, 56, 57.Fonken, G. J., 273, 285.Fontaine, F., 378.Fontana, P. R., 118.Foord, S. G., 29.Foote, J. L., 233.Forbes, J. W., 83, 480.Forchielli, E., 429.Ford, J.E., 405.Foreman, H., 495.Foreman, J. K., 456.Forman, A., 50.Forman, A. G., 213.Forman, J. C., 98.Forman, P., 448.Formbnek, Z., 499.Forrest, H. S., 375.Forsen, S., 198.Forster, R. G., 194.Forstner, J. A., 145.Fort, A. W., 215.Fort, R., 27.Fortune, I., 440.Foss, O., 150.Fossen, S., 150.Foster, A. B., 277, 334, 363,Foster, E. W., 118.Foster, J. F., 21.Foster, P. W., 223.Foster, R. E., 148.Foster, W. E., 133, 256.Fotherby, K., 428.Fothergill, G. A., 263.Fowden, L., 325.Fowler, L. R., 358.Fowles, G. W. A., 129, 156,Fox, J. J., 374, 375.Frackowiak, M., 127.Fraenkel, G. K., 50, 51, 58,Fraenkel-Conrat, H., 381.Fraga, S., 113, 12:.Francis, J. E., 323.Francis, K. E., 153.Franck, B., 335.Frangopd, P.T., 314.Frank, G. H., 482.Franke, J., 341.Frankenfeld, J. W., 325.Franklin, J. L., 102.Franklin, R. M., 382.Franklin, T. C., 164.Franswa, C. E. M., 479.Frantz, A. G., 432.Frantz, A. M., 282, 312.Franzen, V., 241, 265, 280.Fraser, M., 203, 327.366, 367.157, 159.372526 INDEX OF AUTHORS' NAMESFraser, R. R., 200.Fraser, R. T. M., 174.Frawley, T. F., 429.Frazer, J. W., 133, 151.Fredericq, A., 378.Freed, J. H., 58.Freedman, H. H., 282, 283,Freegerde, M., 478.Freeman, E. S., 54.Freeman, J. P., 279, 320.Freeman, P. I., 98, 99.Freeman, R., 71.Freese, E., 373, 376.Freese, E. B., 376.Freiberg, L. A., 196, 198,Freidlina, R. Kh., 156.Freier, E. F., 415.Freifelder, M., 254, 335.Freiser, H., 443, 469.French, D., 369.FrBon, P., 257, 267.Frkre, P., 157.Fresco, J.R., 378.Frese, E., 148.Freund, H., 158.Frey, A. J., 352.Frey, H. M., 241, 321.Freymann, M., 67.Freymann, R., 67.Frid, J., 332.Fridsvich, I., 421.Fridrichsons, J., 503, 513,Friebolin, H., 204.Fried, J., 342.Fried, V., 94.Friedel, R. A., 498.Frieden, C., 425, 426.Friedkin, M., 414.Friedl, W., 120.Friedman, D. L., 404.Friedman, H. C., 412.Friedman, S., 407.Friedmann- Spiteller , M.,Friedrich, W., 374.Friend, J. A., 93.Friese, G., 477.Friis, P., 279.Frisch, M. A., 196.Frischmann, J. K., 487.Frig-GaLega, T., 478.Fristom, R. M., 20, 21.Fritchie, C., 509.Fritchie, C., jun., 283.Fritz, G., 137, 140.Fribz, H. P., 183.Fritz, J. S., 448, 471.Fritzsche, H., 82.Frohlich, H.-O., 166.Frohliger, J.O., 467, 469.Fromm, H. D., 139.Fromm, H. J., 424.Frost, A. A., 114.312.317.514.352, 353.Frost, D. C., 122.Frostling, H., 330.Frush, H. L., 361, 496.Fry, A., 219.Fry, P. W., 124.Frydman, B., 347, 358.Fuchs, F., 276.Fudim, M., 262.Fiirst, A., 341.Fujii, T., 366.Fujimoto, M., 448.Fujimoto, S., 19.Fujishiro, R., 80, 81.Fujita, J., 172, 173.Fujita, K., 233.Fukuchi-Thibaut, Y., 31Fukui, K., 83.Fukushima, D. K., 431.Fuller, N. A., 252.Fuller, W., 378.Funk, H., 160.Funk, H. R., 403.Funk, K. F., 323.FUOCO, L., 411.Furse, C. T., 461.Furukawa, S., 292.Furukawa, Y., 417.Furuki, C., 474.Gabe, E. J., 513.Gabrilove, J. L., 427, 429.Gaertner, G., 339.Gaetjens, E., 246.Gaiffe, A., 262.Gaiser, P., 402, 413.Gal, D., 34.Galbraith, F.J., 497.Galinos, A. G., 137.Gallagher, T. I?., 431, 433,Galmarini, 0. L., 366.Galt, R. H. B., 298.Galus, Z., 52, 482.Gamp, A., 446.Gamsjiiger, H., 441.Gamson, B. W., 98.Ganchoff, J., 456.Ganellin, C. R., 286.Ganter, C., 305.Ghnti, T., 445.Gaoni, Y., 198, 307, 316.Garbisch, E. W., 252, 254.Garbutt, S., 370.Garcia-Fernandez, H., 129.Gardi, R., 256.Gardiner, W. C., 19.Gardner, A. L., 123.Gardner, C. L., 60.Qardner, K. W., 474.Gardner, P. D., 304.Garegg, P. J., 360.Garland, J. H. N., 143.Garman, R. G., 440.Garner, C. S., 174.Garst, R., 234.Garton, G., 138.434.Garton, W. R. S . , 102.Gamin, D., 127.Garwood, R.F., 269.Garz6, T., 449.Gaslini, F., 458.Gasser, R. P. H., 71.Gassman, P. G., 213, 281,Gasson, D. B., 499.Gast, P. W., 497.Gate, S. H., 147.Gates, M., 348.Gatz, C., 123.Gaudemaris, M., 276.Gaudry, R., 265, 266.Gaur, J. N., 450, 470.Gayden, A. G., 100, 112.Gear, J. R., 343.Geary, W. J., 469.Gedda, L., 448.Gee, G., 99.Gee, M., 364.Gegus, E., 473.GBher, J., 487.Geichman, J. R., 159.Geiger, B., 287.Geissmrtn, T. A., 292, 345.Geldard, J. F., 172.Geller, B. E., 97, 487.Gellert, E., 358.Genet, F., 511.Genevois, L., 421.Gen-Ichi Tsuchihashi, 213.Gensler, W. F., 320.George, D. B., 226.George, T., 204, 353, 354.Georgian, V., 303.Gerace, P. L., 170.Gerds, A. F., 153.Gerig, J. T., 234.Gerken, R., 157.Gerlach, H., 328.Gerloch, M., 185.Germain, G., 511.Germain, J.E., 31.Gernert, F., 130.Gero, L., 1'07.Gerrard, W., 133, 136, 206.Gershfeld, N. L., 297.Gersmann, H. R., 58.Gerson, F., 51.Gerstenberg, B., 156.Geschwind, S., 46.Geske, D. H., 50, 57.Gesser, H., 143.Gestblom, B., 201, 202, 323,Gething, B., 310.Gettler, J. D., 246.Getz, H. R., 446.Gewald, K., 323, 330.Gewitz, H. S., 396.Ghosh, A. K., 141.Ghoshal, C. R., 352.Gianni, M. H., 196, 284.Giasto, M. B., 139.283, 303.324INDEX OF AUTHORS’ NAMES 527Gibb, T. R. P., 129.Gibbard, F., 95.Gibbons, W. A., 283.Gibbs, J. A., 490.Gibson, J. F., 48, 189.Gibson, K. D., 386, 397,Gibson, N. A., 472.Gibson, T., 138.Giguere, P. A., 23, 97.Gilani, S.S. H., 331.Gilbert, B., 204, 352, 353,Gilbert, J. M., 471.Gilbert, W., 379.Gilchrist, M., 247.Gilchrist, T., 201, 318.Gilderson, P. W., 223.Giles, J. A., 295.Gilje, J. W., 222.Gilles, P. W., 100, 135.Gillis, B. T., 259, 279.Gillis, J., 493.Gillespie, A. S., 496.Gillespie, R. J., 64, 149.Gilman, H., 263, 266, 276,Gilman, R. E., 358.Gilow, H. M., 245.Gilroy, G. P., 461.Gimesi, O., 454.Ginman, R. F. A., 203.Ginsberg, A. P., 186.Ginsburg, S. I., 468.Ginter, M. L., 106.Giraldi, G., 509.Girard, M., 488.Girdhar, H. L., 83.Gissane, W. J. M., 119.Gisser, H., 276.Giuffre, L., 456.Giuffrida, L., 495.Glarum, S. H., 56.Glasner, A., 152.Glass, M. A. W., 107, 199.Glasstone, S., 17.Gleinig, H., 271.Gleit, C. E., 474.Glemser, O., 147, 444.Glen, N.A., 294.Glew, D. N., 82, 179.Glocking, F., 141.Glockling, F., 166.Glonek, M. D., 164.Gloss, G. L., 281.Gloss, L. E., 281.Glotter, E., 300.Glukhov, I. A., 159.Gmelin, R., 299.Gnatz, G., 157.Gnauck, G., 449.Goates, J. R., 83, 94.Goatley, J. L., 364.Gobbett, E., 131.Gochman, C., 339.Godfredsen, W. O., 300.398.354.342.Godfrey, L. E. A., 279.Golles, F., 97.Goering, H. L., 213, 214,God, R., 148.Gothlich, L., 235, 269.Gotz, M., 349.Goetze, G. W., 502.Goetzee, W., 146.Gohlke, R. S., 496, 498.Gohring, J., 155.Goksoyr, J., 490.Gold, E. H., 335.Gold, H., 279.Gold, N. I., 432.Gold, V., 66, 67, 233, 246,Goldberg, A., 395.Goldberg, S., 65.Goldsby, J. D., 173.Golden, J.T., 240.Gol’der, G. A., 509.Goldfarb, T. D., 207.Gold’farb, Y. L., 276.Goldfinger, P., 100, 120,Goldin, A., 417.Golding, R. M., 46, 184.Goldman, G., 232.Goldschmid, H. R., 367.Gol’dshtein, A. L., 473.Goldstein, D., 441.Goldstein, G., 458, 461.Goldstein, I. J., 368.Gqldstein, J. H., 270, 327,Goldstein, M., 206.Goldwhite, H., 280.Goldzieher, J. W., 430.Goleb, J. A., 476.Goliasch, K., 314.Golightly, D. S., 162.Golovnya, V. A,, 153, 154.Goltzsche, W., 334.Gomel, M., 193.Gomer, R., 10.G6mez-IbQiiez, J., 96.Gonzalez, A. G., 277, 295.Good, C. D., 132.Good, R., 328.Goode, G. C., 468.Goodgame, D. M. L., 160,Goodgame, M., 160, 162,Goodman, G. L., 47.Goodman, L., 365,366,375.Gordon, A. W., 290.Gordon, G., 153.Gordon, L., 452.Gordon, R.D., 128.Gordy, W., 53, 109, 205,Goring, D. A. I., 97, 279,Gorman, M., 204, 353, 355.230.248.127.374.162, 163.163.206.365, 367.Gorokhovskaya, A. S., 487.Gorsich, R. D., 177.Gorsuch, T. T., 438.Gosset, J., 352.Goto, T., 358.Gots, J. S., 374.Gottbrath, J. A., 132.Gotthardt, H., 330.Gottlieb, 0. R., 300, 318.Gottschling, H., 373.Goubeau, J., 139.Goudmand, P., 102.Gough, J., 291.Goulian, M., 410.Gouterel, R., 205, 351, 355,Gover, T. A., 82.Govil, G., 203.Govindachari, T. R., 292,354, 358.Gracheva, E. P., 272.Gracias, 31. &I. T. K., 456.Graddon, D. P., 167.Grafer, P., 277.Graham, J. D., 194, 281.Graham, R. P., 438, 462Graham, W. H., 321.Graig, J. C., 330.Granchimont, E., 270.Grandmontagne, R., 114.Granick, S., 385, 387, 388,390, 393, 394, 395, 397,398.356.Grant, I.G., 301.Grant, I. J., 349.Grant, P. K., 295.Grant, L. R., jun., 144.Grant, W. K., 509.Grashey, R., 330, 337.Grasshoff, K., 483, 485.Grau, A., 206.Graves, J. M. H., 314.Graverman, I. J., 491.Gray, A., 339, 349.Gray, C. H., 394, 427.Gray, D. O., 325.Gray, H. B., 46, 47, 157,159, 163, 175.Gray, J., 42.Gray, J. A., 94.Gray, P., 267.Graybill, B. M., 132, 133.Green, B., 256, 257.Green, I. R., 459.Green, J. A., 20.Green, M., 252, 253, 398.Green, M. L. H., 183.Green, S. I. E., 130.Greene, F. T., 135.Greene, R. E., 154.Greenaway, F., 437.Greenberg, D. M., 407.Greenberger, M., 478.Greenblast, R.B., 429,Greenfield, S., 459, 474.433528 INDEX OF AUTHORS’ NAMESGreenhalgh, R., 478.Greenwood, C. T., 369.Greenwood, N. N., 137.Gregorowicz, Z., 454.Gregory, B., 314, 337.Greizerstein, W., 235.Greuter, F., 292.Griegel, R., 282.Griffin, G. E., 282.Griffith, H. O., 61.Griffith, W. P., 152, 160.Griffiths, D., 504.GrSths, D. E., 415.Griffiths, J. E., 140, 142.Griffiths, J. H. E., 46.Griffiths, J. V., 132.Griffiths, T. R., 61.Griffiths, V. S., 206, 485.Grimm, F. G., 425.Grim, S. O., 261.Grimes, R. N., 132.Grimwood, B. E., 280.Grinberg, A. A., 168, 175.Grindahl, G. A., 229.Grinstein, M., 394.Grisebach, H., 366.Grisolia, S., 425.Griswold, A. A, 198, 285,Griswold, E., 161.Gritter, R. J., 174.Grob, C.A., 218, 219.Grob, E. C., 274.Grobe, J., 177.Gronowitz, S., 201, 202,323, 324, 328, 330.Gros, F., 379, 380.Gross, D. G., 425, 426.Gross, H., 328.Grossman, R. F., 333.Grovenstein, E., 232.Gruber, W., 424.Gruen, D. M., 152, 164.Grune, A., 445.Gruenfelder, C., 20.Grun, H., 196.Grunberg-Manago, M., 37 1,Grundon, M. F., 346, 348.Grunwald, E., 207.Grunze, H., 376.Gual, C., 430.Guarino, J. P., 63.Gudzenko, Zh. D., 486.Guenebaut, H., 62.Gunther, H. L., 372.Guernet, M., 362.Guest, J. R., 406, 407.Giisten, H., 264.Guggenheim, E. A., 88, 90,Guilbault, G. G., 465.Guinn, V. P., 492.Guiseley, K. B., 365.Guisset, J.-L., 95.Guisti, P., 416.314.381.92, 94.Gunderloy, F. C., 133.Gundry, P. M., 14.Gunner, S.W., 359.Gunning, H. E., 283.Gunstone, F. D., 277, 294.Gunter, F., 402.Gupta, B. K., 111.Gupta, G. S., 294.Gupta, J., 483.Gupta, N. K., 420.Gurdjian, E. S., 466.Gurevich, A. I., 289, 318.Guriev, I. A., 473.Gurmnani, S., 404.Gurpide, E., 434.Gusev, S. I., 468.Gut, J., 375.Gut, M., 429, 430.Gut, R., 152, 164.Guthrie, R., 374.Guthrie, R. D., 366.Guthrie, S., 379.Gutmann, V., 171, 482.Gutowslry, H. S., 66, 71,Gutsche, C. D., 218, 241.Gutterson, M., 473.Guttman, L., 94.Guy, R. G., 179.GUZZO, A. V., 46.Gwina, W. D., 149.Gwinn, W. D., 192.Gysin, H., 320.Haahti, E. 0. A., 277.Haake, P., 165, 175.Haas, J. W., 486.Haas, W., 443, 453.Haase, B., 336.Habashi, F., 485.Habbousch, A. E., 449.Haber, H.S., 474.Haber, R. G., 223.Habermann, Z., 484.Habermehl, G., 356.Hebich, A., 237.Hachihama, Y., 369.Hackett, C. M., 237.Hackman, R. H., 447.Haendler, H. M., 157.Haenni, E. O., 444.Haerdi, W., 488.Hliring, W., 338.Hafner, K., 284, 314, 316.Hafner, W., 258.Hague, R., 485.Haguenauer-Castro, D.,Hahn, C.-S., 240.Hahn, E., 313, 342.Hahn, F. L., 466.Hahn, H., 138, 483, 485.Haiduc, I., 168.Haight, G. P., jun., 159.Kaim, A., 173, 174.Hainberger, L., 450.192.442.Haines, A. H., 363.Hai Won Chang, 281, 286.Hakomori, S., 365.H&la, E., 94.Halberstadt, M. L., 220.Hall, A. N., 246.Hall, B. D., 380.Hall, D. M., 232.Hall, G. E., 311.Hall, J. R., 376.Hall, J. H., 232, 244, 325.Hall, J. L., 63, 484.Hall, J.R., 282, 312.Hall, L. D., 201, 204, 364.Hall, N. D., 253.Hall, R. P., 270.Hall, W. B., 446.Halmann, M., 143, 217.Halousek, J., 500.Halpern, O., 305.Halsall, T. G., 296.Halsey, G. D., 88.Hamaguchi, H., 491.Hamans, H., 330.Hambling, J. K., 235.Hambly, A. N., 199.Hameka, H. F., 103, 330.Hamfelt, A., 495.Hamer, J., 332.Hamill, W. H., 63.Hamilton, G. A., 248.Hamilton, J. A., 293, 513.Hamilton, R. J., 377, 295.Hamilton, S. A., 301.Hamilton, W. C., 505.Hamlet, Z., 229.Hamlow, H. P., 399.Hamm, R. E., 461.Hammaker, G. S., 163.Hammer, G. G., 242.Hammond, G. S., 221, 239,241, 262, 283, 288.Hammond, J. B., 376.Hamner, A. J., 471.Hamolsky, M., 416.Hamor, T., 286.Hamor, T. A., 296,301,349,Harnrick, P., 53, 367.Hamway, P., 445, 494.Hanack, M., 284.Hanamura, S., 463.Hanania, G.I. H., 175.Hancock, J. W., 232.Hand, C. W., 20.Hand, E. S., 249.Handa, N., 370.Handschumacher, R. E.,Handler, P., 421.Hanessian, S., 365.Hanker, I., 341.Hannan, H. H., 151.Hansen, R. L., 253.Hansen, R. P., 275.Hansen, R. S., 12.512.375INHansen-Nygaard, L., 195,199, 202, 327. 329Hanson, A. W., 509.Hanson, J. R., 298.Hanst, P. L., 33.Hansing, C. E., 141.Han Toi, 480.Harada, H., 349.Harada, R., 302.Harbron, E., 254.Harburn, G., 503.Harcourt, R. D., 337.Harden, J. C., 499.Harding, A. J., 27.Harding, M. M., 514.Hardy, C. J., 155.Hardy, F. R. F., 32.Hardy, K., 322.Hare, C. R., 47, 159.Hargreaves, A., 507.Hargreaves, M.K., 189.Harley-Mason, J., 268.Harlow, G. A., 457, 471.Harman, K. H., 136.Harnden, M. R., 364.Harper, B. J. T., 343.Harper, K. A., 340.Harrar, J. E., 463, 464.Harris, B. W., 265.Harris, C., 280.Harris, C. M., 164, 166.Harris, D. L., 412.Harris, J. F., 201, 227.Harris, J. J., 134.Harris, E., 407.Harris, E. E., 337.Harris, M. M., 232.Harris, T. M., 264.Harrison, E. C. P., 188.Harrison, I. T., 200, 306,Harrison, P. M., 420.Harrison, S. E., 47.Hart, F. A., 162, 164.Hart, H., 209, 221, 240, 312.Hart, M., 502.Hart, P. A., 365.Hart, P. B., 167.Hartenstein, J., 148.Hartenstein, J. H., 285.Hartke, K., 267.Hartley, J. G., 161.Hartley, F. R., 152.Hartman, C. D., 12.Hartmann, D., 373.Hartmann, H., 94.Hartmann, R., 291.Hartmann, W., 328.Hartung, G. K., 498.Hartzler, H.D., 242, 281.Harvey, L. G., 477.Harwood, H. J., 274.Haschke, J., 166.Hasegawa, H., 201.Hasegawa, S., 368.Haselden, G. G., 98.355.EX OF AUTHORS’ NAMES 529Haskell, J., 429.Haskell, T. H., 339.Hassan, H., 232.Hasse, K., 335.Hassel, O., 82, 512.Hasserodt, U., 195, 281.Hassner, A., 227, 304, 330.Hatch, F. T., 406.Hatchard, C. G., 477.Hatfield, D., 375.Hatfield, W. E., 163.Hathaway, B. J., 167, 171.Hattori, K., 147.Haubenstock, H., 257.Hauge, S., 150.Hauptmann, H., 276, 320,Hauser, C. R., 264.Hausser, K. H., 52.Hauth, H., 348.Hawkins, C. J., 166.Hawkins, J. E., 297.Hawley, W. G., 455.Hawthorne, M. F., 131,132,Hawtin, P., 37.Hay, A.S., 269.Hayakawa, S., 305.Hayano, M., 430.Hayatsu, H., 376.Hayatsu, R., 337.Hayes, J. W., 488.Hayes, M. R., 478.Hayes, W., 46.Hayes, W. K., 291.Hayman, H. J. G., 82.Haymaker, C. R., 263, 276.Haynes, L. J., 296.Hays, H. R., 321.Hayter, R. G., 165, 186.Hazekamp, R., 51 1.Hazell, A. C., 148.Headridge, J. B., 454.Heaney, H., 311.Heard, D. D., 333.Heath, D. C., 101.Heath, D. F., 107.Heath, H., 391, 394.Heaton, B. G., 217.Heaton, J. W., 504.Heavey, H., 235.HBbert, G. R., 112.Hecht, I?., 492, 494.Hecht, H. G., 47.Hecht, R., 254.Heck, R. F., 176.Hecker, E., 278.Hedrich, G. W., 196.Hedrick, R. I., 253.Keeney, H. B., 476.Heeren, J. K., 261.Hegedus, D., 489.Hegre, C. S., 405.Heilbronner, E., 315, 316.Hehann, W., 485.Hein, F.R., 185.503.256.Heine, H. W., 279, 320.Heinecke, K., 178.Heinekey, D. M., 333.Heinemann, G., 216.Heintz, E. A., 158.Heinz, W. D., 152.Helbig-Neubauer, M., 163.Heldt, W. Z., 161.Helfferich, F., 171.Heller, C., 57, 205.Heller, H. G., 308.Heller, L., 477.Hellman, L., 431, 433, 434.Hellstrom, F., 417.Helmholz, L., 46.Helmkamp, G. K., 322,379.Helvenston, E. P., 163.Henbest, H. B., 220, 227,Henderson, A. T., 279.Hendler, R. W., 382.Hendra, P. J., 203, 206.Hendrickson, J. B., 343,351.Hendrickson, Y. G., 196.Henery-Logen, K. R., 322.Henkler, H., 258.Hennart, C., 455.Henninger, W. A., 491.Hennis, H. E., 254.Heppolette, R. C., 218.Herb, S. F., 275.Herber, R. H., 169, 495.Herberich, G.E., 183.Herbert, V., 407.Herbst, P., 271.Herbstein, F. H., 504.Herman, J. I., 178.Herman, L., 101, 120, 123,Herman, R., 120, 123.Herman, Z., 123.Hermans, J. J., 93.Hermsen, R. W., 97.Heriiandez Caiiavate, J.,Herout, V., 292.Herringshaw, J. F., 466.Herrington, T. M., 86.Herran, J., 348.Herrman, G., 179.Hersel, O., 319.Hersh, R. T., 423.Hershaft, A., 147.Hertz, H. G., 65, 71, 73.Herz, W., 200, 292, 294.Herzberg, G., 99, 100, 101,106, 107, 108, 109, 116,119.283.127.455.Herzog, S., 152, 156, 158.Heslop, R. B., 129.Hess, B., 420.Hess, P. H., 223.Hesselbarth, H., 137.Heubner, C. F., 357.Heusler, K., 256, 302, 305.HewIett, C., 145530 INDEX OF AUTHORS’ NATHeying, T. L., 135.Hey, D. H., 226, 232, 234,235, 265, 310, 311.Hiatt, H.H. 379, 380.Hickling, A., 143.Hickmott, T. W., 13.Hicks, W. T., 128.Hieber, W., 176, 177, 178.Higgins, P., 333.Higginson, W. C. E., 142,157, 171, 173.Highet, R. J., 343, 348.Hijmans, J., 93.Hikino, H., 292.Hikita, T., 20.Hilbert, P., 280.Hildebrand, J. H., 73, 74,78, 79, 81, 82.Hill, D. W., 437.Hill, H. A. O., 234.Hill, J. A., 143.Hill, J. W., 219.Hill, R. K., 219, 358.Hill, R. L., 396.Hill, S. A., 336.Hiller, M. A., 152.Hillman, M. J., 374.Hilton, I. C., 232.Hilton, J., 446.Hinckley, A. A., 132, 257.Hindman, J. C., 65.Hine, J., 207, 223, 242.Hine, R., 503, 514.Hine, R. A., 483.Hines, T., 68.Hinman, R. L., 326.Hinshelwood, Sir C. N., 27,Hirano, S., 371.Hiraoka, H., 78.Hirase, S., 369.Hirata, Y., 358.Hirota, E., 192.Hirota, N., 53, 57, 58, 61.Hirschfelder, J.O., 88, 114,Hirst, E. L., 370.Hishida, S., 250.Hitchcock, E. T., 473.Ho, J. C. K., 94.Hoare, D. E., 23, 27, 41, 42.Hoare, D. S., 391, 394.Hobbs, C. F., 220.Hobkova, E., 484.Hobson, J. D., 345.Hobson, J. P., 9, 10.Hoch, F. L., 423.Hocking, M. B., 333.Hockings, E. F., 47, 178.Hochmannovit, J., 292.Hochstein, F. A., 350.Hodge, J. D., 209, 285.Hodge, N., 151.Hodges, R., 201, 301, 318.Hodgkin, D. C., 402, 375,238.126.514.Hodson, H. F., 349.Hogenauer, G., 292.Hoegerle, R. M., 218.Hokfelt, B., 427.Hoeksema, H., 341.Hollerer, G., 139.Koppner, K., 142.Horner, L., 329.Hornfeldt, A.-B., 201, 202,Hoever, H., 282.Hover, H., 307.Hofer, P., 257.Hoffer, M., 374.Hoffman, P., 371.Hoffman, R.A., 201, 202,Hoffmann, A. K., 279.Hoffmann, C. J., 144.Hoffmann, D., 416.Hoffmann, D. E., 132.Hoffmann, H., 233, 261,Hoffmann, R., 131.Hoffmann, R. W., 235, 311.Hoffmeister, E., 235, 311.Hofheinz, W., 366.Hofman, T., 420.Hofmann, A., 352.Hofmann, A. F., 446.Hofmann, H., 332.Hogenaner, G., 200.Hogenkamp, H. P. C., 402.Holah, D. G., 171.Holder, B. E., 151.Holder, G. A., 96.Holden, K. G., 325, 393.Hole, F., 338.Holenaar, E., 340.Holland, G. J., 439.Holland, W. D., 474.Hollander, N., 430.Holleman, Th., 93.Holley, R. W., 382.Holliday, A. M., 136, 143.Holliman, F. G., 339.Hollinghead, S., 240.Hollis, B., 497.Ho116, J., 369.Holloway, H., 170.Holloway, P.W., 360.Holm, R. H., 165.Holmes, J. L., 236.Holmes, R. R., 145.Holmstrom, B., 320.Holmstrom, E. G., 429.Holness, N. J., 223.Holser, W. T., 506.Holt, A. S., 399.Holt, L. B., 394.Holt, P. F., 338.Holton, P. G., 201, 347.Holzbecher, Z., 477.Homann, P., 335.Homberg, K., 368.Homer, J., 363.323, 324.323, 324.472.ESHonyo, M., 417.Hook, S., 410.Hooton, K. A., 141, 166.Hope, H., 512.Hopkins, C. Y., 275.Hopp, M., 278.Hoppe, R., 130, 153, 161.Hoppe, W., 502.Hora, J., 303.HorGek, J., 473, 475.Horitk, V., 341.Hordvik, A., 359.Horii, Z., 358.Horl, W., 182.Hormanski, M., 415.Horn, D. H. S., 278, 297.Horner, L., 261, 264, 316,Horner, S. M., 159.Horning, E.C., 277.Horsfield, A., 53, 54, 55, 56,Horst, R. B., 54.Hort, J., 328.Horton, A. D., 448.Horton, D., 367, 368.Horton, G. R., 499.Horwatitsch, H., 473, 474.Horyna, J., 482.Hoskins, B. F., 163.Hoakinson, R. M., 363.HoBialek, Z., 458.Hoste, J., 452, 489, 490,Hougen, J. T., 118.Hough, L., 201, 204, 361,363, 364, 370.Houk, N. B., 122.House, D. A., 172.House, H. O., 260.Houser, J. J., 209.Hovenkamp, S. G., 507.Hover, H., 281.Howald, R. A., 253.Howard, C. C., 322.Howard, E., jun., 146.Howard, J. W., 444.Howard, W. L., 320,Howe, C. A., 236.Howe, L. L., 100, 101.Howell, C. F., 286.Howick, L. C., 452.Hoyle, W., 440.Hozumi, K., 474.Hrdina, J., 447.Hristidu, Y., 183.Hruky, V. J., 242.Hubbard, N., 395.Hubbard, W.N., 196.Huber, C. O., 471.Huber, K. P., 116, 125.Huber, W., 459.Huber-Buser, E., 287.Huber-Emden, H., 267.Huculak, W. W., 256.Huckel, W., 290.446.57.491, 492, 493, 495INDEX OF AUTHORS’ NAMES 53 1Hudda, F. G., 11, 12.Hudec, J., 197,285,289,309.Hudson, B., 433.Hudson, B. G., 452.Hudson, F. M., 233.Hudson, G. H., 90.Hudson, H. R., 133.Hudson, P., 509.Hudson, R. F., 219, 252,Hudson, R. L., 35.Hubernett, F., 332.Hubner, L., 171.Huttner, W., 192.Huffman, K. R., 338.Huffman, J. W., 258.Hughes, A. N., 338.Hughes, C., 343.Hughes, D. O., 504, 506.Hughes, D. W., 399.Hughes, E. D., 218, 238.Hughes, E. W., 283, 509.Hughes, N. A., 360.Hughes, R. H., 101.Hughes, S. A., 235.Hugo, T. J., 106.Huisgen, R., 312, 323, 330,332, 333, 337.Huitric, A.C., 196, 197.Huka, M., 469.Hukue, N., 277.Hulanicki, A., 449.Huizinga, F., 383.Hulburt, H. M., 114.Hulme, R., 51, 142, 511.Hulthhn, E., 100, 104.Humber, L. G., 357.Humberlin, R., 238.Hume, D. N., 482.Humphreys, S. R., 417.Hung Yu Chen, 480.Hunneman, D. H., 334.Hunt; J. A., 381.Hunt, J. H., 263.Hunt, 5. P., 68.Huntsman, W. D., 270.Hunter, G. J., 495.Hunter, M. J., 249.Hurley, A. C., 113, 121.Hurlbert, B. S., 358.Hurst, G. L., 138.Hurst, J. J., 213.Hurst, P., 37.Hurzeler, H., 125.Hush, N. S., 175.Hutchinson, D. A., 56.Hutchison, C. A., 60.Hutchison, C. A., jun., 63.Hutchison, R. B., 318.Hutton, D. G., 37.Hutton, H. M., 281.Hutton, R. F., 334.Hyde, A.J., 160.Hyde, J. S., 54.Hylton, T. A., 165.Hyne, J. B., 217.253, 254.Iball, J., 503, 509.Ibanez, L. C., 305.Ibers, J. A., 47, 163, 179.Iberson, E., 164.Ibne-Rasa, K. M., 224.Ichimescu, A., 120.Ide, Y., 481.Idris Jones, J., 137.Iino, N., 278.Ikekawa, N., 356.Ikenoue, K., 126.Ilakovac, N., 223.Il’in, V. T., 30.Illuminati, G., 231.Imamura, A., 83.Imri;, P., 499.Inch, T. D., 366.Inghram, M. G., 125.Ingle, R. B., 455.Ingles, D. L., 360.Inglis, G. R., 362.Ingold, C. K. (Sir), 207,218,Ingold, K. U., 199, 254.Ingraham, L. L., 187, 207.Ingram, D. J. E., 47.Inman, D., 167, 472.Innes, K. K., 106.Inomata, Y., 478.Inoue, M., 275.Inoue, T., 265.Inoue, Y., 339.Inukai, T., 219.Inward, P. W., 227.Ireland, R.E., 264, 296,Irudayasamy, A., 441.Irvine, D. H., 175.Irving, H., 170.Isbell, H. S., 359, 360, 361,Isenberg, H. D., 403.Isenberg, I., 62.Isensee, H. J., 499.Ishima, A., 380.Isler, O., 274.Issleib, K., 140, 163, 166.Ito, J., 71.Ito, K., 165.Ito, M., 281.Ito, T., 367.Ito, Y., 368.Itoh, K., 57, 206.Ivanov, 0. A., 24.Ivanov, V. M., 455.Ivanova, T. M., 97.Ivanov-Emin, B. N., 138,Iverach, G. G., 357.Ives, D. J. G., 97.Iwai, I., 360.Iwamoto, R. T., 167.Iwamoto, T., 454.Iwasawa, J., 298.Iwashige, T., 360.Iwatsubo, M., 425.222, 238.298, 302.496.152.Izsak, D., 191, 192.Jaccard, C., 55.Jackerts, D., 372.Jackman, L. M., 198, 273,277, 286, 296, 307, 318.Jackman, M. I., 485.Jackson, A. H., 323, 392.Jackson, H., 444.Jackson, J.A., 67.Jackson, J. E., 429.Jackson, J. F., 417.Jackson, P. W., 411.Jacob, F., 379.Jacobs, G. D., 192.Jacobs, S., 475.Jacobs, W. A., 357.Jacobsen, E., 460.Jacobson, I. A., 324.Jacobson, M., 278.Jacques, J. K., 121.Jager, H., 230.Jaenicke, L., 407.Jaenicke, R., 424.Jaenicke, W., 472.Jaff6, H. H., 240.Jailer, J. W., 432.Jain, B. D., 450, 451, 479.Jain, D. C., 112, 114, 116.Jalkowski, J. F., 490.James, A. T., 274.James, C., 270.James, H., 26.James, M. R., 94.James, T. C., 113.Jamieson, J. C., 501.Janak, J., 448.Jander, J., 143, 151.Jangida, 13. L., 444, 478.Janot, M.-M., 204, 205, 351,Janssen, M. J., 142.Janzen, E. G., 49.Jardetzky, C. D., 205, 418.Jardetzky, O., 71.Jarlsiiter, N., 104.Jarmain, W.R., 111, 112,Jarman, L., 488.Jarvis, J. A., 368.Jarvis, J. A. J., 512.Jaseja, T. S., 53, 205.Jastrow, H., 271.Jayle, M. F., 427.Jeanloz, R. W., 365.Jeannin, Y., 155.Jeffcoat, K., 463.Jefferies, P. R., 278, 298.Jefford, C. W., 240, 338.Jeffrey, G. A., 508.Jeffs, P. W., 343.Jeger, O., 305.JehliEka, V., 482.Jellum, E., 456.Jen, C. K., 57.Jen, M., 191.352, 353, 354, 356.113532 INDEX OF AUTHORS’ NAMESJenc, E., 113.Jenckel, L., 497.Jencks, W. P., 245, 247,248, 249, 252.Jenkins, D. R., 207.Jenkins, F. A., 101.Jenkins, R. W., 209.Jennings, H. J., 365.Jennings, V. J., 453, 467,Jensen, F. R., 196, 282.Jensen, H. B., 324,Jensen, J., 396.Jensen, L. H., 503,504,506,Jensen, S.L., 271, 274.Jenssen, B., 273.Jere, G. V., 155.Jeunehomme, M., 127.Jewell, D. M., 498.Jha, N. K., 161.Jibnil, A., 416.Jira, R., 258.Jirgensons, B., 425, 426.Jirka, M., 487.Jirkovskjr, I., 346.Jizba, J., 292.Job, B. E., 192.Jobsis, F., 418.Joe, F. L., jun., 444.Jorgensen, C. K., 164.Johannesen, 1.-J., 150.Johannesen, W., 150.Johansson, N., 100, 104.John, J. P., 287.John, K., 145.Johns, H. E., 372.Johns, J. W. C., 101, 121.Johns, R. B., 341.Johnson, A. W., 314, 331,337, 375, 389, 402, 409,411.489.509.Johnson, B. C., 403, 404.Johnson, B. F. G., 178.Johnson, C. M., 109.Johnson, C. R., 260.Johnson, D. L., 280.Johnson, D. W., 219.Johnson, E. A., 232, 233.Johnson, F., 334.Johnson, F. A., 54, 144.Johnson, 0.R. A., 42.Johnson, H. E., 265, 279.Johnson, H. W., jun., 286.Johnson, L. F., 203, 296,Johnson, Le R. F., 297.Johnson, M. D., 207, 338.Johnson, R. C., 175.Johnson, R. D., 223.Johnson, R. W., jun., 196.Johnson, S., 139, 232, 319.Johnson, 5. L., 247, 248.Johnson, W. S., 196, 224,Johnston, G. A. R., 210.365.267, 306, 355.Johnston, J. D., 288, 318.Johnston, N. C., 277.Jolly, W. L., 139, 141, 148.Jones, D., 184.Jones, G. R. H., 44.Jones, G. W., 20, 21, 373.Jones, H. C., 482.Jones, H. G., 359.Jones, J. H., 37.Jones, J. K. N., 359, 360,365, 366.Jones, J. M., 252.Jones, K., 142.Jones, M., jun., 200.Jones, M. M., 233.Jones, M. R., 88.Jones, M. T., 60.Jones, N. D., 512.Jones, 0. W., 381.Jones, P.D., 478.Jones, R. A. Y., 64, 189,Jones, R. C., 51.Jones, R. H., 170.Jones, R. L., 193.Jones, R. N., 191.Jones, W. A., 278, 329, 447.Jones, W. M., 227, 252.Jongerius, H. M., 120.Jordan, J., 161.Jordan, T., 230, 507.Jorgensen, C. K., 46.Jorgenson, M. J., 257.Jortner, J., 63.3osefsson, L., 466.Joseph, A., 460.Josephson, R. R., 214.Joshi, K. C., 119.Joshi, K. K., 177, 183.Joshua, C. P., 333.Josse, J., 373, 378.Jost, E., 262.Joule, J. A., 348, 355.Joullie, M. M., 335.Joyce, B. K., 425.Joyner, T. B., 163.Juardo-Soler, A., 362.Julia, M., 270, 273, 274.Julia, S., 273.Julietti, F. J., 280.Julita, P., 411.Jungalwela, F. B., 274.Jungermann, E., 261, 323.Jurale, J. B., 219.Jursa, A. S., 123.Jutz, C., 314.Kabasakalian, P., 267, 287.Kabat, E.A., 368.Kabuss, S., 204.Kacmarczyk, A., 131.Kacmarek, A. J., 147.Kader, A. R., 216.Kaeding, W. W., 263.Kagi, W., 219.203, 338.Joschek, H.-I., 265.Kagan, F., 263.Kagan, G. I., 190.Kagawa, Y., 415.Kagi, H. H., 287.Kagi, J. H. R., 423,Kahn, N. H., 357.Kahn, R. K., 378.Kahnt, F. W., 429.Kainz, G., 473, 474.Kaiser, E. T., 248.Kaiser, H., 316.Kakihara, N., 20.Kakisawa, H., 290, 302.Kalinin, A. I., 485.Kalinowska, Z. E., 465.Kallen, R. G., 374.Kalman, Z. H., 477.Kalsi, P. S., 290.Kalvoda, J., 305.Kamal, M. R., 95.Kamata, H., 345.Kambara, S., 155.Kampmeier, J. A., 235,Kan, R. O., 232, 337.Kanamori, K., 454.Kanda, T., 68.Kandalic, G. A,, 97.Kandel, S.I., 343.Kandler, J., 164.Kane, P. O., 482.Kanekar, C. R., 203.Kaneko, T., 345.Kanjpr, H., 338.Kaniecki, T. J., 263.Kanthamani, S., 355.Kapallo, W., 96.Kapbtanidis, I., 468.Kaplan, A. M., 478.Kaplan, J., 125.Kaplan, N. O., 413, 415,416, 417, 418, 419, 421,424.311.Kapoor, A. L., 512.Karabatsos, G. J., 194, 217.Karapetyan, M. G., 289,Karetskaya, N. I., 346.Karimoto, R. S., 331, 358.Karle, I. L., 503, 508.Karle, J., 503.Karlbn, B., 194.Karmalkar, P. K., 82.Karmen, A., 495.Karmilova, L. V., 28, 29,Karpathy, 0. C., 448.Karplus, M., 50.Karrer, P., 273.Kartha, G., 503, 512.Kasai, P. H., 62.Kase, N., 428, 429.Kaska, W. C., 266, 334.Kasteleyn, P. W., 94.Kasturi, T. R., 256.Katayama, M., 53, 206.318.30INDEX OF AUTHORS' NAMES 533Katayama, T., 97.Katchalski, E., 253.Kates, M., 274.Kats, N., 358.Katritzky, A.R., 64, 189,203, 232, 324, 332, 336,338.Katsuhiko Ichikawa, 233.Katti, M. R., 114.Katz, F. H., 432.Katz, I., 274.Katz, J. J., 325.Katz, T. J., 228, 282, 283,312, 314.Kau, H., 484.Kauer, E., 96.Kauffmann, T., 235, 258,330, 335.Kaufman, F., 43.Kaupp, G., 332.Kawai, K., 175.Kawanisi, M., 277.Kawasaki, I., 345.Kawazoe, Y., 201.Kay, I. T., 325.Kay, J. G., 102.Kaziro, Y., 404.Kealey, T. J., 338.Keefe, J. R., 253.Keefer, R. M., 82, 217, 220,Keeler, B. T., 487.Keeler, R. N., 89.Keen, N., 65, 56.Keeney, M., 274.Kehlen, H., 95.Keijer, J. H., 340.Keller, C., 446.Keller, H. J., 183.Keller, R.A., 448.Kellerman, G. M., 404.Kellermeyer, R. W., 405.Kellie, A. E., 433.Kelly, H. C., 139.Kelly, W. G., 431.Kempton, A. G., 478.Kende, H. J., 399.Kende, I., 34.Kenner, G. W., 323, 332,Kenney, M. E., 137.Kenney, T. E., 190.Kent, P. W., 365.Kenty, C., 123.Keresztesy, J. C., 407.Kern, R. J., 223.Kerr, J. R. W., 496.Kerwin, J. F., 303.Kerwin, L., 128.Kesser, S. IT., 338.Ketova, L. A., 468.Ketteringham, J. M., 126.Kettle, S. F. A., 177.Keuning, R., 275.Kevill, D. N., 223, 224.Kewley, R., 207.226, 233.338.Kezdy, F., 248.Khabibullin, B. M., 72.Khachishvili, V. I., 131.Khalique, A., 360.Khan, B. T., 427.Khan, M. A., 127, 448.Khan, I. A., 177.Khandelwal, B. L., 458.Khanna, B. N., 128.Kharasch, N., 188,235,269.Khazanova, N.E., 98.Khazova, I. P., 441.Khdanov, G. S., 509.Khetrapel, C. L., 203.Khodeeva, S. M., 98.Khopkar, S. M., 443.Khorana, H. G., 376, 377,Khorana, M. L., 300.Khorlina, I. M., 262.Khoroshin, A. V., 486.Khudyakovg, T. A., 459.Khu Khun-ven, 230.Khuong-Hu, Q., 356.Khym, J. X., 377.Kibbel, H. U., 136.Kibly, C. K., 132.Kida, S., 172.Kidd, R. G., 171.Kiefer, E. F., 210.Kielar, E. A., 348.Kielich, S., 92.Kierstead, R. C., 296.Kies, H. L., 458, 462.Kiese, M., 396.Kiess, N. H., 116.Kihara, T., 89.Kikino, Y., 292.Kikuchi, G., 386.Kikuchi, K., 316.Kikumoto, R., 350.Killean, R. C. G., 513.Killheffer. J. V.. 261. 323.378.Killick, R. A., 490. 'Kilzer, J., 350.Kim, Y. S., 229.Kindler, K., 323.King, A.B., 123.King, A. D., 92.King, D. M., 472.King, G. W., 128.King, N. J., 370.King, P. A., 224.King, W. R., 95.Kingston, A. E., 89.Kingston, W. R., 169.Kinsey, J. L., 19.Kirby, G. W., 343.Kircher, H. W., 364.Kirei, G. G., 207.Kirk, A. D., 31.Kirk, D. N., 306.Kirk, K., 285.Kirkien-Konasiewicz,Kirkland, A., 364.253.Kirksey, C. H., 338.Kirkwood, J. G., 84.Kirkwood, S., 367.Kirschfeld, S., 373, 403,Kirschner, S., 171.Kirsten, W. J., 474.Kishida, Y., 294.Kiss, S. A., 470.Kister, A. T., 98.Kistiakowsky, G. B., 19,Kitaigorodski, A. I., 506.Kitao, T., 336.Kitaoka, S., 368.Kitaoka, Y., 336.Kiuvila, H. G., 233.Kivelson, D., 58, 59.Kjaer, A., 279, 331.Kjerlberg, O., 370.Klanberg, F., 137.Klassen, hT.V., 232, 233.Klavins, J. E., 362.Klein, E., 289.Klein, J. R., 395.Klein, M. J., 147.Klein, O., 113.Klein, P. D., 444.Kleinberg, J., 181, 227.Kleine, K.-M., 271.Kloinert, H., 330.Kleinfetter, D. C., 209.Kleinman, L., 604.Kleinschmidt, A., 378.Kleman, B., 106, 119.Klemer, A., 368.Klemm, W., 161.Klenow, H., 417.Klesper, E., 151.Kliever, M., 403.Klinedinst, P. E., 335.Klinedist, P. E., 214.Klinedist, P. E., jun., 416.Kling, O., 158.Klingelhoefer, W. C., 465,Klingsberg, E., 319, 333.Klink, W., 261.Klonowski, R. S., 322.Klopman, G., 219.Kloster-Jensen, E., 270.Klug, E. D., 369.Klyne, W., 197, 256, 298.Klynning, L., 127.Knaap, H. F. P., 86, 87.Knappe, J., 330.Knessl, O., 480.Knight, C., 394.Knight, C.S., 448.Knight, H. T., 128.Knight, J. C., 256.Knight, S. A., 289.Knipmeyer, H. E., 196.Knipple, W. R., 176.Kniseley, R. N., 193.Knobler, C. M., 87.Knobler, C., 103.409.20, 241534 INDEX OF AUTHORS’ NAMESKnoester, M., 87.Knoke, J., 335.Knorr, R., 312.Knoth, W. H., 131.Knowles, A., 286.Knowles, J. W., 502.Knowles, P., 157.Knox, G. R., 230, 258.Knox, J. H., 22, 31, 32, 33,Knox, J. R., 278.Knox, K., 46, 158.Knuppen, R., 433.Knyazev, D. A., 494.Kobayashi, H., 299.Kobayashi, S., 302.Kobayashi, T., 350.Koch, H. J., 271.Koch, W., 232, 278.Kochetkov, N. K., 331, 346.Kocor, M., 290.Kodera, K., 358.Kobrich, G., 230, 261.Koechlin, W., 268.Koehelik, I. H., 403.Koehler, W. R., 320.Konig, H., 230.Konlg, K., 142.Konigk, E., 374.Koffman, L., 100, 104.Kofler, M., 274.Kofman, A.N., 98.Kofron, W. G., 264.Kogan, E. A., 97.Kohler, F., 90.Kohlhage, H., 376.Kohlschutter, H. W., 136,Kohn, J. P., 98, 99.Kohnstan, G., 214,217, 218Koizumi, K., 367.Kojha, T., 195.Kokeritz, P., 199.Kokko, J. P., 374.Kokot, E., 166.Kolat, R. S., 152.Kolb, A., 341.Kolbasov, V. I., 480.Kolbe, A,, 95.Kolbin, N. I., 161.Kolditz, L., 147.Kolesnikova, R. V., 43, 44.Kolewe, O., 246.Kolinskii, R., 269.Kolos, W., 113.Kolosov, M. N., 318.Kolysko, L. E., 91, 95.Kompa, K. L., 144.Kon, S. K., 411.Konaka, R., 260.Kondo, K., 277.Kondo, N., 380.Kondrashev, Yu. D., 507.Kondratiev, V. N., 25, 26.Konereva, G. P., 32.Konf PO Mirnomu, 369.34, 35.168, 422.Konigsberg, W., 333.Konowalow, D.D., 126.Kopanica, M., 441, 484.Kopecky, K. R., 241, 262.Kopp, I., 127, 128.Koppel, H. C., 339, 374.Kopple, K. D., 174.Koransky, W., 376.Korbl, J., 473.Koreshkov, Yu. D., 322.Korkisch, J., 483.Kormendy, C. G., 335.Korn, J. K., 136.Kornberg, A., 373,374, 378.Kornberg, S. R., 373.Kornblum, N., 279.Kornis, G., 300.Korte, F., 195, 281.Korst, J. J., 288, 318.Korving, J., 86.Korwar, V. M., 112.Kosak, J. R., 240.Kosel, C., 258, 330.Koshijima, T., 370.Kosicki, G. W., 246.Koski, W. S., 205.Kosower, E. M., 187, 229,281, 335, 413, 416, 418,423.Koster, G. F., 46.Kotake, M., 345.Kotera, K., 198.Kotzian, H., 455.Koubeck, E., 186.Kovacic, P., 233.KOVACS, I., 107, 117, 118.Kovalenko, P.M., 481.Kovalskii, A. A., 26.Kovar, J., 344.Kowkabany, G. N., 359.Kowal, J., 428.Kowalski, E., 388.Kozak, G. S., 465.Kozima, T., 299.Krall, R. E., 253.Kramer, D. N., 465.Kramer, K., 139.Kramer, K. S., 475.Krapcho, A. P., 219, 279.Krasinski, A. H. A., 277.Krasna, A. I., 411.Kratochvil, M., 328.Kratzer, O., 274.Krauch, C. H., 328, 340.Kraus, J. W., 179.Krauss, H.-L., 157, 159.Kraut, J., 503, 514.Krebs, A., 286.Krebs, E. G., 414.Kreevoy, M. M., 222, 269.Kreibach, A., 166.Kreienbring, F., 365.KFepinskjr, J., 292.Kresge, A. J., 233.Kreshkov, A. P., 457, 462.Krespan, C. G., 323.Kretsinger, R. H., 514.Kretszchner, R., 417.Krichevskii, I. R., 98.Krijn, G.C., 451.Krilrorian, 0. H., 128.Krhm, S., 192.Krischke, R., 337.Krishnamurti, M., 269.Kritsyn, A. M., 346.Krivoglaz, M. A., 504.Krohnke, F., 309, 335.Kroger, C., 38.Kroh, J., 49.Krohs, W., 319.Kronenberger, K., 482,497.Kruck, T., 177.Kruger, C. R., 140.Krueger, P. J., 193.Krueger, R. C., 395.Kruh, J., 380.Krumholz, P., 175.Kruse, F. H., 154.Kruseman Aretz, F. E. J.,Kubo, H., 425.Kubo, M., 165.Kubota, T., 295.Kucan, D., 303.Kuchen, W., 146.Kuck, A. M., 347.Kuckertz, H., 140.Kuczynski, E. R., 463.Kuebler, N. A., 102.Kuehner, E. C., 440.Kung, W., 219.Kiinzel, O., 182.Kuffner, F., 268.Kuge, T., 369.Kugel, L., 143.Kuhn, R., 272.Kuhn, S. J., 232, 233, 268.Kukushkin, Yu. N., 175.Kulanek, M., 95, 96.Kul’ba, F.Ya., 138.Kul’borskaya, N. K., 272.Kuljian, A., 427.Kulkarni, B. D., 355.Kumar, A., 386.Kumar, S., 153, 450.Kumazawa, Z., 298.Kumler, W. D., 193, 194,Kump, C., 354.Kump, W. G., 354.Kun, E., 246.Kunchur, N. R., 168.Kung, W., 287.Kunin, R., 447.Kunkel, W. B., 123.Kuno, S., 373.Kuo, C. H., 318.Kuo, M. C. C., 320.Kupchan,, S. M., 250, 306.Kupfer, D., 257.Kuri, Z., 51.Kuriakose, A. K., 231, 270.94.246Kurihara, T., 278.Kurita, Y., 165.Kurland, C. G., 379.Kuroda, R., 491.Kursanov, D. N., 322.Kurtz, P., 269.Kurz, H., 396.Kurzer, F., 279, 333.Kusch, K., 431.Kushner, D. J., 274.Kusomoto, S., 345.KUSSY, M. E., 444, 492.Kustin, K., 246.Kuteinkov, A. F., 454.Kutek, F., 458.Kutschke, K.O., 40, 236.Kutsenko, Yu. I., 154.Kutzelnigg, W., 194.Kuwama, T., 60.Kuzel, P., 183.Kuznetsova, N. L., 44.Kuzyakov, Yu. Ya., 127.Kwart, H., 197, 237, 284.Kwie, W. W., 304.Kydd, P. H., 20.Kyogoku, Y., 372, 379.Kyryacos, G., 32.Labbe, R. F., 393, 395.LabbB, J. P., 450.Lacher, J. R., 282.Lack, R., 201.Ladd, J. N., 401, 402.Ladd, M. F. C., 169.Ladeinova, L. V., 155.Laffitte, P., 37.Lagerkvist, U., 382.Lagerqvist, A., 101, 106,116, 124, 128.Lai, M. G., 495.Laidler, K. J., 17.Laine, F., 356.Laitinen, H. A., 459.Lakom9, J., 459.Lakshmikanthan, M. IT.,Lamantia, L., 417.Lamb, D. C., 277.Lambert, M., 86.Lamberton, J. A., 278.Lamborg, M. R., 416.Lampetaz, J.-C., 442.Lamprecht, W., 437.Lamyaeva, V.N., 184.Lancaster, J. E., 366.Landau, R., 258.Lander, A., 185.Lander, W. R., 480.Landor, S. R., 272.Landry, B. J., 233.Lane, A. P., 145.Lane, C. A., 224.Lane, M. D., 405.Laney, D. H., 263.Lang, A. R., 502.Lang, D., 229, 378.358.INDEX OF AUTHORS’ NATLangan, T. A., 418.Langford, C. H., 162.Langford, P. O., 162.Langley, B. W., 299, 359.Langworthy, W. C., 230.Lansbury, P. T., 257.Lanskoi, G. A., 454.La Paglia, S. R., 107.Lapinski, R., 246.Lapisova, N. P., 473.Laplante, J. P., 485.Laporte, H., 175, 182.Lapp, M., 110.Lappert, M. F., 131, 133,142, 156.Lapworth, A., 232.Larionova, L. E., 138, 152.Larkin, J. A., 93, 95.Larkworthy, L. F., 143.Larrabee, A. R., 406, 407.Larroqube, J., 421.Lascelles, J., 386, 388, 409.Lassner, E., 441, 455.Laszlovsky, J., 441.Lathan, R., jun., 155.Latif, N., 321.Latscha, H. P., 148.Lattermann, H., 438.Laubengayer, A.W., 137.Laug, P., 303.Laune, J., 196.Lauritzen, C., 427.Laursen, R. A., 373.Laver, M. L., 370.Laver, W. G., 386.Lavie, D., 300.Law, H. D., 332.Law, J. T., 13.Law, P. A., 209.Lawley, D., 373.Lawrence, R. V., 297.Lawrey, D. M. G., 497.Lawson, A. W., 501.Lawson, D. D., 446.Layne, D. S., 430.Layton, R., 165.Lazar, J., 224.Lazarova-Girsamof, V.,Leake, L. R., 466, 470.Learner, R. C. M., 113, 116.Le Bargy, R. C., 124.Lebedeva, A. I., 475.Lebedeva, A. S., 346.Lebedeva, E. S., 98.LeBel, N. A., 224.LeBel, R. G., 97.Leboeuf, M., 355.Leckie, A. H., 125.Lecomte, J., 198.Le Count, D.J., 354.Leddicotte, G. W., 489.Lederer, E., 278.Ledwith, A., 219.Lee, C. C., 213.Lee, C. M., 193, 336.128.ES 535Lee, E. E., 367.Lee, E. K. C., 494.Lee, H. A., 403, 409.Lee, H. A., jun., 420.Lee, H. Y., 482.Lee, J. K., 494.Lee, J. S., 497.Lee, K. T., 440.Lee, M. N., 400.Lee, W. G., 224.Lee, W. H., 169.Lee, W. W., 375, 424.Leermakers, P. A., 241.Leete, E., 342.Lefebvre, C., 95.Lefebvre-Brion, H., 1 13.Le Fkvre, R. J. W., 190,191, 192, 199, 201, 203.Le Goff, E., 235, 283, 311,315.Legrand, M., 200.Le Gras, J., 272.Lehar, L., 459.Lehman, I. R., 373.Lehmann, G. J., 242.Lehmann, H.-A., 137.Lehma.nn, J., 363, 366.Lehmann, W. J., 132, 135.Lehn, J.-M., 200, 303.Lehr, W., 146.Leibnitz, E., 34.Leicht, C.L., 350, 351.Leies, G. M., 115.Leigh, G. J., 141, 155.Leigh, K., 197.Leigh, R. T., 142.Leland, T. W., 98.Leliaert, G., 492.Lelov, N. F., 505.Le Men, J., 204, 205, 351,352, 353, 354.Lemieux, R. U., 365, 418.Lemons, J. F., 67.Lengnick, G., 137.Lengyel, P., 381, 404.Lenkert, P. G., 375, 402.Lenzer, S. L., 166.Leonard, G. W., 483.Leonard, J. A., 232, 234,Leonard, J. E., 467.Leonard, N. J., 260, 342,Leonov, V. N., 306.Lepard, D. W., 190.Lerch, A., 242.Lerwill, B. R., 142.Lesigang, M., 494.Leskowitz, S., 368.Leslie, R. T., 440.Lesnevskaya, L. S., 98.Lester Smith, E., 409.Letort, M., 30, 31.Letsinger, R. L., 252.Levenson, L. L., 9.Lever, A. B. P., 162.235, 310, 311.373536 INDEX OF AUTHORS’ NALevelt, J.M., 88.Levin, P. L., 32.Levine, C. A., 491.Levine, I. N., 194.Levine, L., 419.Levine, S., 365.Levinskii, M. I., 486.Levisalles, J., 200.Levisalles, J. E. D., 293.Levitan, I. O., 198, 200.Levitus, R., 172.Lewandowski, K. M., 208.Lewin, A. H., 197.Lewin, N., 294.Lewis, C. H., 139.Lewis, D. T., 496.Lewis, E. S., 233.Lewis, J., 154, 158, 162,Levy, A., 21, 416.Levy, J. F., 213.Levy, J., 352.Li, T. K., 420.Libergott, E., 441, 442.Lichten, W., 118.Lichtenthaler, F. W., 280.Lichtin, N. N., 362.Lide, D. R., 121, 1189, 190,Lide, D. R., jun., 190.Liebe, W., 153.Lieberman, S., 429, 430,Lieberman, S. L., 434.Liede, V., 327.Liehr, A. D., 168.Lieser, K. H., 136.Lightner, D.A., 291.Lightowlers, E. C., 491.Likhosherstov, A. M., 346.Liljegren, D. R., 350.Lilly, R. L., 308.Limanov, V. Y., 306.Lindberg, B., 360, 368.Lindberg, J. J., 97.Linde, H., 446.Lindgren, B., 127.Lindner, E., 176, 178.Lindner, H. R., 428.Lindqvist, S., 119.Lindsey, J., 514.Linevsky, M. J., 103.Linford, H. B., 460.Linnenbom, V. J., 449.Linnett, J. W., 100, 114,Linstrom, F., 454.Lions, F., 172.Lipman, M. M., 432.Lipmann, F., 382.Lipowitz, J., 250.Lippincott, E. R., 113, 114,130, 190.Lipscomb, W. N., 131, 132,181, 230, 501, 502, 507,512.167.191, 193.431, 432, 433.131.Lipsett, M. B., 427, 428.Liptay, G., 500.Liptay, W., 82.Lis, A. W., 376.Lischlre, G., 34.Lisitsa, M. P., 207.Lissitzky, S., 494.Lister, J.H., 320.Little, E. L., jun., 279.Little, W. F., 250.Littlehailes, J. D., 302.Liu, I. D., 23.Livingston, R., 47, 55.Livingstone, J. G., 185.Livingstone, S. E., 165, 172.Ljunglin, J. J., 95.Llewellyn, F. J., 164.Lloyd, H. A., 348.Lloyd, I. R. L., 361.Lobaneva, 0. A., 162.Lock, C. J. L., 160.Lockhart, J., 210, 281.Lockhart, J. C., 135.Locksley, H., 300.Lockwood, W. H., 390.Lockyer, T. N., 166.Lodemann, E., 372.Loder, J. W., 292.Lodish, H. F., 204, 354.Loeb, A. L., 506.Loebeck, M. E., 374.Loeffler, L. J., 348.Loewenstein, A., 269.Loewenthal, H. J. E., 294,Lofthus, A., 122.Loginov, G. M., 156.Lohmann, D. H., 130, 165Lohning, U. E., 380.Loley, F., 490.Lombaert, R., 490.Long, F. A., 246, 316.Long, L., jun., 365.Long, L.H., 185.Longo, J., 161.Longone, D. T., 200, 258,Longuet-Higgins, H. C., 47,Lonsdale, K., 504.Lontz, R. J., 53.Lord, R. C., 195.Lordi, N. G., 488.Lorentso, R. V., 21.Lorenz, M. R., 138.Lorenz, O., 457.Los, M., 297, 318.Lott, K., 47.Loubser, J. H. N., 192.Loudon, J. D., 308.Louloudes, S. J., 277.Love, D. L., 495.Loveday, G. W., 246, 362.Loveridge, B. a., 494.Lovins, R. E., 217.Low, D. I. R., 96.298.317.59, 81.ESLowde, R. D., 504.Lown, J. W., 200.Lowry, B. R., 288.Lowry, 0. H., 414.Lu, B. C.-Y., 94.Luborsky, S. W., 378.Lucas, J., 154.Lucquin, M., 38.Luddy, F. E., 275.Ludoweig, J., 416.Ludwig, M. L., 249.Ludwig, P., 48, 60.Luttringhaus, A., 204, 341.Lui, J.S., 209.Luijten, J. G. A., 142.Lukas, S., 133.Lukes, R., 344.Luk’yanychev, Yu. A., 154.Lumbroso, H., 192, 193,Lumpkin, H. E., 199, 497,Lund, E., 197.Lupton, 33. A., 496.Lust, W. A., 145.Lutz, E. F., 321.Lutz, R. P., 240.Luxmoore, A. R., 181.Lwowski, W., 230, 244.Lyke, W. A., 445.Lykos, P. G., 339.Lyle, G. G., 326.Lyle, R. E., 326, 335.Lynch, B. M., 235.Lynch, C. C., 486.Lynch, E. R., 235.Lynden-Bell, R. M., 61.Lynen, F., 404.Lynen, P., 404.Lyon, R. K., 20.Lyssy, G. H., 474.Lythgoe, B., 299, 359.Ma, J. C. N., 200.Ma, T. S., 442, 473.Mabry, T. J., 327.McAfee, K. B., jun., 142.McBee, E. T., 229, 231,McBride, D. W., 177, 180.McBride, J. J., jun., 261,McCaffery, A. J., 169.McCaldin, D. J., 343.McCall, E.R., 235.McCall, M. A., 279.McCallum, K. S., 320.McCapra, F., 297, 298.McCarley, R. E., 158.McCarthy, R. L., 236.McCarty, M., 102.McCaskill, E. S., 338.McClenaghan, I., 283.McCleverty, J. A., 185.LOW~Y, 0. W., 413.LOW~Y, T. H., 230.206, 510.498.288.323INDEX OF AUTHORS’ NAMES 537McCloskey, A. L., 135.McCloskey, J. A., 194, 204,Maccoll, A., 224, 253.McConnell, H. M., 46, 51,McConnell, J. F., 289, 513.McCormick, J. R. D., 319.McCoubrey, J. C., 90.McCready, R. M., 364.McCrindle, R., 300.McCullough, J. D., 512.McCnllough, J. J., 227, 283.MeCully, K. S., 378.MacDiarmid, A. G., 139,McDonald, A. J., 478, 489.Macdonald, P., 429.MacDonald, P. C., 432.MacDonald, S. F., 389, 391,392, 393, 394, 396.McDonald, W.S., 134, 137.McDonough, J. M., 147.McDowell, B. L., 309.Macdowell, C. A., 43, 51, 56,McDowell, J. W., 256.McElhinney, R. S., 322.McEwen, W. E., 227.MacFarlane, M. G., 274.McFarlane, W., 176.McGarvey, B. R., 47, 71.McGarvey, J. E. B., 348.McGarvey, J. J., 101.McGarvey, F. X., 447.McGeachin, S. G., 301.McGhie, J. F., 263, 276,MacGillavry, C. H., 507.McGillivray, R., 474.McGlashan, M. L., 73, 74,76, 83, 88, 90, 91, 93, 94,95.61.141, 149.60, 122.280.McGlothlin, R. E., 146.McGrat,h, D., 367.McGrath, W. D., 101.McGreer, D. E., 201, 227.McGregor, A. T., 112.McGregor, L. L., 425, 426.McGuire, J. S., 416.Machata, G., 449.Machida, K., 193.Machin, D. J., 154.Maciera-Vidan, A., 452.McIver, P.J., 489.Mack, D. L., 476.Mack, W., 332.McKay, J. E., 370.Mackay, K. J. H., 503.Mackay, M., 514.McKay, R. H., 424.MacKellar, F. A., 201, 337.McKellar, J. F., 42.McKelvey, S. A., 370.McKelvie, N., 261.McKenna, R. H., 489.Mackenzie, A. C., 499.Mackenzie, J. D., 147.McKetta, J. J., 75, 98.Mackey, J. L., 152.McKim, A. M., 334.McKinley-McKee, J. S.,420, 421, 422.Mackor, E. L., 51.McKusick, B. C., 323.McLachlan, A. D., 51, 60,MeLafferty, F. W., 498.McLane, C. K., 23.McLaren, L., 362.McLauchlan, K. A., 201,MacLean, D. B., 357.McLean, S., 353.McLellan, A. L., 82.MacLeod, W. D., jun., 293.McMahon, P. E., 192.McMillan, J. A., 55, 58,McMillin, C. K., 220.McNally, S., 221, 362.McNeal, R. J., 156.McOmie, J.F. W., 309.McPhail, A. T., 293, 513.McQuillan, G. P., 142.McSherry, W. F., 369.MacVicar, K., 165.McWhinnie, W. R., 162.Maeck, W. J., 444, 492, 493,Markl, G., 308.Maerten, G., 280.Magalhaes, M. T., 318.Magee, R. J., 467, 476.Maggio, F., 162.Magidman, P., 275.Maguire, K. D., 233.Mahesh, V. B., 429, 433.Rlahler, H. R., 418, 421.Mahler, J. E., 180, 286,Mahony, J. D., 492.Maier, H. J., 448.Maier, L., 146.Maier, W., 189, 204.Mai-Ling-Yih, I., 469.Maina, G., 255.Mais, A., 261.Maish, W. G., 113, 114.Maitlis, P. M., 183, 184, 269,283, 308, 320.Maizus, Z. I<., 39.Majumdar, A. K., 451.Majumdar, K., 119.Maiumdar, M. K., 133.Mak, T. C. W., 509.Makarov, S. Z., 155.Makashev, Yu. A., 138.Maki, A. H., 47, 50, 52, 57,Maki, H., 56, 58.Malet, G., 278.Malhotra, K.C., 459.61, 236.202, 204, 364, 366.167.495.313.58.Malhotra, S. K., 264, 298,Malik, M. S., 358.Malik, W. U., 485.Malissa, H., 455, 458, 490.Mallett, M. W., 496.Mallory, F. B., 202, 332.Malm, J. G., 130.Mamedov, I. A., 453.Manastyrskyj, S., 180.Mandel, L. R., 374.Mandelkern, L., 130.Mandell, L., 270.Mandlsberg, C. J., 153.Mangoni, L., 295.Mangum, B. W., 46.Manh, D. D., 354.Mann, D. E., 103, 121, 190.Mann, F. G., 342.Manners, D. J., 370.Mannerskantz, H. C. E.,Manning, D. L., 458, 461.Manning, R. E., 350.Mannsfeld, S.-P., 328.Manolopoulos, P. T., 362.Manson, E., 403.Manson, L. A., 409, 410.Marais, D. J., 190.Marascia, F. J., 322.Marburg, S., 252.Marchart, H., 440.Marckwald, W., 322.Marcus, R., 261.Marcus, R.A., 233.Margoliash, E., 386.Margrave, J. L., 100, 130,Margulis, T. N., 507.Marhol, M., 447.Mari, R., 30, 31.Marino, G., 232.Marion, L., 353, 358.Mark, H. B., 463, 483.Mark, V., 272.Markert, C. L., 419.Markevich, A. M., 26, 27,Markezich, A. R., 369.Markham, E., 389.Markham, J. J., 62.Markham, K. R., 341.Markham, R., 381.Markl, G., 268, 340.Mark6, B., 177.Mark6, L., 177.Markov, V. P., 153.Markovitz, A., 365.Markowitz, S. S., 492.Marks, G. S., 391, 393, 395,Marks, P. A., 380.Marmet, P., 128.Marmur, J., 374, 378.Marnati, M. P., 411.Maroudas, A., 93.306.176.196.38.396538 INDEX OF AUTHORS' NAMESMarple, L. W., 471.Marpy, K., 150.Marquardt, F.H., 250.Mmr, P. A., 342.Marrian, G. F.,Marriott, J. E., 232.Marsh, R. E., 504, 510, 512,Marsh, S. F., 493, 495.Marshall, G. F., 495.Marshall, J. A., 264, 302,Marshall, L. M., 359.Marshall, R. L., 170, 173.Marshall, W., 46.Marsigny, L., 123, 128.Marston, H. R., 403, 405.Martell, A. E., 173, 422.Martens, R. J., 235, 335.Martens, W., 462.Marti, M., 428.Martin, B., 162.Martin, D. F., 174.Martin, D. G., 263.Martin, D. S., jun., 171.Martin, G., 65, 192.Martin, J. C., 253.Martin, M. M., 253.Martin, R., 34.Martin, R. B., 251, 253.Martin, R. G., 381.Martin, W. W., 480.Martin-Smith, M., 277, 296,Martinez, A. P., 424.Martres, R. W., 460.Martsokha, B. K., 331.Marty, T., 194.Marunina, A.T., 460.Marvell, E. N., 237.Masamure, S., 339.Maslen, V. W., 121.Mason, E. A., 113, 114.Mason, R., 185.Mason, S. F., 82, 169, 198,Mason, S. G., 368.Mason, W. H., 482.Massad, M. K., 280.Masschelein, W., 196.Massey, A. G., 148, 150.Massingill, J. L., 273.Masuda, Y., 68.Mateescu, G., 309.Matherny, M., 475.Matheson, M. S., 55.Mathews, G., 296.Mathewson, J. H., 391.Mathieson, A. McL., 289,503, 513, 514.Mathis, R., 194.Mathot, V., 88.Mathur, N. K., 461.Matic, M., 488.Matijevich, B. L., 417.Matlack, G. M., 493.513.306, 355.330.286.Matschki, D. E., 98.Matsen, J. M., 460.Matsubara, I., 195.Matsui, M., 281.Matsutani, S., 345.Mattauch, H., 130.Matten, J., 146.Matthaei, J. H., 380, 381.Matthew, M., 386.Matthies, D., 323.Mattingly, T.M., 244.Mattock, G., 466.Mattocks, A. R., 345.Mattson, R. H., 277.Maulbecker, D., 136, 168.Mauret, P., 198.Maurice, M. J., 471.Mautner, H. G., 336.Mauvernay, R. Y., 4'79.Mauzerall, D., 325,385,388,390, 393, 394, 395.Mavel, G., 65.Mawby, R. J., 160.Maxwell, E. S., 381.Maxwell, J. A., 438, 462.May, P., 491.Mayer, B. E., 158.Mayer, D. B., 277.Mayer, J., 474.Mayne, J. E. O., 461.Mayer, R., 323, 330.Mayer, V., 439.Mayling, A. H., 482.Mays, M. J., 140.Mayor, L , 22, 23.Maza, R. M., 452.Mazliak, P., 278.Mazumder, R., 404.Mazur, Y., 287, 289, 305,Meadows, J. W. T., 493.Meakin, J. E., 126.Mecke, R., 194.Meckel, L., 446.Mechoulam, R., 289.Medeiros, F. W., 322.Mehra, V.S., 98.Mehrotra, R. C., 155, 453.Mehta, M. L., 156.Meiboom, S., 66.Meier, H., 370.Meier, W., 315, 316, 341.Meineker, F. W., 51.Meinhart, J. O., 414.Meinke, W. W., 496.Meinnel, J., 192.Meinwald, J., 213, 283, 287,Meister, W., 133.Meites, L., 487.Melchior, M. T., 52.Melera, A., 203, 327.Melnick, I., 395.Melson, G. A., 174.Menapace, H. R., 32.Mencis, I., 493.327.303.Meng, B. H., 476.Mengler, H., 327.Mercier, M., 327.Meredith, R. F. K., 347,Merer, A. J., 128.Merkle, F. H., 465.Merrill, S. H., 382.Merritt, C., 497.Mertz, C., 265, 280.Mervyn, L., 375, 409.Merz, E., 491.Meselson, M., 379.Mesirov, M. E., 209.Mesnard, P., 362.Mestres, R., 270.Metcalfe, J., 478.Metzner, W., 328.Meuche, D., 315, 316.Meuwsen, A., 148.Meyer, B., 103.Meyer, K., 371, 446.Meyer, M.W., 240.Meyer, R., 341.Meyer, W. H., 418.Meyer, W. K., 151.Meyer, W. L., 306.Meyerson, S., 236.Meystre, C., 305.Michalowicz, W. A., 273.Michael, D., 233.Micheel, F., 364.Nichel, G., 278.Michels, A., 88, 120.Michelson, A. M., 371, 376,Michelson, M. J., 330.Michl, J., 393.Middleton, W. J., 323.Mielert, A., 229.Miescher, E., 116, 124, 125.Migchelsen, T., 511.Miginiac, P., 280.Migliacci, A., 411, 412.Mihai, G., 314.Mihfika, I., 475.Mikawa, Y., 191.Mikhailichenko, A. I., 494.Mikhailov, B. M., 133, 135.Mikhailov, Yu. N., 153.Miki, T., 293.Milazzo, G., 479.Miliotis, J. A., 137.Milks, J. E., 307, 340.Millar, D. B. S., 419, 424.Millar, I.T., 333.Milledge, H. J., 502.Millen, D. J., 193, 195.Miller, B., 240.Miller, F. A., 195.Miller, H. C., 131.Miller, I. M., 411.Miller, J. G., 191.Miller, J. M., 186.Miller, J. R., 164.Miller, K. E., 263, 276.348.377INDEX OF AUTHORS’ NAMES 539Miller, P. A., 319.Miller, R. L., 339.Miller, R. R., 174.Miller, S. I., 224, 231, 270.Miller, S. J., 405.Miller, V. B., 32.Milleron, N., 9.Milligan, D. F., 54.Mills, I. M., 100.Mills, J. A., 405.Mills, J. N., 431.Millward, B. B., 322.Milne, G. W. A., 250, 306.Milner, G. W. C., 464.Milton, A. S., 445.Milton, E. R. B., 107.Mims, S. S., 295.Minczewski, J., 448.Minghetti, A., 411.Minkoff, G. J., 18, 28.Minshall, E., 445.Minutilli, F., 301.Mironov, V. E., 138.Mirsky, A.E., 380.Mishima, H., 299.Mishra, H. C., 47, 151, 161.Mislow, K., 189, 197, 199,Missen, R. W., 96.Mistry, S. P., 404.Misumi, S., 269.Mitchell, A., 267.Mitchell, B. D., 499.Mitchell, D. W., 158.Mitchell, P. C. H., 158.Mitra, A. K., 365.Mitsui, H., 380.Mitsui, T., 474.Mitzner, B. M., 480.Miyazaki, M., 294.Mizuno, N., 380.Mochalova, N. I., 506.Mock, W. L., 258, 309.Modest, E. J., 338.Mobus, B., 471.Mockel, K., 320.Moeller, T., 145, 152.205, 286, 306, 347.Moelwyn-Hughes, E. A., 96,217.Moerikofer, A. W., 227,255.Moffatt, J. G., 376.Mohaupt, G., 160.Mohr, G., 326.Molin, N. Yu., 52.Moller, F., 419.Mollin, D. L., 407.Molloy, B. B., 203, 327.Molodkin, A. K., 153.Monaco, M., 337.Monaghan, J.J., 89.Monagle, J. J., 267.Monfila, A., 100, 116, 119.Monk, R. G., 438, 464.Monnier, D., 488.Monod, J., 379.Monseur, X., 205, 351, 356.Monson, R. S., 219.Montavon, M., 274.Montequi, R., 442.Monty, K. J., 403.Moody, G. J., 361.Mooney, E. F., 133, 136,Moore, B., 329.Moore, C. G., 280.Moore, J. A., 322.Moore, J. H., 406.Moore, M., 356.Moore, P. T., 224.Moore, R. B., 235.Moore, R. E., 352, 355.Moore, R. H., 361, 367.Moore, R. N., 297.Moore, W. R., 224.Moores, M. S., 240.Morachevsky, A. G., 97.Morales, A., 470.Moran, P. R., 62.Morato, T., 430.Morawetz, H., 246, 250,Morcom, K. W., 74, 93.Morell, C. E., 232.Morgan, E., 128.Morgan, H., 497.Morgan, L. O., 59, 66.Morgan, L. R., 243, 306,Morgan, L.R., jun., 340.Morgan, W. T. J., 368.Mori, B., 155.Moriarty, R. M., 210.Morimoto, M., 269.Morimoto, T., 277.Morimoto, Y., 173.Morin, R. D., 273, 334,Morita, S., 191.Moritz, A. G., 193, 199.Moritz, K. L., 316.Moriyama, H., 417.Mork, P. C., 273.Morley, H. V., 399.Moros, S. A., 460.Moroshkina, T. M., 475.Moroz, E., 303.Morozov, I. S., 154.Morrel, D. B., 396.Morris, A. G. C., 488.Morris, D. F. C., 444, 490.Morris, G., 262.Morris, G. F., 222.Morrison, A., 294.Morrison, G. A., 317.Morrison, G. H., 443.Morrison, J. D., 125.Morrison, M., 396.Morrison, R. T., 236.Morse, B. K., 207.Morse, P. M., 114.Morsingh, F., 394.Mortimer, C. T., 330, 333.206.253.324.348.Morton, J. R., 53, 54, 55,Morton, K.B., 300.Morton, R. K., 417.Mosby, W. L., 319.Moscowitz, A., 197, 306.Moser, C., 113.Moses, P., 202, 324, 330.Mosher, H. S., 203,224,366.Moss, H., 442.Moss, J. B., 205, 350.Motl, O., 292.Motes, J. M., 230.Mott, W. E., 491.Moulton, W. G., 194.Mourkides, G. A., 416.Moustafa, 2. H., 372.Mowat, J. H., 366.Mower, H. F., 279.Moyle, M., 268.Moynehan, T. M., 203, 338.Mozdokeli, T. G., 131.Mrazek, R. V., 94.Miihle, G., 331.Miiller, E., 267.Miiller, G., 375.Muller, H., 330.Mi.iller, K., 192, 494.Muller, O., 375, 402, 411,Muller, R., 147, 182.Mueller, R. G., 487.Muller, R. J., 231.Mueller, W. A., 227, 229.Mueller, W. H., 92.Miinch, G., 376.Muetterties, E. L., 70, 131,Mujagawa, I., 57, 206.Mukai, T., 315.Mukaroski, I., 345.Mukerjee, S.K., 329.Mullen, R. T., 242.Muller, J. M., 302.Muller, R., 316.Muller, T. C., 233.Mulliken, R. S., 82, 100,106, 107, 109, 110, 117,122, 123, 128, 190.56, 57, 101.413.142, 152.Mulrow, P. J., 427.Munch-Petersen, A., 400,Munday, L., 167.Munn, R. J., 90.Munster, G., 159.Murata, T. G., 370.Murdoch, H. D., 181, 222.Murdock, K. C., 283.Murphy, D., 366.Murphy, J., 66.Murray, A. W., 417.Murray, K., 447.Murray, K. E., 275.Murray, R. W., 60,466,472.Murrell, J. N., 51, 64, 82.Murthy, A. R. V., 457.401540 INDEX OF AUTHORS’ NAMESMurthy, N. S., 112.Murthy, V. R., 497.Murti, P. S., 96.Murto, J., 235.Murty, K. S., 454.Musgrave, B., 494.Musgrave, W. K. R., 185.Musil, A., 443.Musil, F.J., 502.Musulin, B., 114.Musya, M., 302.Muth, C. W., 471.Muxfeldt, H., 288, 318.Myers, A. L., 89, 92.Myers, D. B., 84.Myers, H. W., 480.Myers, L. S., 490.Naar-Colin, C., 192.Nabivanets, B. I., 154, 156.Nabors, C., 429.Nace, H. R., 272.Nachbaur, E., 144.Naemura, K., 272.Nagarajan, K., 339, 354.Nagasawa, K., 365.Nagase, K., 255.Nagata, C., 83.Nagel, C. W., 368.Nagy, B., 445, 494.Nagy, P. L. I., 183.Nahabedian, K. V., 234.Nahum, L. Z., 458.Naik, A. R., 330.Naiman, M., 237.Nair, V. S. K., 469.Nakagawa, M., 268,269,272.Nakagawa, K., 260.Nakagawa, Y., 204, 351,Nakajima, M., 298.Nakamichi, M., 447.Nakaminami, G., 268.Nakamoto, K., 173.Nakamura, D., 165.Nakamura, K., 248.Nakanishi, K., 299, 302.Nakano, T., 358.Nakao, A., 407.Nakata, T., 260.Nakazaki, M., 291, 292.Nakulesparan, K., 463.Nalbandyan, A.B., 24, 25,27, 28, 29, 30, 38, 42.Nambury, C. N. V., 202.Namioka, T., 123.Namtseva, L. I., 459.Naqui, N., 166.Narath, A., 192.Narayanan, C. R., 355.Nardelli, M., 164, 509, 510.Nash, C. P., 193.Nast, R., 163, 182.Natarajan, A. R., 441.Nathan, H. A., 403.Natsuma, M., 201.353.Natta, G., 151.Naville, A. H., 429.Naya, S., 503.Nayler, J. H. C., 322.Naylor, C., 379.Naylor, P. G., 269.Neal, D. J., 492.Nebbia, L., 471.Nebergall, W. H., 468.Nedbalek, E., 482.Neeb, R., 482, 488.Needleman, S. B., 320.Nbel, J., 65.Neeman, M., 267.Neff, L. D., 14.Negri, R. C., 448.Neher, R., 427, 429, 430.Neikam, W.C., 282, 312.Neilson, A. H., 318, 341.Neilson, T., 257.Neiman, M. B., 32, 33.Neiman, R., 58.Nelson, D. A., 335.Nelson, I. V., 167.Nelson, L. S., 102.Nemec, I., 467.Nemeth, A. M., 388.Nemodruk, A. A., 477.Nenitzescu, C. D., 309.Neparko, E., 95.Neronova, N. N., 505.Nesbet, R. K., 113.Nesmeyanov, A. N., 147,Neuberger, A., 386, 387,Neugebauer, F. A., 204.Neuman, R. C., 232.Neumann, C. L., 198.Ncumann, W. P., 142.Neunhoffer, H., 376.News, N., 204, 353, 355.New, R. A., 393.Nevell, T. P., 368.Neveu, M. C., 246, 247.Neville, R. G., 144.Newbould, J., 296.Newitt, E. J., 39.Newman, E. J., 478.Newman, M. S., 250.Newmann, G., 166.Newnham, I. E., 154.Newns, G. R., 143.Ney, W. O., 253.Neyens, A. H., 232.Nguyh, D., 191.Nichol, C.A., 408.Nicholls, D., 129.Nicholls, R. W., 101, 102,Nichols, P. N. R., 479.Nicholson, J. S., 308.Nickels, W., 138, 482.Nickless, G., 469.Nicksic, S. W., 49.Niclause, M., 30, 31.155, 156.388, 397, 398.111, 112.Niclause, N., 34.Nicolaus, B. J. R., 323.Nicole, L., 265.Niedenzu, K., 133.Nielsen, N. A., 273.Nier, A. O., 496.Niermann, H., 142.Nigam, R. K., 83.Niggli, A., 505.Nightingale, R., 142.Nihei, T., 378.Niki, E., 462.Nikolaev, N. S., 154.Nikoleti6, M., 209.Nilsson, M., 198.Nilsson, W., 263.Nirenberg, M. W., 380, 381.Niselion, L. A., 138, 152.Nishikawa, H., 162.Nisizawa, K., 370.Niskanen, R. A., 494.Nisselbaum, J. S., 420.Nist, B. J., 288.Nitta, I., 52, 508.Niu, H. Y., 313.Nixon, J.F., 157.Niyogi, S. K., 448.Noack, K., 191.Noble, G. A., 62.Nocke, W., 433.Noth, H., 133,134,139,147.Noggle, J. H., 144.Nogina, 0. V., 155.Noland, W. E., 332, 511.Nolle, A. W., 59.Nonhebel, D., 262.Nonhebel, D. C., 222.Nooi, J. R., 270.Norcross, B. E., 335, 416.Norell, J. R., 322.Norin, T., 290.Norman, B. 0. C., 449.Norman, R. 0. C., 48, 232,Norman, J. J., 194.Norment, H. G., 503, 508.Norrish, R. G. W., 20, 27,29, 30, 42, 101.Norton, F. J., 10.Norton, W. T., 277.Novtik, E., 445.Novak, K., 465, 467.Novtik, V., 484.Novakovskaya, E. G., 460.Novikova, N. V., 147.Novoa, W. B., 424.Novoselova, A. V., 130.Novotn9, L., 292.Nowaki, E., 343.Nowicki, L., 402, 412.Noxon, J. F., 109.Noyce, D.S., 196, 219, 224.Noyce, W. K., 452.Nozik, Y. Z., 502.Nozoe, T., 315, 316.Niirnberg, H. W., 482.236, 310INDEX OF AUTHORS’ NAMES 541Nugent, L. J., 190, 195.Nukada, K., 191.Nussbaum, A. L., 200, 267,Nussbucker, B., 147.Nussim, M., 287.Nuttall, R,. H., 166.Nygaard, A. P., 418.Nyholm, R. S., 154, 158,160, 162, 163, 167, 171.Nyman, F., 149.Nfvlt, J., 95.Oae, S., 336.O’Brien, R. E., 199, 260.O’Brien, R. J., 165.Ochiai, H., 368.Ochoa, S., 381, 404.O’Colla, P. S., 367.Ocone, L. R., 170.Odabashyan, G. V., 150.O’Donnell, J. P., 230.O’Donnell, T. A., 159, 469.Ofele, K., 180, 183.Offer, G., 449.Oftedahl, M. L., 364.Ogawa, M., 106, 107, 125,Ogle, P. R., 159.O’Grady, B: V., 199.Ogura, F., 268.Ohlman, G., 34.Ohloff, G., 289.Ohme, R., 321.Ohnishi, S., 52.Ohta, M., 218.Okamoto, T., 201.Okamy, A., 343.Okazaki, R., 377.Okazaki, T., 377.Okhlobystin, 0.Yu., 266.Oksne, S., 332.Okuda, S., 345.Okuzumi, Y., 245, 269.Olah, G. A., 232, 233, 240,Olcott, R. J., 175.Oldenberg, O., 102, 110,Oldershaw, G. A., 101.Oldfield, J. H., 476.Oliveto, E. P., 267.Ollis, W. D., 318.Olsen, C. J., 253.Olsen, R. E., 231.Olson, C., 482.Olson, J. M., 418.Omar, M. H., 79, 92, 98.O’Mara Bockris, J., 472.Onak, T. P., 132.Onken, U., 96.Ono, H., 268, 368.Ono, S., 369.Onodera, K., 368.Onyszchuk, M., 142.Oota, Y., 380.305.126.268, 285.123.Opalovskii, A. A., 154.Openshaw, H. T., 260.Opitz, H. P., 171.Oranskaya, M. A., 156.Orazi, 0.O., 354.O’Reilly, D. E., 45, 63.Oreskes, I., 250.Orgel, L. E., 50, 176, 184.Origlio, S., 13.Orioli, P. L., 164.Ortenberg, F. S., 112.Ortiz, P. J., 404.Orzech, C. F., 217.Orzeck, C. E., 231.Osaka, K., 315.Osawa, S., 380.Osbond, J. M., 276.Osborne, A. G., 177.Osborne, B. P., 159.Osiecki, J. H., 376.Oskam, H. J., 120.Oskay, E., 269.Ostermayer, F., 218.Ostermeier, J., 149.Ostler, O., 320.Osuma Itoh., 233.Otaka, E., 380.Oth, A., 378.Otomo, Y., 62.Ott, H., 367.Ott, J. B., 83, 94.Ott, w., 393.Otte, H. M., 502.Ottemann, J., 477.Ottendorfer, L. J., 490.Otting, W., 204.Ottinger, R., 198.Otto, P., 355.Ourisson, G., 200, 303.Ovenall, D. W., 55.Overath, P., 404.Overberger, G. C., 330.Overend, W.G., 246, 360,Overwien, H., 345.Owellen, R. J., 204, 354.Owen, A. J., 132.Owen, E. D., 182.Owen, J., 46.Owen, J. E., 137.Owens, A. F., 494.Owings, F. F., 303.Owston, P. G., 178, 510.Oyama, II., 395.Pabst, A., 505.Pace, R. J., 131.Pachler, K., 204.Packer, J., 246.Packer, K. J., 146, 150.Paddock, N. L., 144.Padilla, J., 348.Pagani, B., 471.Page, J. A., 438, 462, 464.Pagel, H., 345.Pahil, S. S., 459.362, 363.Pai, B. R., 292, 354.Painter, T. J., 368.Pal, B. C., 373.Palebek, M., 468.Palistrant, A. F., 505.Palit, S. R., 96.Pallaud, R., 262.Pallotti, M., 329.Palm, C., 183, 184.Palmer, J. W., 66.Palmer, K., 353.Palmer, T. A., 448.Panella, J. P., 334.Pa#nizzi, L., 295.Pankhurst, K. S., 480.Pannetier, G., 102, 123, 128.Panwar, K.S., 470.Panzer, H. P., 364.Panzer, R. E., 154.Pasletti, P., 164.Papadopoulos, E. P., 220.Papaliolios, C., 112.Pappas, S. S., 285, 307.Paquette, L. A., 337.Paquot, C., 274.Paraskevopoulos, G. C., 96.Parcell, A., 253.Parham, W. E., 286.Parihar, D. B., 375.Parikh, I., 327.Park, J. D., 196, 282.Parks, C. R., 457.Parker, A. J., 254.Parker, C. A., 476, 477.Parker, R. E., 233.Parker, W., 290.Parker, W. J., 482.Parkin, R. A., jun., 196.Parkin, C., 182.Parkinson, W. H., 101, 102.Parraclr, J. D., 235.Parry, R. W., 135.Parshall, G. W., 131, 148,Parsonage, N. G., S6,88, 95.Parsons, C. R., 164.Partington, E. J., 91.Partos, R. D., 230.Partyka, R. A., 298.Pascual, J., 270.Paslo, D.J., 198.Pasqualini, J. R., 432.Passoneau, J. V., 413, 414.Pasternak, R. A., 13.Pasto, D. J., 285, 314.Pastore, E. L., 414.Patai, S., 223, 225, 231.Patel, C. C., 155.Paterson, W., 341.Patin, D. L., 370.Patmore, E. L., 174.Patrick, C. R., 310.Pats, R. G., 483, 488.Patterson, A., 71.Patterson, D., 99, 439.Patterson, H., 496.180542 INDEX OF AUTHORS' NAMESPatterson, J. M., 324.Patton, J. W., 230, 416.Patzelt, H., 316.Paudler, W. W., 337.Paul, I., 286.Paul, I. C., 296, 317.Paul, K. G., 396.Paul, R. C., 459.Paulik, F., 500.Paulsen, H., 360.Paulson, J. F., 497.Paulus, K. F., 51.Pauson, P. L., 177,183,184.Pavlenko, L. I., 475.Pavlovid, D., 223, 224.Pawelke, G., 420.Pawelkiewicz, J., 402, 411,Pawley, G.S., 505.Payne, D. S., 145.Payne, G. B., 259.Payne, M., 442.Peach, M. E., 136, 151.Peacock, R. D., 159.Peak, D. A., 308.Pearn, E. J., 206.Pearson, R. G., 66,175,223,Pearson, R. K., 133.Pechacek, R. E., 463.Pechanec, V., 473, 475.Pecherskaya, Yu. I., 27.Pechman, M., 447.Peck, P. F., 443.Pecsok, R. L., 154.Pedersen, H. C., 494.Pedinoff, M. E., 196.Peel, J. L., 410, 411.Peeling, E. R. A., 254.Peifer, J. J., 446.Peiffer, G., 272.Peisach, J., 228.Pelster, H., 316.Peltier, D., 193.Pelz, K., 346.Penfold, A. R., 294.Penneman, R. A,, 154.PQrano, J., 82.Percival, E., 370.Perego, G., 151.Pereira, N. A., 204, 352.Pefilova, I. L., 156.Perkins, D. F., 478.Perkins, M., 495.Perkins, N. A., 313.Perlin, A.S., 362, 367, 370.Perlman, D., 411.Perlmutter, H. D., 286.Perrin, D. D., 166,203,329,Perrin, D. R., 203, 329.Perry, C. W., 269.Perry, M. B., 359, 366, 370.Perry, S. G., 252.Person, W. B., 82, 83.Pesez, M., 442.412, 413.254.339.Peterkofsky, A., 413.Petrow, V., 306.Peters, G. A., 338.Petersen, D. R., 283.Petersen, R. C., 220.Peterson, E. R., 337.Peterson, J. O., 257.Peterson, L., 496, 499.Peterson, L. E., 201.Peterson, L. I., 282.Peterson, P. E., 210, 225.Petit, G. S., 154.Petix, J., 396.Petrissans, J., 198.Petropoulos, A. G., 464.Petrou, A. A., 206.Petrov, A. A., 272.Petrov, A. D., 150.Petrov, V. G., 502.Petrus, V., 484.Petterson, A. V., 127.Pettit, D. J., 322.Pettit, G. R., 256, 257, 276,Pettit, R., 180, 286, 313.Pevzner, M.S., 479.Peyron, M., 107.Pfab, W., 474.Pfahl, D., 409.Pfeiffer, M., 278.Pfister, K., 337.Pflaum, R. T., 467, 469.Pflegher, K., 335.Pfleiderer, G., 414,415,419,Phillips, D. J., 167.Phillips, D. S., 444.Phillips, G. O., 361.Phillips, J. C., 504.Phillips, J. G., 100, 255.Phillips, L., 219.Phillips, S. L., 489.E'hillips, W. D., 52, 61, 70,Phillipson, M., 462.E'hilpot, J. L., 101.Piatak, D. M., 204.Piatelli, M., 396.Piazzi, M., 469.k'iccolini, R., 311.Pick, J., 94.Pickard, P. L., 262.?ickering, W. F., 476.?ickhardt, W. P., 456.lidcock, A., 170.lierce, A., 335.?ierce, L., 201, 321.lierce, T. B., 443.liercey, M. R., 266.lieterse, M. J., 335.lietilii, I., 97.'ietrzak, R.F., 452.?ietrzyk, D. J., 486.'iette, L. H., 48, 49, 54, 60.'ijck, J., 492, 493, 495.?ike, E. R., 501.320.424.152.Pike, M. A., 95.Pilato, L. A., 196, 284.Pillai, M. G. K., 194.Pillai, V. S. N., 460.Pillar, C., 227.Pillow, M. W., 113.Pilsater, U., 100, 104.Pimentel, G. L., 82.Pinar, M., 354.Pinchas, S., 199, 204.Pinchera, A., 494.Pinchot, G. B., 415.Pine, S. H., 230.Pines, H., 240.Pinhey, J. T., 293.Pink, R. C., 49.Pinte, G., 491.Piper, T. S., 107, 169, 172.Piras, R., 360.Piret, P., 511.Pisarevskii, Yu. P., 111.Pischel, H., 375.Pitcher, E., 176, 180, 185.Pitman, I. H., 252.Pitman, M., 365.Pitochelli, A. R., 131, 132.Pitra, J., 445.Pitteroff, W., 242.Pitts, J. N,, 60.Pitwell, L. R., 438.Pitzer, K.S., 89.Piwowarska, R., 454.Plane, R. A., 422.Plat, M., 204, 205, 353, 354.Platz, G. M., 147.Plieninger, H., 285, 324,Plieth, K., 508.Pliev, T. N., 198.Pliska, V., 486.Plisko, E. A., 369.Ploger, W., 422.Plowman, R. A., 176.Plunkett, A. O., 338.Plust, H. G., 139.Pocker, Y., 207.Poesche, W. H., 333.Poschl, G., 114.Pohlke, R., 286.Poindexter, E. H., 349.Poirier, R. J., 334.Poisson, H., 204.Poisson, J., 351.Polak, R. J., 135.?olger, N., 275, 276.Pollak, J. K., 376.?ollak, V. L., 63.?ollard, F. H., 469.?ollard, Gt. E., 196, 287.?ollock, F. J., 247.lolonsky, J., 299.lolster, R., 223.?oltorak, V. A., 34.lonomarenko, V. A., 150.lool, R. A. H., 86.'ooley, D., 61.327INDEX OF AUTHORS’ NAMES 543Popa, G., 450.Popea, F., 450.Popjtik, G., 419.Pople, J.A., 64.Popov, E. M., 190.Popova, R. A., 494.Popowicz, J., 447.Popp, F. D., 257, 338.Poppenburg, G., 140.Porai-Koshits, M. A., 506.Porte, A. L., 145, 201, 318.Porter, G., 20, 82.Porter, R. F., 124, 125, 279,Porter, T. L., 119.Porterfield, W. W., 46.Portnoy, H. D., 466.Portnoy, S., 276.Porubszky, I., 489.Post, B., 504.Post, G. G., 361.Postnikov, L. M., 42.Potter, D. J. B., 91.Potter, J. C., 492.Potter, R., 511.Potts, K. T., 350.Powell, D. B., 166, 203.Powell, H. M., 161.Powell, J. E., 152.Powell, V., 291.Power, U., 426.Powers, R. M., 480.Poulson, R. E., 69, 70.Povyshev, L. V., 97.Pozharski, F. T., 331.Prasad, K., 112.Prasad, S., 153, 458.Prasad, S.S., 112.Pratt, E. A., 373.Pratt, L., 176, 184.Prausnitz, J. M., 76, 83, 84,89, 90, 92, 97.Prelog, V., 219, 287, 328.Prengle, H. W., 95.Presnyakova, V. M., 510.Preston, D. R., 348.Preston, J., 246.Prey, V., 364.Pzibil, M., 465.Pribil, R., 441, 454, 455,469, 484.Price, C. C., 335, 341.Price, R., 150.Price, W. C., 100.Prigogine, I., 84.Prilezhaeva, E. N., 280.Prinzbach, H., 285, 322.Pristavka, D., 439.Pritchard, J., 15.Proctor, G. R., 341.Prohaska, C. A., 191.Prokhorov, A. M., 46.Prokof’eva, I. V., 468.Proll, P. J., 162.Protheroe, J. B., 23, 27.Protsenko, G. P., 481.318.Prout, C. K., 161.Prue, J. E., 64.Pruett, R. L., 180.Pruguard, J., 437.Pruitt, K. M., 252.Pruitt, M. E., 495.Prunty, F.T. G., 427, 432.Prusoff, W. H., 372.Pryor, W. A., 207.Prystas, M., 375.Przybylska, M., 357, 503,Pshenitsyn, N. K., 468.Ptichkin, I. I., 26.PiilkrBb, P., 477.Pullman, B. J., 147.Pump, J., 140.Punqor, E., 458, 473.Purdie, J. W., 399.Purdy, S. J., 446.Purdy, W. C., 458, 466.Puri, D. M., 155.Purushothaman, K. K., 292.Purvis, J. L., 415.Putkey, T. A., 212.Pyaivinen, E. A., 369.Pysz, J. F., jun., 168.Quacchia, R. H., 233.Quagliano, J. V., 164, 172.Quattrone, J. J., 470.Queen, A., 214.Quijada, C. L., 425.Quilico, A., 327.512, 513.Raaen, H. P., 482.Raasch, M. S., 263.Rabin, B. R., 423.Rabinowitz, R., 261, 410.Rabourn, W. J., 320.Rabovik, Ya. I., 138.Rachman, A., 199.Radda, G. K., 232, 236,Radding, C.M., 378.Radford, H. E., 116.RBdy, G., 454.Ragade, I. S., 358.Rahn, R., 46.Rajaratnam, A., 102.Rajadurai, S., 292.Rajappa, S., 354.Rajic, M., 303.Rajopalan, K. V., 421.Rakhit, S., 256.Rakovic, M., 489.Rakutis, R. O., 200, 303.Ralph, R. K., 378.Ralph, W. D., 493.Rama Rao, C., 441.Ramage, R., 290.Raman, S., 502, 503, 512.Raman, S. P., 301.Ramcharan, S., 430.Ramirez, F., 261.Rammler, D. H., 361, 377.310.Ramp, F. L., 255.Ramsay, D. A., 100, 101,Ramsay, 0. B., 223.Ramayne, M. R., 63.Randall, E. W., 47.Randic, M., 173.Randles, C. H., 408.Randolph, D. R., 443.Rank, D. H., 109.Ransil, B. J., 113, 121.Rao, B. S., 109.Rao, D. V. G. L. N., 53,205,Rao, G. G., 454, 467, 468,Rao, G. P., 457.Rao, G.V., 96.Rao, K. B., 454.Rao, K. S., 109.Rao, K. V., 301.Rao, N. V., 470.Rao, P. K., 101.Rao, P. M., 128.Rao, P. T., 127, 128.Rao, P. V. K., 454.Rao, T. A. P., 128.Rao, V. V., 450.Rao, Y. V., 127.Raphael, R. A., 290, 295,Rapin, A. M. C., 365.Rapkin, E., 490.Rapoport, H., 263,309,325,339, 352, 355, 393, 399.Rapoport, S. A., 372.Rappoport, Z., 223, 225.Rasburn, J. W., 217.Raschig, F., 139.Rasish, J. C., 463.Raskovan, J., 172.Rasmusson, G. H., 260.Rastogi, R. P., 83.Rastrup-Andersen, J., 195,199, 202, 329.Rathjens, G. W., jun., 196.Ratnam, A. V., 96.Rauch, E., 258.Raudenbusch, W., 218.Rauther, J., 367.Raval, D. N., 425.Ray, N. H., 150.Ray, W. J., jun., 382.Raymond, S., 447.Razuvaen, G. A., 184.Re, G.D., 331.Read, S. H., 113, 114.Read, T. O., 233.Reamer, R. H., 98.Records, R., 197, 306.Reddy, G. S., 327.Reddy, J., 512.Redfield, B., 413.Redford, D. G., 203.Redhead, P. A., 13.Redlich, O., 98.102, 128.206.470.301544 INDEX OF AUTHORS’ NAMESRedmond, W., 266.Redpath, C. R., 194.Reed, T. M., 90.Reed, W. L., 224.Reed, H. J., 514.Reed, H. J., 503.Rees, A. L. G., 113.Rees, D. A., 371.Rees, C. W., 232, 234, 235,246, 310, 311, 326, 336.Rees, M. W., 381.Rees, W. T., 476, 477.Reese, C. B., 253, 377.Reese, R. M., 496.Reeves, E. M., 101.Reeves, L. W., 79.Reeves, R. L., 245.Regnaud, F., 454.Reich, E., 382.Reichard, P., 377, 410.Reichel, L., 367.Reichel, S., 320.Reichle, W. T., 147.Reichmann, M.E., 381.Reid, D. H., 203, 327.Reid, R. C., 34.Reid, S. T., 324, 330, 337.Reid, W., 327, 331.Reif, L., 230.Reilley, C. N., 440,455,461,463, 466, 472, 483.Reimlinger, H., 267.Rein, J. E., 492, 493.Rein, J. S., 444.Reinberg, A. R., 62.Reiner, B., 444.Reiner, J. E., 135.Reiner, J. M., 444.Reinhart, I<. L., 330.Reinheimer, J. A., 219.Reinheimer, J. D., 234.Reinhold, H., 140.Reinisch, R. M., 149.Reinmuth, W. H., 481.Reisch, J., 329.Reisse, J., 198.Reist, E. J., 365, 366, 375.Reitz, D. C., 50.Remanick, A., 228.Rembmz, G., 362, 365.Remeikrt, J. P., 46.Remily, C., 416.Relyee, D. I., 336.Renner, H., 103.RBrat, C., 334, 510.Rerick, M. N., 256.Resnick, I?. R., 299.Reuter, W., 337.Reutov, 0. A., 217, 230.Reynolds, G.F., 466, 470.Reynolds, R. D., 227.Reynolds- Warnhoff, P.,&m56, Z., 476, 479.Rhodes, D. F., 491.Rhum, D., 232.211.Ribar, T., 214.Ricca, A., 327.Richards, G. N., 369.Richards, J. P. G., 507.Richards, L. W., 19.Richards, R. E., 71, 73, 170.Richards, W. G., 127.Richardson, A. C., 363, 366.Richardson, E., 147.Richardson, J. M., 92.Richardson, 0. W., 118.Richert, D. A., 386.Richey, H. G., 209.Richmond, J. E., 398.Richter, H. G., 496.Richter, H. J., 260.Richter, M., 369.Richter, S., 330.Rickard, R. R., 495.Rickards, R. W., 360.Rickborn, A. B., 230.Riddiford, A. C., 482.Ridd, J. H., 232, 310, 338.Riddle, F. C., 209.Ridgewell, B. J., 232, 336.Rieger, P. H., 51.Rieke, C. A., 110.Riemschneider, R., 204.Rigamonti, J., 266.Rigg, B., 469, 485.Riley, J.P., 478.Riley, T., 233, 246.Rimai, L., 46.Rimington, C., 385, 386,Ringold, H. J., 264, 305,Ringstrom, U., 116.Rink, J. P., 128.Risebrough, R. W., 379.Ritchie, A. C., 347, 348.Ritter, J. J., 263.Rivaille, P., 365.Rizzo, H. F., 135.Ro, R. S., 223.Roach, M. K., 479.Robbins, P. W., 376.Roberts, D., 408.Roberts, D. D., 208, 219.Roberts, E. R., 166.Roberts, H. L., 149, 150.Roberts, .J. C., 320, 329,341.Roberts, J. D., 189, 208,210, 217, 240, 311.Roberts, K. D., 433.Roberts, L. E. J., 153.Roberts, L. R., 98.Roberts, M. B., 495.Roberts, R. M., 237.Roberts, R. J., 235.Roberts, R. W., 13.Roberts, W. K., 375.Robertson, A. V., 201, 202,Robertson, E.W., 121.389.306.323.Robertson, J. E., 220.Robertson, J. H., 509.Robertson, J. M., 296, 301,349, 351, 609, 512, 513.Robertson, M. S., 338.Robertson, R. E., 218.Robertson, W. W., 92.Robins, P. A., 306.Robins, R. K., 339, 373,Robinson, B., 349.Robinson, B. H., 161.Robinson, C. H., 267, 305.Robinson, D., 112, 424.Robinson, E. A., 146, 149.Robinson, G. W., 102.Robinson, J. R., 294.Robinson, M. J. T., 338.Robinson, P. L., 129.Robinson, R., 232.Robinson, R. J., 499.Robinson, R. M., 254, 335.Robinson, R. R., 246.Robinson, W. G., 420.Robson, A., 486.Rocholl, M. G., 140.Rochow, E. G., 140.Rock, M. K., 413, 414.Rodgers, H., 83.Rodder, K.-M., 130, 153.Roehrscheid, F., 184.Rsmming, Chr., 82.Rossler, S., 468.Rogalski, W., 318.Rogan, J.B., 210.Rogers, L. B., 486, 499.Rogers, M. T., 151, 193.Rogers, N. A. J., 294, 299,Rogovin, Z. A., 369.Rohr, O., 428, 429.Roisich, R. S., 298.Roitman, J., 168.Roizenblat, E. M., 486.Rollinson, C. L., 159.Romand, J., 123.Romanov, V. F., 482.RomaAuk, M., 292.Ronsch, H., 356.Rooney, J. J., 49.Root, J. W., 494.Rooney, R. C., 483, 489.Roothaan, C. C. J., 113.Roper, W. R., 161.Ropp, R. C., 500.Rosen, N., 114.Rosenberg, B. H., 371.Rosenberg, E., 367.Rosenberger, M., 314.Rosenblum, C., 411.Rosenfeld, G., 427.Rosenkranz, R. E., 328.Rosenthal, S., 407.Rosevear, D. T., 162.Ross, D. L., 224.Ross, S. D., 220.374.302INDEX OF AUTHORS’ NAMES 646Ross, S. T., 261.ROSS, W. A., 263.Rossipal, E., 430.Rossmann, M.G., 502.Roth, W. R., 238.Rothaas, A., 393.Rothberg, I., 470.Rother, A., 204, 344.Rother, M., 96.Rothschild, W. G., 195.Rouhi-Laridjani, M., 260.Rousselet, F., 488.Routly, P. M., 118.ROUX, M., 502.Row, L. R., 301.Rowe, C. A., 231.Rowe, G. A., 160.Rowe, J. M., 178, 180, 510.Rowland, F. S., 494.Rowland, L. P., 403.Rowlands, J. R., 51, 53, 54.Rowlinson, J. S., 73, 81, 84,Roy, J., 238.Ruamps, J., 119.Ruban, G., 508.Rubins, R. S., 46.Ruch, R. R., 496.Rucker, B., 407.Rudin, V. Ya., 97.Rudner, B., 134.Rudolph, H. D., 195.Rudorff, W., 164.Rudzats, R., 358.Ruchardt, C., 254.Ruedenberg, K., 1 7 1.Ruff, J. K., 133, 137.Ruherwein, R. A., 19.Ruhkopf, H., 364.Ru-Jen Lee Han, 365.Rundle, R.E., 508.Runge, H., 449.Ruoff, P. M., 365.Rupert, C. S., 372.Ruppert-Mesche, H., 163.Rusconi, A., 412.Rushbrook, P. R., 491.Rushton, J. D., 302.Russell, C. S., 386, 388, 393.Russell, G. A., 49.Russell, J., 235, 310.Russell, J. R., 262.Rutenburg, A. C., 67.Rutherford, D., 364.Rutherford, K. G., 266.Rutkin, P., 199.RBiiEka, J., 489, 493.Ruzicka, L., 429.Ryan, D. W., 428.Ryan, K. J., 429, 430.Ryback, G., 419.Rybalko, K. S., 292.Ryberg, C. E., 466.Rydberg, R., 113.Ryder, G. A., 95.Rydon, H. N., 246.88, 91, 92, 98, 99.BRyf, H., 305.Ryhage, R., 191.Rzheznikov, V. N., 306.sabel, A., 258.3abe1, H. D., 296.Sacco, A., 163.sacconi, L., 162, 164.Sackman, H., 95.Safarov, 8.A., 334.Safronov, V., 130.Sage, B. H., 98.Sagi, S. R., 468.Sah, P., 116.Saha, S. B., 456.Sahyun, M. R. V., 258.Said, A., 159.Saisho, H., 444.Saito, A., 277.Saito, S., 358.Sakami, W., 407.Sakurai, H., 462, 463, 464,Sakurai, T., 508.Sala, O., 175.Salem, A. Y., 262.Salesin, E. D., 452.Salim, N., 367.Salmon, G. A., 42.Salmon, J. E., 160.Salomon, K., 398.Salooja, K. C., 28.Salsburg, Z. W., 84, 88.Salt, M. L., 342.Salzer, F., 459.Sam, D., 495.Samkoff, N., 236.Samn6, S., 257.Samsonov, G. V., 144.Samuel, D., 204.Samuelson, O., 448.Samuelsson, B., 276, 284.SAnchez, S. C., 450.Sanchez Pedreno, C., 455.Sandalova, L. Yu, 98.Sandberg, A. A., 429.Sandberg, R., 253.Sander, C., 379.Sandermann, W., 290, 294,Sanders, R.N., 46.Sanderson, I. P., 440.Sanderson, P. M., 333.Sanderson, W. A., 224.Sandler, S., 32.Sandner, W. J., 144.Sandor, E., 505.Sandorfy, C., 203.Sendoval, A., 352.Sandri, J. M., 209.Sann, E., 414.Sano, S., 394.Sanson, L., 123.Santaram, C. V. V. S. N. K.,Santer, J. O., 300.465.318.127.laran, M. S., 470.Sarma, P. L., 441.Sarma, V. R., 502.Sasakawa, T., 404.sass, R. L., 506.3asse, W. H. F., 308.Sassu, G., 327.Satake, K., 366.Sato, A., 368.Sato, S., 43.Yato, Y., 201, 305, 356.Yatoda, I., 291.Sattar, A. B. M. A., 284.Satterfield, C. N., 23, 34.Saucy, G., 274.Sauer, J., 229.Sauers, C. K., 224.Sauers, R. R., 313.Saunders, B. C., 263.Saunders, M., 335.Saunders, W. H., 224.Sauter, W., 474.Savage, C.A., 165.Savard, K., 429.Savereide, T. J., 252.Saville, G., 86.Sawistowska, M., 257.Sawyer, D. T., 448.Sawyer, P., 456.Saxby, J., 190.Saxton, J. E., 349.Scales, B., 299, 359.Scarano, E., 470.Scatchard, G., 74.Schaefer, F. C., 279, 338.SchSifer, K., 96.Schaefer, T., 281.Schgfer, W., 147.Schaeffer, R., 132.Schafer, C., 343.Schafer, H., 157.Schaffer, R., 360.Schaffner, K., 303, 305.Schaleger, L. C., 222.Schall, E. D., 331, 358,Scharf, R., 455.Schatzki, T. F., 88.Schauble, J. H., 200, 303.Scheaver, W. R., 358.Schechter, H., 245, 260.Scheel, H., 185.Scheer, M. D., 27.Scheit, K. H., 376.Schell, P., 376.Schellenberg, M., 182.Schenck, G. O., 328, 340.Schenk, P. W., 143.Scheuerman, R.F., 506.Schiff, H. I., 21, 44.Schiffman, G., 368.Schill, G., 449.Schilt, A. A., 453.Schiltz, J., 119.Schimmel, K. F., 259.Schiweck, H., 367.489546 INDEX OF AUTHORS’ NAMESSchlafer, H. L., 154, 168,Schlenk, F., 417.Schlesinger, A. H., 210.Schleyer, P. von R., 209.Schlittler, E., 320, 353.Schmerling, L., 226.Schmialek, P., 338.Schmid, H., 237, 354.Schmid, K., 429.Schmid, R. F., 107.Schmid, W., 427.Schmidbaur, H., 141.Schmidt, H.-J., 280.Schmidt, M., 140, 141, 148.Schmidt, R., 330.Schmidt, U., 277.Schmidtke, H.-H., 94.Schmitt, R. A., 492.Schmitz, E., 321.Schmitz, F. J., 224, 320.Schmitz, R., 257.Schmitz-Dumont, O., 157.Schmutzler, R., 146.Schnalke, K. E., 335.Schneider, G., 86, 376.Schneider, H.J., 284.Schneider, I., 158.Schneider, J., 316.Schneider, R. A., 443.Schneider, W. G., 64, 200,Schnoes, H. K., 204.Schober, G., 171.Schober, G., 482.Schoeborn, B. P., 513.Schoedler, C., 462, 466.Schollkopf, U., 242, 280.Schoen, L. J., 103.Schonberg, A., 148, 317.Schoenborn, B. P., 289.Schoener, B., 418.Schonfeld, T., 493.Schonowsky, H., 271, 329.Schoental, R., 345.Schottlander, M., 202, 327.Schofield, K., 203, 338, 377.Schogt, J. C. M., 275.Scholes, P. H., 488.Scholfield, C. R., 275.Schon, H., 172.Schonauer, G., 175.Schonbaum, G. R., 248.Schott, G., 136.Schott, G. L., 19.Schriigle, W., 134.Schram, E., 490.Schram, E. P., 136.SchraufstQtter, E., 338.Schrauzer, G. N., 135, 179,Schreiber, A. M., 333.Schreiber, K., 356.Schreiber, K.C., 207, 210,Schreurs, J. W. H., 59.171.316.181, 183.219.Schrier, B., 234.Schriesheim, A., 231, 273,Schroder, I., 409.Schroder, K., 460.Schroeder, G. L., 491.Schroeder, H., 135.Schroepfer, G., 419.Schubert, W. M., 233.Schuberth, H., 94, 98.Schiihrer, K., 335.Schueler, K. E., 332.Schuett, W., 339.Schuit, G. C. A., 169.Schulenberg, J. W., 296.Schuler, R. H., 48.Schuller, W. H., 297.Schulman, M. P., 386.Schulte, K. E., 329.Schultz, D. W., 413.Schultz, H. P., 257.Schultz, J. L., 498.Schulz, G. J., 103.Schulz, J., 258.Schulze, J., 316.Schumacher, J. N., 295.Schumacher, R. T., 63.Schumann, D., 345.Schumann, H., 148.Schunior, R., 324.Schurdak, E. J., 467.Schuster, H., 376.Schuster, R., 156.Schutte, H.R., 343.Schutz, R. S., 342.Schwabe, K., 94, 96.Schwane, R. A., 359.Schwarting, A. E., 204, 344.Schwartz, H. C., 395, 396.Schwartzman, L. H., 273.Schwarz, J. C. P., 362.Schwarz, W., 219.Schwarz, W. M., 335.Schwarz, W. M., jun., 416.Schwarz-Bergkampf, E.,Schwatzenbach, G., 182.Schweers, W., 290.Schweiger, M., 382.gchweigert, B. S., 409.Schweitzer, G. K., 443.Schwendeman, R. H., 192.Schwenker, G., 195.Schwert, G. W., 419, 424.3chwieter, U., 274.Scintee, V., 457.Scott, A. I., 288, 297, 298,Scott, C. B., 311.Scott, C. C., 330.Scott, J. J., 386, 389, 392.Scott, P. G. W., 463.Scott, R. L., 73, 74, 76, 77,78, 81, 84, 92, 93, 95, 97.3cotts, G. T., 377.Scroggie, L. E., 482.335.441.319.Scroweton, R.M., 299, 359.Seakins, M., 33.Searcy, A. W., 100, 129.Searle, R. J. G., 309.Searles, S., 321.Sederholm, C. IF., 196.Sedlmeier, J., 258.Seefelder, M., 261, 269.Seel, F., 144.Seese, W. S., 304.Segal, R., 414.Segatto, P. R., 464.Seidl, J., 484.Seifert, H.-J., 156.Seifert, W. K., 219.Seifter, E., 403.Sela, M., 253.Selen, H., 199.Selig, H., 130.Selin, L.-E., 104, 119.Sellers, D. E., 483, 487.Selmer-Olsen, A. R., 478.Seltzer, S., 229.Selva, A., 255.Semenenko, K. N., 130.Semenov, D. A., 311.Semenov, I. N., 161.Semler, G., 326.Semmler, H., 144.Semochkina, T. V., 483.Sen, S., 160.Seng, F., 261.Seo, M., 350.Sepall, O., 368.Sequeira, J., 246.Serber, R., 103.Serdyuk, N. K., 33.Serebryakov, E.P., 263.Sergeant, G. A., 440.Serrano, J., 442.Serratosa, F., 270.Seshadri, T. R., 329.Setlow, R., 372.Settine, R. L., 196.Severin, T., 257.Seyferth, D., 129, 185, 243,Shachat, N., 269.Shackelford, J. M., 273.Shafer, J., 250.Shafer, J. A., 253.Shafi, M., 115.Shain, I., 335, 489.ShakhtakhtinskKG. B., 453.Shakirov, T. T., 347.Shalgosky, H. I., 488.Shalitin, Y., 253.Shaluvina, I. F., 276.Shamma, M., 205, 347, 350.Shamseldin, A. M., 469.Shanin, M., 40.Shapfro, I., 132, 135.Shapiro, M. Y., 441.Shapiro, R., 375, 377.Sharf, B., 63.Sharif, L. E., 163.261, 266INDEX OF AUTHORS’ NAMES 547Sharkey, A. G., 498.Sharkey, W. H., 258.Sharma, D., 106.Sharma, J. P., 457.Sharman, S. H., 233.Sharp, D.W. A., 166, 181.Sharp, J. H., 60.Sharpless, R. L., 126.Sharts, C. M., 281.Shatkin, A. J., 382.Shatkina, T. N., 217.Shavel, J., 351.Shaw, B. L., 179, 180.Shaw, G., 331, 339.Shaw, K. B., 389.Shaw, N., 375, 402, 409.Shaw, R., 246.Shaw, R. A., 145.Shaw, W. H. C., 440.Shawky, M., 262.Shcherbakov, V. A., 64,Shchukarev, S. A., 156,161,Shearer, H. M. M., 509.Shechter, H., 282.Sheehan, J. C., 322, 325.Sheehan, J. T., 332.Sheldon, J. C., 158.Sheline, R. K., 175, 176.Shemin, D., 386, 388, 393,Shemyakin, M. M., 260,289,Shen Han-Li, 450.Shepard, M. S., 348.Sheppard, N., 64, 190, 290.Sheppard, R. C., 332.Sheppard, W. A., 149, 263.Sheridan, J., 192.Shetty, P. S., 483.Shida, J., 51.Shields, B. D. C., 86.Shields, H., 53, 367.Shifrin, S., 413.Shigeru Oae, 230.Shihren Hu, 196.Shildkraut, C.L., 378.Shilov, A. E., 47.Shim, J., 99.Shimanouchi, T., 372, 379.Shimizu, T., 491.Shimo, K., 265, 279.Shiner, V. J., 216, 247,Shiner, V. J., jun., 421.Shingu, K., 272.Shingu, T., 349.Shinoda, K., 80, 81.Shinozuka, F., 461.Shipman, J. J., 192.Shipman, W. H., 452.Shirai, H., 489.Shishido, N., 315.Shoemaker, D., 55.Sholette, W. P., 136.65.162.403, 411.318.421.Shome, S. C., 451.Shoolery, J. N., 65, 246,Shoppee, C. W., 201, 210.Short, G. D., 471.Short, R. V., 428, 429.Shorter, J., 233, 253, 336.Shostakovskii, M. F., 272,Shoulders, B. A., 304.Showell, J. S., 262,274,280.Shrebkova, L. M., 455.Shreeve, J. M., 150.Shridhar, D.R., 302.Shrivastava, S. P., 453.Shriver, D. F., 137.Shtern, V. Ya., 22.Shtifman, L. M., 473.Shubnikov, A. V., 505.Shulgin, A. T., 263.Shulman, R. G., 45, 46.Shults, W. D., 464.Shukla, R. C., 114.Shute, S. H., 363.Shvo, Y., 300.Sh;yrkova, L. A., 462.Sibatani, A., 380.Sicher, J., 287, 344.Siddiqui, S., 349.Sidyakin, G. P., 347.Sieber, R., 258.Siegel, E., 259.Siegel, L., 425.Sierra, F., 455.Sievers, R. E., 171.Sigsby, J. E., 449.Sikes, J. H., 479.Silbert, L. S., 259, 274.Silsbee, R. H., 62.Silva, R. A., 343.Silver, H. B., 136.Silver, M. S., 208, 250.Silverstone, N. M., 468.Silvey, W. D., 476.Sim, G. A., 286, 291, 293,294, 296, 297, 298, 301,317, 330, 349, 351, 607,509, 512, 513.Simamura, O., 236.Simatupang, M.H., 318.Simes, J. J. H., 300.Simkin, J., 170.Simmler, W., 430.Simmons, H. E., 311.Simmons, R. F., 24.Simmons, W. C., 135.Simon, H., 224, 361.Simon, M., 86, 374.Simon, R. W., 258.Simon, W., 232, 474.Simonov, A. M., 331.Simonson, R., 448.Simpson, M. V., 371.Simpson, W. R. J., 297.Singh, A., 217, 358.Singh, B., 470.352, 431.280.Singh, B. R., 450.Singh, D., 460, 461.Singh, J. J., 451.Singh, J. L., 114.Singh, N., 358.Singh, N. L., 112, 114.Singh, R. P., 478.Singleton, M. F., 364.Sinsheimer, R. L., 379.Sirois, J. C., 485.Sisido, K., 277.Sisler, H. H., 145.Sisman, E., 457.Sisti, A., 262.Sitaram, P., 109.Sitdykova, N. S., 130.Sivasankaran, K., 254.Sizer, I. W., 425.Sjoberg, B., 190, 194.Sjolander, N.O., 319.Sjovall, J., 284.Skahan, D. J., 497.Skaric, V., 325.Skeil, P. S., 216.Skidmore, S., 337.Skinner, G. B., 19.Skinner, W. A., 424.Skirrow, G., 35, 37.Sklar, R., 353.Sklarr, R., 351, 513.Sklarz, B., 300.Skoda, J., 447.Skoludek, H., 154.Skomoroski, R. M., 335.Skorcz, J. A., 235, 416.Skripov, F. I., 69.Skripov, V. P., 97.Skrube, H., 494.Slade, P., 250, 306.Slagel, R. C., 292.Slater, C. D., 236.Slaughter, C., 405.Slaunwhite, W. R., 429.Slavik, V., 467.Sleight, A. W., 161.Sleva, S. F., 465.Sloan, A. D. B., 308.Sloan, H., 185.Slomba, A. F., 109.Slomp, G., 201, 337.Small, A., 210, 281.Small, R. W. H., 159, 501,Smaller, B. O., 55, 58.Smalley, H. M., 271.Smallwood, S.E. F., 113.Smart, J., 377.Smellie, R. M. S., 382.Smidt, J., 47, 258.Smiley, K. L., 403.Smirnov, B. P., 494.Smirnova, G. S., 369.Smith, B. C., 145.Smith, B. R., 208.Smith, B. V., 232.Smith, C. R., jun., 275.504, 506548 INDEX OF AUTHORS' NAMESSmith, D. L., 181, 488.Smith, E. A., 159.Smith, E. B., 74, 75, 81, 94.Smith, E. L., 375, 395, 407.Smith, E. M., 463.Smith, F., 95, 367.Smith, F. T., 123.Smith, G. F., 349, 355, 439.Smith, G. L., 258.Smith, G. N., 276.Smith, G. S., 503.Smith, H., 492.Smith, H. E., 290.Smith, H. G., 502.Smith, J., 258.Smith, J. A. S., 194.Smith, J. C., 269.Smith, J. D., 137.Smith, J. H., 168.Smith, L. L., 432.Smith, L. W., 346.Smith, M., 266, 306.Smith, M. V., 277.Smith, N.L., 145.Smith, 0. W., 429.Smith, P. A., 244.Smith, P. A. S., 220, 232,Smith, P. W., 158.Smith, R. A., 84.Smith, R. A. D., 459, 474.Smith, R. M., 403, 405.Smith, S., 259.Smith, S. G., 213, 229.Smith, W., 230, 275, 276,Smith, W. A., 223.Smith, W. B., 273.Smith, W. C., 149, 263.Smith, W. V., 109.Smithen, C. E., 326.Smithies, O., 419.Smolina, T. A., 230.Smolinsky, G., 60,244, 309,Smolyar, B. Ya., 131.Smyth, R. D., 400, 401.Snavelly, F. A., 202.Sneen, R. A., 208,209,214.Snell, J. F., 319.Sniegoski, L. T., 361, 496.Snodgrass, P. J., 423.'Snow, R. L., 94.Snowden, P., 98.Snowden, F. F., 27.Snyder, L. C., 56, 60, 240.Snyder, R. G., 179.Sobell, M., 362, 363.Sobolov, M., 403.Soderberg, R. H., 163.Soeder, R.W., 286.Soderberg, B., 104.Sorensen, N. A., 271.Sorlin, G., 328.Soffer, L. J., 427, 429.Sokoleva, N. A., 38.325.507.321.Sokolov, S. D., 331.Soler, A. J., 362.Solliday, N., 216.Sollott, G. P., 146.Solomon, I. J., 147.Solomon, J., 487.Solomon, S., 432.Solon, E., 463.Somcynsky, T., 99.Somerville, S. M., 238.Sommer, L., 440, 441.Sommer, L. H., 207, 254.Sommer, N., 261.Sommer, P. F., 474.Son Bredenberg, J. B., 299.Sondheimer, F., 198, 305,Sonnenberg, J., 313.Somevald, W., 275.Sorenson, T. S., 418.fiorm, F., 277, 292, 303,375, 377.Sorokin, M. I?., 44.Sosey, A. D., 52.Soto, A., 338.SouEek, J., 465, 474.Souchay, P., 486.Souciec, M., 295.Soulal, M. J., 322.Soulen, J. R., 499.Sousta, J. A., 336.Sowden, J.C., 364.Sowerby, D. B., 137, 149.Sowinski, F. A., 342.Soyama, T., 425.fipaEkovB, A., 475.Spalla, C., 411, 412.Spalthoff, W., 65.Spanier, E. J., 139.Sparatore, F., 395.Spare, C. G., 278.Sparks, R. A., 514.Speakman, J. C., 509.Specht, H., 449.Spees, S. T., 171.Spell, W. H., 409.Spence, R., 27.Spencer, E. Y., 294.Spencer, I. D., 343.Spencer, J. F. T., 279.Spencer, M., 378.Spencer, R. D., 471.Spencer, R. R., 366.Sperry, J. A., 232.Speyer, J. F., 381.Spiegelmann, S., 380.Spikner, J. E., 477.Spilners, I. J., 497.Spinks, J. W., 49.Spinner, E., 203.Spinner, I. H., 94.Spiteller, G., 204, 352.Spiteller-Friedmann, M.,Spitzy, H., 494.Sponer, H., 100.307, 316, 327.204.Spray, G. H., 410.Springer, R.H., 339, 374.Sprinson, D. B., 411.Spritzer, M., 487.Srinivasan, R., 287, 502.Srivastava, K. C., 467.Srivastava, T. N., 142.Straab, H. A., 261, 262, 320.Stacey, F. W., 227.Stacey, M., 361, 364, 366,Stadtman, E. R., 404.Stadtman, T. C., 402, 410.Stgllberg-Stenhagen, S.,Stafford, F. E., 119, 120.Stafford, S. L., 177.Staiff, D. C., 197.Stam, C. H., 507.Stamberg, J., 484.Stammreich, H., 175.Stamper, J. G., 121, 122.Stangl, H., 323.Stanier, R. Y., 274.Stanko, V. I., 135.Stansfield, F., 314.Stanton, G. M., 333.Stanton, R. E., 478, 489.Staples, C. E., 191.Starer, I., 216.Stark, G., 355, 430.Stark, G. R., 462.Starkey, J. H., 277.Starman, B., 379.Starnes, W. H., 235.Starodubtsev, S. V., 361.Starova, N.G., 280.Starratt, A. N., 300.Stary, J., 493.Stary, Z. P., 486.Staskun, B., 262.Staszewski, R., 448.Statz, H., 46.Stauffacher, D., 348, 352.Staum, M. M., 212.Staveley, L. A. K., 88.Stedman, R. J., 393.Steed, K. C., 464.Steele, D., 113, 114.Steele, E. L., 492.Steffens, J., 361.Steglich, W., 263.Stehling, F. C., 497.Stein, G., 414.Stein, P. C., 493.Stein, T. W., 23.Steinberg, D. H., 199.Steinberg, M., 152.Steinbrecher, M., 96.Steiner, A., 332.Steiner, R. F., 371.Steinert, H., 34.Steltenkamp, R. J., 280.Stenhagen, E., 191, 275.Stephan, A., 316.spumy, z., 479.367.191, 275INDEX OF AUTHORS’ NAMES 549Stephen, A. M., 367.Stephens, B. G., 454.Stephens, F. B., 463, 464.Stephens, R., 311.Stephenson, M.L., 382.StBrba, J., 445.Stern, E. W., 179.Stern, J. R., 404.Sternbech, B., 141.Sternhell, S., 260.Sterlicht, H., 61.Sterlyadkina, Z. K., 130.Stetter, H., 320.Steudel, W., 342.Stevens, A., 407.Stevens, C. L., 339..Stevens, I. D. R., 241, 321,Stevens, M. A., 373.Stevenson, D. P., 83.Stevenson, R., 300.Stevenson, R. W. H., 46.Steward, E. G., 167.Stewart, C. A., 228.Stewart, C. A., jun., 281.Stewart, D. F., 159, 469.Stewart, F. H. C., 264.Stewart, R., 230.Stiddall, T. H., tert., 191.Stiddard, M. H. B., 177.Still, J. E., 459.Stimson, V. R.. 224.Stirling, C. J. M., 216.Stjernholm, R., 404.Stock, A., 414, 415.Stock, D. I., 170.Stock, J. T., 458, 461, 466.stock, L. M., 232.Stocker, J. H., 254.Stoicheff, B., 190.Stoicheff, B.P., 189, 190,Stollar, D., 424.Stolz, I. W., 175, 176.Stone, A. J., 47.Stone, E. W., 56, 58.Stone, F. G. A., 176, 177,180, 184, 185, 254, 255,283.331.195.Stone, G. R., 335.Stone, T. J., 48.Stone, W., 90.Stoner, G. A., 477.Stoodley, R. J., 361.Storey, J. D., 486.Stork, G., 201, 270, 296,306, 318, 328.Storms, E. K., 156.Storonkin, A. V., 97.Storr, A., 137.Storr, R., 143.Stothers, J. B., 219, 284,Stotz, E., 396.Stout, G. H., 503, 509.Stout, V. F., 509.337.Stove, E. R., 322.Stover, E. D., 67.Strachan, R. G., 279.Stradling, S. S., 237.Strain, H. H., 325.Strandjord, P. E., 415.Strating, J., 340.Strauss, H. L., 50.Street, H. V., 448.Streib, W. E., 501.Streibl, M., 277.Streitwieser, A., 207, 214,Strehlow, H., 246.Strem, M.E., 308.Streuli, C. A., 458.Stricks, W., 487.Striegler, K., 318.Strivens, T. A., 463.Strohmeier, W., 130, 175,Strolenberg, K., 146.Strom, E. T., 49.Strominger, J. L., 377.Strong, R. L., 82.Struck, J., 425.Strunin, B. N., 265.Stuart, R., 46.Stubbs, W. H., 184.Stubley, D., 92, 99.Studer, P., 446.Sturm, B. J., 158.Sturm, H. J., 323.Stutz, A. I., 141.Style, D. W. G., 27.Su, D., 378.Subbaraman, P. R., 483.Subba Rao, G. S. R., 301.Subbaratham, N. R., 40.Subramanian, E., 503.Such$, M., 292.Sucrow, W., 271.Sueoka, N., 378.Sueur, R., 31.Sugano, S., 46.Sugden, T. M., 20, 100,207.Sugimoto, N., 358.Sugita, Y., 395.Sui, C. W., 477.Suld, G., 341.Sulkowski, T.S., 339.Sullivan, E. A., 132, 257.Sullivan, P. J., 205.Sullivan, R. A. L., 507.Sullivan, R. J., 83.Sully, B. D., 438.Summa, A. F., 487.Sund, H., 422.Sundaram, A., 191, 199.Sundaram, K. M. S., 199.Sundermeyer, W., 138, 140,Sung Moon, 210.Sunjaraman, M. G., 170.Sunko, D. E., 209.Supin, G. S., 483.230, 232.182.151.Suresh, K. S., 333.Surls, J. P., 491.Suschitzky, H., 337.Sustmann, R., 139.Susz, B. P., 155.Sutcliffe, L. H., 145, 162.Sutherland, I., 411.Sutherland, I. O., 318.Sutherland, J. K., 286.Sutherland, M. D., 290,291.Sutherland, S. A., 301, 513.Suttle, J. F., 154.Sutton, G. J., 158, 160, 167.Suydam, F. H., 202.Suzuki, I., 193.Suzuki, M., 19.Suzuki, N., 493.Suzuki, S., 362, 370.Svehla, G., 500.Svendsen, A.B., 448.Svensson, R., 466.Svoboda, M., 287.Swain, C. G., 213, 218, 219,Swalen, J. D., 47, 58.Swaminathan, K., 165, 174.Swaminathan, S., 287.Swan, G. A., 235.Swanholm, C. E., 204, 354.Swartz, M. N., 378.Sweat, M. L., 427, 429.Sweeley, C. C., 275.Sweeney, D. M. C., 190.Sweet, T. R., 493.Swern, D., 259, 262, 274,Swift, T. J., 68.Swinnerton, J. W., 449.Swor, R., 445.Sykes, A. G., 173.Sykes, P. J., 277.Symons, M. C. R., 45, 47,48, 49, 51, 54, 55, 56, 57,58, 61, 63, 68, 150, 151,161, 171.311.280.Symons, R. H., 381.Syrkin, Ya-K., 165.Szab6, L., 362, 365.Szabo, Z. G., 82.Szantay, C., 321.Szejtli, J., 369.Szkrybalo, W., 198.Szot, Z., 388.Ta-Chuang Lo Chang, 275.Tada, M., 382.Taft, It.W., 218.Taguchi, I., 508.Taha, I. A. I., 208.Taher, N. A., 218.Taikova, N. K., 279.Tait, G. H., 386, 397, 398.Tait, J. F., 430, 431.Tait, S. A. S., 430, 431.Takahashi, T., 462, 463,464, 465, 489550 INDEX OF AUTHORS' NAMESTakahashi, Y., 302.Takai, M., 380.Takamoto, S., 441.Takamuru, S., 369.Takanami, M., 382.Takase, M., 278.Takenaka, Y., 419.Takeoka, Y., 196.Takeshita, H., 284.Takeyama, S., 406.Takiura, K., 367.Talipova, L. L., 455.Tallent, W. H., 299.Tallmann, R. L., 130.Talmage, P., 386.Talrose, V. L., 24.Tamiya, N., 498.Tamres, M., 82.Tamura, Y., 358.Tan, L., 355.Tan, S. H., 458.Tanaka, K., 417.Tanaka, Y., 106, 107, 123,125, 126, 364.Tanawv, I. V., 154.Tandon, K. N., 453.Tanei, T., 52.Tanida, H., 223.Tanner, H., 263.Tao, L.C., 94.Tao, R. C. C., 197.Taqui Khan, M. M., 422.Tarbell, D. S., 237.Tarlton, E. J., 389.Tarrant, P., 196.Tartari, A., 481.Tashkentsk, Tr., 369.Tashmukhamedova,K.,361.Tate, D. P., 176.Tate, M. E., 359, 366.Tatievskii, V. M., 127.Tatlow, J. C., 310, 311.Tatum, E. L., 382.Taub, D., 318.Taub, I. A., 236.Taube, H., 67, 153.Taurog, H., 494.Tavs, P., 275.Tawde, N. R., 112.Taylor, A., 502.Taylor, B., 154.Taylor, C. A., 503.Taylor, D. R., 357.Taylor, E. C., 240, 337, 338.Taylor, F. B., 136.Taylor, H. G., 440.Taylor, J. B., 343.Taylor, L. J., 219.Taylor, M. S., 454.Taylor, P. M., 359.Taylor, R. C., 137.Taylor, W. I., 326, 351, 362,Tedder, J. M., 324.Tedeschi, P., 416.Teekell, R.A., 445.353, 513.Teijgeler, C. A., 446.Tekhonova, E. A., 504.Telang, S. A., 341.Teller, E., 114.Temperley, H. N. V., 94.Templeton, D. H., 507.Tener, G. M., 376, 377.Tengler, H., 178.Tennigkeit, J., 376.Tenseldam, C. A., 120.Tera, F., 483.Teraoka, A., 348.Terashima, M., 348.ter Borg, A. P., 307, 313Terent'eva, E. A., 484.Ter Haar, G., 135.Terry, W. G., 323.Testa, C., 444.Testa, E., 323.Tetenbaum, M. T., 480.Thacker, R., 81.Thaller, V., 296.Thayer, J. S., 140.Theal Stewart, E., 113.Theobald, R. S., 368.Theorell, H., 418, 421, 422Thesing, J., 326.Theubert, F., 177.Thickbroom, P. D., 269.Thiessen, W. E., 299.Thierig, D., 135.Thilo, E., 146.Thodos, G., 98.Thofern, E., 396.Thoma, J.A., 369.Thomaes, G., 90.Thomas, A. F., 301, 302.Thomas, G. M., 343.Thomas, I. M., 157.Thomas, J. D. R., 449.Thomas, J. R., 53.Thomas, L. F., 363.Thomas, L. M., 466.Thomas, M. R., 325.Thomas, S. S., 43.Thompson, A., 367.Thompson, A. R., 97.Thompson, H. M., 126.Thompson, L. C., 152.Thompson, M. C., 173.Thompson, R., 259.Thompson, R. Y., 377.Thomson, C., 53.Thomson, J., 369.Thomson, J. F., 424.Thornson, P. J., 319.Thornson, R. H., 235, 310.Thomson, R. S., 233.rhomson, S. J., 254.I'hornley, J. H. M., 46.rhornton, E. R., 218.rhorp, N., 78.rhrush, B. A., 20,102,121,rhurmond, C. J., 120.314, 315.314.Thurn, R. D., 222.Thyret, H., 183.Tichf, M., 344.Tidy, D., 217.Tiers, G. V. D., 282.Tietz, T., 114.Tighe, J.J., 21.Tjebbes, T., 338.Tikhomirova, N. N., 47.Tikhomolova, M. P., 361.Till, F., 449.Till, I., 449.Tilney-Bassett, J. F., 244.Timell, T. E., 370.Timmons, P. S., 235.Tipper, C. F. H., 18, 31, 35,Tipson, R. S., 359.Titkov, Yu. V., 144.Titova, V. A., 97.Tiwari, R. D., 457.Tobe, M. L., 174.Tobias, I., 113, 114.Tochtermann, W., 311,313,Tockstein, A,, 82, 484.Todd, Lord, 318, 375, 377,Todd, R., 490.Toekelt, W. G., 226.Tolg, G., 443.Tomoskozi, I., 260.Tokes, L., 235, 269.Tokoroyama, T., 292.Tolbert, T. L., 262.Tolchinskaya, R. Ya., 280.Tolgyesi, W. S., 240.Tolgyest, W. S., 285.Tolles, W. C., 149.Tolmacheva, T. A., 156.Tolnas, E. L., 120.Tomalia, D. A., 320.Tomasz, M., 270, 318, 328.Tomita, K., 360, 372.Tomita, M., 348.Tomko, J., 356.Tomlin, J.E., 263, 276.Tomljenovi6, T., 219, 287.Tommila, E., 235.Tompkina, F. C., 14, 15.Tomkins, G. M., 425, 416,Tong, E., 424.Tooney, J. I., 401, 403.Toporowski, P. M., 97.Topping, G., 193.Topping, R. M., 244.Toptygina, G. M., 154.Torgov, I. V., 306.Torresani, J., 494.I'oscano, V. G., 261.roubiana, R., 276.Toussaint, A., 198.rowe, R. H., 185.Tome, J. C., 477.rownley, E. R., 267,287.37.342.383, 341, 411.426INDEX OF AUTHORS’ NAMES 551Towns, D. L., 230.Townsend, M. G., 48, 82.Trager, L., 372, 373, 409.Traetteberg, M., 190.Trager, W. F., 196.Trahanovsky, W. S., 202.Trajmar, S., 127.Traore, K., 161.Trapasso, L. E., 255.Trapnell, B. M.W., 13.Trapp, W. B., 254.Trautner, T. A., 378.Travers, S., 501.Travis, D. N., 101,119,121.Treanor, C. E., 126.Treanor, C. T., 111.Treble, D. H., 420.Trecker, D. J., 267, 287.Tregellas-Williams, J., 194.Trego, B. R., 280.Treiber, A., 183.Treibs, A., 393.Treichel, P. M., 176.Trkmillon, B., 459.Trenczek, G., 137.Trepka, W. J., 266.Trevalion, P. A., 55, 171.Trifan, D. S., 209.Tripathi, J. B. P., 143.Tripp, T. B., 92.Trippett, S., 299, 359.Trohenko, S., 279.Trombe, I., 153.Trond, S. S., 159.Trotman-Dickenson, A. F.,Trotter, J., 161, 507, 508,Trowell, F., 440.Trozzolo, A. M., 60.Truce, W. E., 258,280,322.Trueblood, K. N., 514.Trumbull, E. R., 224.Truscheit, E., 278.Truter, E. V., 446.Truter, M. R., 181.Tsaboi, M., 372.Tsapkina, I.V., 153.Tschesche, R., 355.Tseng, W. S., 417.Tsiklis, D. S., 98.Tsinsius, V. M., 156.Ts’O, P. 0. P., 379.Tsou~aris, G., 510.Tsuboi, M., 379.Tsuchida, R., 162.Tsuda, K., 201.Tsuda, S., 345.Tsuda, Y., 349.Tsugita, A., 381.Tsukahara, I., 491.Tsukamoto, A., 262.Tsunakawa, S., 191.Tsutsui, M., 283.Tsymbal, L. V., 280.Tiirk, G., 161.35.509.Tuleen, D. L., 253.Tulloch, A. P., 279.Tundo, A., 329.Tunitskii, L. N., 127.Turco, A., 160.Turnbull, A. H., 166.Turnbull, J. P., 294.Turner, D. W., 36.Turner, H. S., 134.Turner, J. C., 360, 366.Turner, J. M., 388.Turner, M. A., 222.Turner, W. J., 393.Turner- Jones, A,, 506.Turova, N. Ya., 130.Turro, N. J., 283, 288.Turvey, J.R., 365.Tur’yan, Ya. I., 482, 486.Tuttle, T. R., 50.Twigg, G. H., 258.Tyler, B. J., 24.Tyler, C. M. B., 338.Tyree, S. Y., jun., 159.Tyte, D. C., 123.Tze Yung-Schaing, 450.Ubell, E., 510.Uchikawa, H., 478.Uchiyama, M., 281.Ud-Din, B., 165.Ueberwasser, H., 305.Ueda, S., 348.Onseren, E., 240.Ugelstad, J., 273.Ugi, I., 252.Uhle, F. C., 306.Uhlenbrock, W., 311.Uhler, R. O., 282.TJhler, U., 127.Uhlig, E., 172.Ukafi, T., 192.Ukita, T., 365, 376.Ukshe, E. A., 129.Ulbricht, T. L. V., 320,374, 375, 376.Ulick, S., 430.Ullman, E. F., 307, 310,331, 340.Ulm, K., 183.Ulmann, M., 369.Ulmer, D. D., 420, 423.Umland, F., 135, 443.Umori, T., 493.Undes, R., 466.Underhill, A. E., 167, 171.Underwood, J. G., 329.Undheim, K., 190.Ung, A.Y. M., 44.Ungar, F., 416.Uno, T., 193.Urata, G., 387.Urenovitch, J. V., 139.Urquhart, J., 427.Urry, G., 136, 140.Urry, W. H., 267, 287.Urusovskaya, L. G., 473.Ushakaova, N. I., 165.Ustkins, I., 407.Utkin, L. M., 346.Utley, J. H. P., 253.Utzinger, E. C., 305.Uyeo, S., 348, 349.Uzelac, V., 478.VBgo, G., 487.Vagurtova, N. M., 331.Vahlquist, B., 389.Vahvaselkii, E., 447.Vainshtein, B. K., 507.Vainshtein, E. E., 154.Valenta, Z., 299, 357, 358.Valentin, P., 31.Valiev, K. A., 72.Vallee, B. L., 413, 420, 422,Valnf, Z., 469.Van Ammers, M., 336.van Atta, R. E., 487.van Auken, T. V., 330.van Beers, G. V., 275.Vance, R. N., jun., 166.Vandenheuvel, W. J. A.,van der Helm, H. J., 420.van der Kerk, G.J. M., 142.Vanderslice, J. T., 113, 114.van der Waals, J. H., 93.van der Want, G. M., 143.Vanderwerf, C. A., 220.Vandewiele, R. L., 429,432,Vhndorffy, M. T., 473.Vane, F. M., 194.van Egmond, J. C., 142.Van Ehrenstein, G., 382.van Erkelens, P. C., 493.van Eys, J., 417, 420.Vangedal, S., 300.van Heijningen, R. J. J.,van Helden, R., 313, 314,van Koeveringe, J. L., 120.van Meerssche, M., 511.van Ness, H. C., 94, 95.van Norman, J. D., 465.Van Praag, D., 375.van Sickle, D. E., 230.van Steenwinkel, R., 90.van Tamelen, E. E., 276,285, 303, 307, 320.van Tiggeln, A., 21.Van Zanter, B., 492.Varga, L. P., 158.Varhenikovh, A., 446.Varma, A., 460.Varshni, Y. P., 114.Vasedeve Murthy, A. R.,Vasilevskii, K.P., 128.Vasiliev, R., 457.Vasisht, S. K., 459.423.210.433, 434.86, 87.315.149552 INDEX OF AUTHORS’ NAMESVaska, L., 178, 186.Vassalls, D. A., 499.Vatakencherry, P. A., 291.Vaughan, E. J., 436.Vaughan, J., 246.Vaughan, W. R., 253, 322.Vaver, V. A., 260.Vdovenko, V. M., 65.VeEeFa, M., 459, 474.Velasco, R., 121.Velick, S. F., 413, 418.Venanzi, L. M., 160, 161,Venkataraman, K., 341.Venkatesan, K., 287.Venkateswarlu, P., 127.Venkateswarlu, V., 450.Vercellotti, J. R., 368.Verderame, F., 191.Vereikina, L. I,., 144.Verhaegen, G., 119, 120,Verhoek, F. H., 163.Verkade, J. G., 172.Verma, B. C., 470.Verma, R. D., 101,106,128.Verma, R. M., 453.Verma, V. K., 333.Vermont, G. B., 236.Vernon, C. A., 244.Vernon, J.M., 324, 325.Verron, H., 278.Verwoerd, D. W., 376.Vesell, E. S., 419, 420.Vesety, V., 454, 455.Vessman, J., 449.Vetter, H. J., 147.Vickery, M., 338.Viehe, H. G., 270.Viennet, R., 200.Vilfm, O., 94.Vilkov, L. V., 506, 510.Villotti, R., 305.Vinard, D. R., 269.Vincent, B. F., jun., 258.Vinogradov, A. V., 451.Virmani, Y. P., 203.Virtanen, A. I., 278, 320.Viswanathan, N., 354, 358.Vitali, R., 256.Vizsolyi, J. P., 377.Vlad, P., 295.Vodar, B., 123.Voevodskii, V. V., 24, 25,Vogel, A. I., 203.Vogel, E., 341.Vogel, G., 130, 340.Vogel, J., 485, 488.Vogler, A., 183.Vogt, F., 145.Voitovich, B. A., 157.Volcani, B. E., 401, 403.Vol’kenshtein, M. V., 198,Volkin, E., 379.165, 170.128.34, 52.200.Volpenhein, R.A., 277.Volpin, M. E., 322.Volpp, G., 342.von Dobeneck, H., 334.von Euler, H., 417.Von Hobe, D., 175, 182.von Planta, C., 274.von Rosenberg, J. L., 313.von Rosenberg, J. L., jun.,von Stackelberg, M., 482.von Veh, G., 322.von Witteneu, M. S., 327.Voorhies, J. D., 467.Vo-Quang, L., 269.Vorbrueggen, H., 204, 352.Vos, A., 511.Vreugdenhil, A. D., 266.Vriassen, C. H., 47.Vu, H., 103.Vulterin, J., 452, 453.Vydra, F., 469.Vyshinskaya, L. I., 184.286.Wacber, A., 372, 373, 409.Wade, K., 137.Wade, M. A., 479.Waddington, H. R. J., 322.Waddington, T. C., 136,Waelbroeck, F., 91.Wagener, S., 13.Wagenhofer, H., 323.Wagner, A., 367.Wagner, C. R., 221.Wagner, F., 411, 412.Wagner, G., 375, 458.Wagner, O., 413.Wagner, R.I., 134.Wagner, R. P., 145.Wahba, A. J., 381.Wahl, D., 412.Waichiro Tagaki, 230.Waind, G. M., 162.Waiss, A. C., 214, 345.Waite, B. D., 480.Wakamatsu, S., 265, 279.Walborsky, H. M., 230.Waldenstrom, J., 389.Walerych, N., 413.Waley, S. G., 187, 207.Walia, J. P., 253.Walker, G. N., 254, 335.Walker, H. G., jun., 364.Walker, J., 306.Walker, P., 244.Walker, R. W., 24, 25.Walker, T., 347, 348.Walkiewitz, D., 142.Walkley, J., 74, 75, 81, 82.Wallace, L., 123, 127.Wallace, R. M., 179.Wallbridge, M. G. H., 137,Wallenfels, K., 416, 422.Walling, C., 228, 237.151.223.Wallis, E. S., 210.Walls, F., 352.Walrafen, G. E., 150.Walsh, A. D., 23, 27, 42, 55.Walsh, P. N., 102.Walter, P., 416, 418.Walter, P.H. L., 161.Walter, S. I., 420.Walter, W., 280.Walter, W. F., 276, 320.Walton, H. F., 170.Walvekar, A. P., 112.Walwick, E. R., 375.Wampler, D. L., 138.Wandrey, P., 345.Wang, 1.-C., 69, 71.Wang, R. H., 98.Wang, S. Y., 372.Wannagat, U., 140.Wanzlick, H. W., 242.Wasicky, R., 446.Wasserman, E., 60, 244.Warburg, O., 396.Ward, C. H., 206.Ward, E. R., 232, 266, 333.Ward, G. M., 476.Ward, J. C., 49.Ward, L. G. L., 139.Ward, R., 161.Ward, R. B., 367.Ward, R. L., 51, 53, 57.Wardi, A. H., 486.Waris, A., 39.Warne, R. J., 134.Warren, C. L., 200, 317.Warren, F. L., 343.Warton, J. W., 448.Warwicker, E. A., 32, 39.Warzecha, K., 424.Watanabe, H., 294.Watanabe, I., 379.Watanabe, K., 125.Watanabe, T., 366, 508.Watari, H., 425.Waters, A.H., 407.Waters, E. L., 47.Waters, J. M., 164.Waters, 0. J., 290.Waters, W. A., 48, 244.Watkins, J., 326.Watling, J., 488.Watson, A. A., 280.Watson, D. G., 509,Watson, H. R., 164, 171.Watson, J. D., 379.Watson, J. S., 42.Watson, T. R., 366.Watson, W. H., 223.Watt, G. W., 154, 163,165.Watton, E. C., 167.Watts, D. C., 419.Watts, D. W., 174.Watts-Tobin, R. J., 380.Wawrzyczek, W., 442.Vlfawszkiewicz, E. J., 400.Wawzonek, S., 480INDEX OF AUTHORS’ NAMES 553Wayne, R., 267.Wayne-Meinke, W., 492.Webb, G. B., 347.Webb, J. S., 366.Webb, R. E., 403.Webb, W. E., 194.Webber, J. M., 366, 367.Weber, G., 418.Weber, K. H., 316.Weber, M. J., 46.Weber, R., 258.Weberndorfer, V., 333.Webster, B., 324.Webster, B.R., 338.Webster, D. E., 254.Webster, G., 383.Webster, 0. W., 258.Weedon, B. C. L., 269, 273.Wehrli, H., 303, 305.Wei, P. E., 336.Weidler, A. M., 190.Weidmann, G., 443.Wei-Hsien Chang, 446.Weil, J. A., 47.Weimann, G., 376.Weinberg, K., 305.Weinblum, D., 372, 373.Weiner, H., 214.Weiner, M., 130.Weinhold, P., 311.Weinstein, B., 296.Weinstein, S., 223.Weinstock, J., 223.Weir, H. E., 475.Weis, C. D., 328.Weis, W., 335.Weisblum, B., 382.Weiss, A., 275.Weiss, E., 181.Weiss, H. G., 132.Weiss, H. V., 452, 495.Weiss, J., 199.Webs, U., 289, 297.Weissbach, H., 400, 401,Weiss-Broday, M., 204.Weissman, S. I., 45, 50, 53,58, 59, 60, 61, 136.Weisz, D., 147.Weisz, H., 438, 490.Weitkamp, H., 195, 281.Weitz, G., 513.Welch, C.A., 231.Welch, V. A., 365.Welcman, N., 146, 150.Weliky, I., 427.Wellington, C. A., 41.Wells, A. F., 129.Wells, C. H. J., 34.Wells, R. J., 293.Welsh, H. L., 190.Welsh, M. J., 509.Welti, D., 191, 195.Weltner, W., 102.Wempen, I., 374.Wender, S. H., 446.413.Wendlandt, W. W., 166,Wendler, N. L., 318.Wenger, P. E., 468.Wenger, R., 305.Weniger, S., 118.Wenkert, E., 343, 349, 350,Werbin, H., 427.Werhagen, E., 106.Werner, D., 144.Werner, H., 184.Werner, L., 320.Werner, R. P. M., 180.Wertheim, G. K., 169.Wertz, J. E., 50, 68, 71.West, B. O., 147, 155, 162,West, C. D., 429.West, R., 130,138, 140, 313.West, T. S., 440, 469, 478,Westall, R. G., 389.Westenberg, A.A., 20.Westerlund, B., 106, 124.Westheimer, F. H., 249,335, 415, 416.Westin, B., 434.Weston, J. F., 91.Wettermark, G., 336.Wettstein, A., 256, 305,Weygand, F., 224, 263.Whalley, E., 96.Whalley, W. B., 358.Wharton, P. S., 306, 355.Whealy, R. D., 485.Wheatley, P. J., 140, 144,Wheeler, D. H., 71.Whelan, W. J., 359, 370.Whiffen, D. H., 53, 54, 55,Whipple, E. B., 326.Whistler, R. L., 360, 364,Whitaker, D. R., 366.Whitaker, J. R., 247.White, A. M., 405, 406.White, D., 103.White, D. C., 397.White, D. E., 298.White, E. H., 287.White, E. M., 219.White, J. C. B., 203.White, J. G., 514.White, R. C., 159.White, R. F. M., 64.White, R. W., 259, 294.White, W. N., 236, 240.Whitear, B., 289.Whitehead, E. P., 423.Whitehead, R.W., 408.Whitehurst, J. S., 306.Whiteley, T. E., 365.Whitham, G. H., 210.499.351, 353.168.484.427, 429.508, 511.56, 57.369.Whiting, D. A., 329.Whiting, K. D. E., 347, 348.Whitley, A., 165.Whitlock, H. W., 312, 341.Whitlock, H. W., jun., 288.Whitman, S. L., 383.Whitney, D. R., 502.Whitney, R. B., 246.Whittaker, D., 191, 195.Whittaker, N., 260.Wibberley, D. G., 327.Wiberg, K. B., 288, 312.Wiberg, N., 139.Wickberg, B., 350, 351.Wieber, M., 140, 141.Wieland, A., 335.Wieland, K., 102.Wieland, P., 305.Wieland, T., 419, 424.Wiesendanger, H. U. D., 13.Wiesener, K., 94, 96, 299,Wiest, H., 229.Wigen, P. E., 55.Wiggins, T. A., 109.Wilcox, C. F., 209, 210.Wilcox, H.E., 510.Wilcox, W. S., 132.Wilde, G., 163.Wildman, W. C., 343, 348.Wiley, P. F., 341.Wilharm, G., 412.Wilhelm, G., 86.Wilkas, M., 260.Wilke, G., 179.Wilkins, C. J., 160.Wilkins, M. H. F., 378.Wilkins, R. G., 174.Wilkinson, G., 129, 160,Wilkinson, P. G., 100, 106,Willcott, M. R., tert., 200,Wille, F., 332.Willemert, A., 269.Willey, F. G., 304.Willey, G., 145.Willey, R. H., 191.William Johnson, A., 242.Williams, A., 35.Williams, A. A., 179.Williams, A. R., 336.Williams, D. E., 508.Williams, D. L. H., 224.Williams, F. T., jun., 260.Williams, G. H., 235.Williams, H., 337.Williams, J. C., 277.Williams, J. H., 444.Williams, J. M., 368.Williams, M., 451.Williams, M. J., 111.Williams, N. R., 360.Williams, N. J., 332.Williams, P. L., 438.357, 358.176, 180, 181, 184.107, 109, 122.289554 INDEX OF AUTHORS’ NAMESWilliams, R., 163.Williams, R. E., 132.Williams, R. G., 156.Williams, R. J. P., 158, 423.Williams, R. L., 131.Williams, R. M., 221.Williams, R. P., 381.Williams, T. H., 284.Williams, T. P., 365.William, T. R., 218, 460,Williams, W. L., 62.Williamson, A. G., 74, 84,Williamson, S. M., 150.Willis, C. J., 142.Willis, C. P., 477.Willis, H. A., 206.Willis, J. B., 480.Willis, R. G., 269, 282.Willner, D., 211.Wills, L. J., 410.Wills, R., 217.Willson, C., 380.Wilmans, W., 407.Wilmarth, W. K., 173, 174.Wilson, A. D., 439, 440.Wilson, A. F., 476.Wilson, A. L., 444.Wilson, C. L., 476.Wilson, C. O., jun., 135.Wilson, D. V., 331.Wilson, E. B., 189, 195.Wilson, H., 428.Wilson, H. N., 462.Wilson, H. W., 496.Wilson, J. M., 200,204,205,303, 351, 352, 353, 354.Wilson, J. W., 216.Wilson, R. M., 400, 401.Wilson, T. L., 275.Wilson, W. B., 153.Wilt, J. W., 208, 219.Wilucki, I., 340.Whner, D. C., 471.Winchester: J. W., 491.Windmueller, H. G., 417.Winer, A. D., 418.Winey, D. A., 287.Wingrove, A. S., 230.Winkler, C. A., 143.Winnewisser, M., 192.Winstead, M. B., 279.Winstein, J., 336.Winstein, S., 107, 207, 209,210, 214, 219, 223, 229,313.Winter, J., 290.Winter, M., 278.Winterfeld, K., 338.Winterfeldt, E., 345.Wintersteiner, O., 356.Wintrobe, M. M., 395, 396.Wion, J. W., 203.Wise, H., 123.Wise, J. H., 151.467.93, 95.Wish, L., 493.Wisotsky, M. J., 209, 285.Wisser, K., 485.Witkop, B., 202, 323.Witkowski, A., 116.Witkowska, S., 476.Witt, W. P., 102.Wittenberg, J., 393.Wittig, G., 144, 223, 235,286, 311, 313, 342, 508.Wittke, O., 505.Wittstruck, T. A., 204.Witwit, A. S., 467.Witz, P., 303.Wolfel, E., 513.Woese, C. R., 382.Woessner, D. E., 66.Wojtowicz, P. J., 84.Wold, F., 377.Wolf, A. P., 240, 242.Wolf, J., 426.Wolf, L., 190.Wolf, S., 471.Wolf, W., 188, 235, 269.Wolfe, R. G., 416, 425.Wolff, M. E., 303.Wolfrom, M. L., 365, 367,Wolfsberg, K., 494.Wolinaky, J., 331, 358.Wollenweber, P., 446.Wollrab, V., 277.Wolovsky, R., 198, 307,Wondratschek, H., 605.Wonkka, R. E., 217.Woo, P. W. K., 203, 365,Wood, C. S., 332.Wood, D., 51.Wood, D. F., 489.Wood, H. C. S., 257.Wood, H. G., 404, 405.Wood, S. E., 94.Woodbrey, J. C., 193.Woodruff, C., 230.Woods, D. D., 406, 407.Woods, M. C., 298.Woodson, E., 356.Woodward, R. B., 228,288,Woolley, D. W., 403.Woolley, H. W., 114.Woolfolk, E. O., 259, 442.Worden, E. F., 151.Wray, D., 299, 359.Wrede, F., 393.Wright, A., 139, 370.Wright, A. N., 143.Wright, C. V., 101,106, 121.Wright, D. A., 513.Wright, F. J., 32, 37.Wright, J., 150.Wright, P., 235.Wulfert, P., 152.Wulff, D. L., 372.368, 370.316.366.318, 325.Wuller, J. E., 155.Wurster, W. H., 111, 126.Wuscherpfennig, V., 204.Wyatt, E. I., 495.Wyer, J. A., 366.Wyld, G. E. A., 457.Wyler, H., 327.Wylie, A. G., 257.Wylie, A. W., 152.Wyman, G. M., 133.Wyss, E., 322.Yag Dutt, 478.Yager, W. A., 60, 244.Yakovleva, T. V., 206.Yakubov, I. T., 112.Yale, H. L., 342, 487.Yamada, S., 162, 163.Yamagata, Y., 71.Yamaguchi, K., 51.Yamamoto, A., 155.Yamamoto, R., 491.Yamamura, S. S., 479.Yamato, Y., 349.Yamzin, I. I., 502.Yanai, M., 299.Yang, T. H., 358.Yankovsky, S. A., 380.Yarym-Agaev, N. L., 97.Yasaitis, E., 55.Yates, F. E., 427.Yates, K., 246, 364.Yates, P., 243, 287, 338.Yeadon, R. E., 99.Yen, L. C., 75.Yethon, A. E., 342.Yielding, K. L., 425, 426.Yi-Noo Teng, 494.Yoe, J. H., 479.Yoke, J. T., tert., 163,Yokel, H. L., 504.Yokeley, C. R., 32.Yoneda, Y., 20.Yonemitsu, O., 350.Yoneyama, Y., 395.Yonezawa, T., 83.York, J. L., 396.Yorke, B. A., 73.Yoshii, E., 291.Yoshikawa, K., 474.Yoshikaya, H., 395.Yoshioka, I., 292.Youden, W. J., 440.Young, D. M., 135.Young, D. W., 297, 298,Young, J. A., 88.Young, J. F., 160.Young, L. G., 475.Young, M. A., 134.Young, P. A., 107, 111.Young, R. A., 123, 126,Young, R. J., 250, 306.Young, R. S., 406, 408.Young, W. G., 254.513.504INDEX OF AUTHORS’ NAMES 555Young, W. L., 170, 173.Youssef, A. A., 230.Yuan, E., 267.Yuan-Lang Chow, 296.Yudis, M. D., 267.Yukio Nakatsukasa, 448.Yung, N. c., 374.Yunusov, s. Yu., 347.Yura, Y., 332.Yur’ev, Yu. K., 279.Zaalishvili, Sh. D., 91,Zabolotny, E. R., 143.Zachau, H. G., 382.Zacherl, M. K., 473.Za eetko, O., 200, 267.Zagan, A., 51.Zahradnik, R., 341.Zaitsev, P. M., 486.Zaikov, G. E., 39.Zakharkin, L. I., 135, 262,Zalewski, K., 115.ZaIubas, R., 100.Zalusky, R., 407.Zambelli, A., 151.95.265.Zamecnik, P. C., 379, 382,Zamenhof, S., 367.Zamorzaev, A. M., 505.Zander, J. J., 429.Zandstra, P. J., 59.Zarinskii, V. A., 473.Zarnack, U., 345.ZBvada, J., 287.Zavgorodnii, V. S., 206.Zecher, W., 309, 335.Zeetenberg, A. P., 32.Zeeman, P. B., 119.Zefirova, A. K., 47.Zeibler, J., 299.Zeil, W., 192.Zeiss, H., 185.Zeldes, H., 47, 55.Zelle, A., 490.Zerner, B., 248.Zeronian, S. H., 368.Zewe, V., 424.Ziegler, G. R., 231.Zielinski, A. Z., 229.Ziffer, H., 289, 297.Zil’borman, E. N., 279.Zillig, W., 376.418.Zimmerman, S. B., 373.Zimmerman, U. P., 233.Zingaro, R. A., 146.Zinner, H., 365.Zinnes, H., 351.Zittel, H. E., 458, 461, 483.Zizlsberger, H., 177.Zhadanov, A. A., 141.Zhigunov, I. S., 97.Zhirova, V. V., 488.Zollinger, H., 232.Zorkii, P. M., 506.Zozulya, A. P., 465.Zubay, G., 382.Zueeh, E. A., 342.Zurn, L., 250.Zuman, P., 482.Zumoff, B., 431, 434, 453.Zu Reckendorf, W. M.,Zu Stolberg, U. G., 139.Zverev, G. M., 46.Zweifel, G., 255.Zwilling, E., 419.Zwolenik, J. J., 314.Zjrka, J., 452, 453, 467,468,367.470, 484

ISSN:0365-6217    

DOI:10.1039/AR9625900515

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

INDEX OF SUBJECTSAbbreviations used in this Index:biosyn. = biosynthesis identn. = identificationconfign. = configuration prepn. = preparationconformn. = conformation 8.s.r. = election spin resonancedtmn. = determination n.m.r. = nuclear magnetic resonanceAcanthoidine, identn. of, 358.Acenaphthenequinone, ring enlargementAcetanilide, spectrum of, 193.( + )- l0-Acetoxy-cis-hexadec-7-en-l-ol,j-Acetylacraldehyde, identn. of, 376.Acetylenes, 268.metals, 182.of, 317.synthesis of, 278.Acetylene complexes, reaction of withAcetylene, t-butyl-, spectrum of, 190.Acetylenic acids, a and B, prepn. of, 268.Acetylenic carbon, nucleophilic substi-9-Acetyl-cis-decalin oxime, rearrangementN-Acetylglycine, structure of, 514.N-Acetylmethionone, structure of, 206.Acids, fatty and related compounds, 274.long-chain, synthesis of, 276.in natural glycerides, 277.tution at, 231.of, 219.unsaturated, biosyn.of, 275.Actinides, 153.Actonospectacin, structure of, 341.Acyclic compounds, structure of, 506.Acyclic imides, confign. of, 193.Adsorption, chemical, 14.migration in, 15.physical, 14.process of, 13.rate of and desorption, 16.AfEnin, properties of, 277.Ajmaline, confign. of, 352.Akuammigine, identn. of, 350.Alanine, spectrum of, 206.Alcohols, dehydrogenation of, 259.Aldehydes, gas-phase oxidation of, 38.Aldosterone, tetrahydro-, structure of, 431.Alicylic compounds, 281.Aliphatic compounds, 190, 268.Alkali borohydrides, uses of, 257.Alkanes, gas-phase oxidation of, 32.Alkaloids, Amaryllidaceae group, 348.gas-phase oxidation of, 39.prepn. of, from nitriles, 262.reaction of, 244.[7-SH]Aldosterone, prepn.of, 430.biogenesis of, 344.indole, 349.isoquinoline, 347.lycopodium, 356.pyridine group, 344.p yrrolizidine , 34 5.quinoline, 346.Solanum, 356.lupin, 345.Alkaloids, steroid, 355.Alkylation, control of site of, 264.Alkyl radicals, gas-phase oxidation of, 39.Uenes, 272.Alstoniline, synthesis of, 350.Aluminium hydride, use as reducing-nitrogen compounds, prepn. of, 137.Aluminole, derivatives of, 334.Ambidentat 8 nucleoph iles , 2 2 0.Americium, quadrivalent, stabilisation of,Amidines, formation of, 279.8-Aminolaevulic acid, conversion of, 388.terpene, 357.agent, 256.154.synthesase, identn.of, 386.use in biosyn., 385.2 -Amino - 4-methylthiazole, synthesis of,Ammonium ozonide, prepn. of, 147.Anaferine, synthesis of, 344.Analytical apparatus, 438.Analytical balances, design of, 439.Analytical results, accuracy of, 440.Analytical standards, 439.Androstenedione, biosyn of, 429.Androst-4-ene-3,17-dione, isolation of, 429.Angstroms, conversion of X-units into,Angustifoline, partial synthesis of, 345.Anions, aromatic, prepn. of, 313.Annulenes, prepn. of, 316.Annuloline, synthesis of, 331, 358.Anthocyanins, identn. of, 340.9,lO-Anthraquinol dibenzoate, planarityAntimony332.502.spectra of, 198.of, 508.Antimonic acid, polymeric forms of,Homotropylium hexachloroantimonate,Pentaphenylantimony, structure of,147.prepn. of, 313.508.Apiose, Bynthesis of, 360.Aromatic compounds, 307.hydroxylation, mechanism of, 3 10.ions and radicals, 31 2.reactivity, definition of, 307.Aromatic molecules, planarity of, 507.Aromatic substitution, electrophilic, 232.nucleophilic, 233.radical, 235.Aromaticity, definition of, 307.ArsenicBromodiphenylarsine, rotation of, 508.55INDEX OB'Ar~enic, Chlorodiphenylarshe, rotation of,Diarsine, prepn.of, 146.Dimethyl-3-methylthiopropyl arsine, re-Trisilylarsine, prepn. of, 146.Arylazopyrazolones, spectra of, 202.Arylsulphur trifluorides, synthesis of, 263.Aspidocarpine, structure of, 354.Aspidospermantine, structure of, 351.Aspidospermine, structure of, 354.Atractylon, autoxidation of, 292.Atrovenetin, structure of, 317.Azines, synthesis of, 338.Aziridine, combination of, 320.Azoles, synthesis of, 330.Azulene, structure of, 509.Azulenes, synthesis of, 3 15.508.action of, 172.1,2,3-Triphenylazulene, formation of,283.Bacimethrin, identn.of, 339, 374.Balances, analytical, design of, 439.Benzene derivatives, formation of, 307.Benzenoid polycylic compounds, forma-3,4-Benzocoumarin, formation of, 234,Benzofurazan oxide, spectrum of, 202.Bendonitriles, spectra of, 199.Benzophenone, spectrum of, 199.1,2,3-Benzothiadiazole, reactions of, 333.Benzyne, formation of, new methods, 31 1.Beryllium, reaction of, 130.Betanidin, reactions of, 327.Beyerol, structure of, 298.Biaryls, optically active, spectra of, 199.Bicyclo[2,2,0]hexadiene, structure of,Biogenesis of alkaloids, 342.Biosynthesis of chlorophyll, 397.tion of, 307.310.intermediate, chemistry of, 31 1.307.cholesterol, 427.hzem, 394.porphyrins, 385.protoporphyrin IX, 394.steroids, 427.Biphenyl-2-carboxylic acid, nitration of,Bis-m-bromobenzoylmethane, structure of,Bismuth monochloride, structure of, 147.Blood group A, isolation of new sugar in,Bond distances and angles, 189.Boron, prepn.of, 131.reactions of, with oxygen, 135.Boron hydrides, formula of, 131.subhalides, chemistry of, 136.Amine borines, synthesis of, 256." Borazorene," synthesis of, 342.Borazynes, prepn. of, 134.Diborane, reactions of, 132.Nitronium tetrafluoroborate, as nitrat-310.508.368.ing agent, 267.Boron-nitrogen ring compounds, 133.3UBJECTS 557o-Bromobenzoic acid, planarity of, 507.m-Bromonitrobenzene, charge transferButadiene, dtmn.of, 273.Butadieneiron carbonyls, prepn. of, 181.Butene, cis- and tram-, formation of, 322.Byssochlamic acid, structure of, 286.Cadmium, 167.Cafestol, confign. of, 297.Calarene, constitution of, 292.Calycanine, synthesis of, 350.Calycanthidine, structure of, 349.Camphor. Norcamphor, photolysis of, 287.Capsorubin, stereochemistry of, 273.Carbazole, reduction of 2-nitrosobiphenylCarbene, dichloro-, formation of, 243.Carbenes, formation of, 280.Carbohydrates , 3 5 9.bonds of, 507.spectrum of, 190.to, 258.difluom-, formation of, 241.generation of, 240.amino-derivatives of, 366.cyclic derivatives of, 363.degradations of, 363.deoxy-derivatives of, 365.esters of, 364.ethers of, 364.oxidation of, 361.Carbon-13 resonance study of, 71.Carbon monoxide, gas-phase oxidation of,Carbonium ions, transient, 207.Carbonyl, butadieneiron, prepn.of, 181.26.compounds, Friedel-Crafts reaction,cyclopentadiene-metal, prepn. of, 183.cyclopentadienyl cations, prepn. of, 183.Carbonyls, molecular-orbital energy-level262.scheme for, 175.Raman spectra of, 175.reactions of, 246.Carboxylic acids, prepn. of, 262.p-Carotene, 274.Carotenoids, 273.Cascarillin, structure of, 296.Catabolism of CIS, 433.Ci9, 432.CZ1, 430.Cations, aromatic, reactions of, 312.Ceanothenic acid, structure of, 300.Cedrelone, stereochemistry of, 301.Celastrol, structure of, 302.Cellulose, crystal structure of, 368.Cembrene, structure of, 299.Cerium(m) chloride alcoholates, compo-Chalcose, synthesis of, 365.Charge-transfer complexes, study of, 60.Chelates, octahedral, photoracemisationChimonanthine, reduction of, 349.Chloranil, analysis of, 508.ethers, relative reactivities of, 369.sition of, 152.of, 171.structure of, 51 1558 INDEX OF SUBJECTSChloranil-hexamethylbenzene complex,Chlorine-35 resonance, study of, 70.6-Chlorobenzofuroxan, crystal structure2 -Chloro - 5-nitrobenzoic acid, planarity of,Chloroform, spectrum of, 191.Chlorophyll, biosyn.of, 397.Cholestanones, phenyl-, transition of, 197.Cholesterol, biosyn of, 427.(+) -tram-Chrysanthemic acid, synthesisChromatography, column, 444.planarity of, 512.of, 332.507.of, 281.gas, 448.paper, 445.thin-layer, 446.for dtmn.of radioactive species, 493.Chromium, 158.diperoxide, magnetic moment of, 160.Cladinose, identn. of, 366.Cleavamine, prepn. of, 355.Cobalt, 1El.acetylacetonates, spectra of, 169.Hydroxoamminecobalt(II1) complexes,Nitroso (dimethyldithio-carbamato)-Tetramethylammonium tetranitratoco-isomerisation of, 174.cobalt, structure of, 178.baltate(II), prepn. of, 192.Cobamide coenzymes, structure of, 400.Cobamides, biosyn. of, 411.Coenzyme A, synthesis of, 376.Coenzyme, cobamide, isolation of, 400.dehydrogenases, 417.modifications, 416.NAD+, 413.NADH, 414.NADPH, 416.Methylmalonyl-coenzyme A isomerisa-tion, 403.NADH-X, 414.Cogeijerene, optical inactivity of, 290.Colensenone, correlation of, 295.Communic acid, structure of, 295.Complexes, donor-acceptor, 81.inorganic, acetylene, 182.mechanisms of reaction, 173.o l e h , 179.with aromatic systems, 174.bases, 172.of, 174.tetrahedral, formation from bicyclichydroxoamminecobalt(II1) isomerisat ionCondylocarpine structure of, 352.(&)-Conessine, synthesis of, 355.Copper, 166.Coproporphyrinogen 111, formationof, 393.Cortisol, catabolism of, 431.5cr-Cort01, isolation of, 432.5a-Cortolone, isolation of, 432.Coulostatic analysis, 481.Coumarin, photoisomerisation of, 340.Coumarins, spectra of, 203.Cryostat, construction of, 501.synthesis of, 427.Crystallography, experimental techniquesin, 501.symmetry and geometrical, 505.isomorphous, replaceable atoms in, 502.perfect, temperature factors in, 504.Crystals, thermal effects in, 604.Cubane, octaphenyl-, prepn.of, 269.Cucurbitacins, structure of, 300.Curves, rotary dispersion, of inorganicCyanocobalamin, conversion into theCyanogen, synthesis of, 144.Cyanomaclurin, structure of, 329.Cyclic dibasic acid anhydrides, spectra of,Cyclic molecules, planarity of, 507.Cyclodkanones, enolisation of, 245.trans-4-Chlorocyclohexanol, stability of,Cyclodecane, conformn. of, 287.Cyclohexane, conversion of, 196.Cyclo-octatetraenein carbonyls, Moss-cis-Cyclo-octene, formation of, 262.trans-Cyclo-octene, formation of, 262.Cyclopentadiene, dimerisation of, 283.-metal carbonyls, prepn.of, 183.1,2-Cyclopenbanophenanthrene, planhrityCyclopentene, spectrum of, 196.Cylindrocarpidine, structure of, 353.Cylindrocarpine, structure of, 353.Cytochromes, formation of, 396.Dalbergiones, isolation of, 318.Dehydroepiandrosterone, detection of,structure of, 283.complexes, 169.coenzyme, 4 12.191.196.bauer spectra of, 168.of, 509.429.isolation of, 432.occurrence of, 429.glutamic, 425.horse liver-alcohol, 420.lactic acid, 423.malic acid, 425.NADH, folded conformn. of, 418.NADH, stereochemistry of, 418.yeast-alcohol, 423.Dehydrogenation of alcohols, 259.Denudatine, structure of, 358.Desoamine, identn. of, 366.Deuteroformyl radicals, spectrum of, 205.Dewar-benzene derivative, prepn.of, 285.Diagrams, phase, 97.Di-t-alkyl nitroxides, prepn. of, 279.Diatomic molecules, spectroscopy of, 99.Diazirine, photolysis of, 241.Dehydrogenases, activity of, 417.prepn. of, 321.structure of, 201.Ethylmethyldiazirhe, rearrangement of,derivative of, 507.241.Diazoaminobenzene, pp’-dibromonitro-Diazoisofenchone, conversion of, 243.Diazonium compounds, prepn. of, 266INDEX OF SUBJECTS 559Dibenzocyclo-octadiene, dimerisation of,1 -Dichlosomethylpiperidine, formation of,Di-( p-chlorophenyl)amine, valency angleDiels-Alder reaction, mechanisms of, 227.Diethyl oxalate, spectrum of, 191.Differential thermal analysis, 499.1 ,l-Difluoropropene, synthesis of, 255.Digicitrin, isolation of, 341.9,10-Dihydro-9-hydroxy-9-phosphaphe-AT”- Dime t h yleth ylenediamine hydro -4,12-Dimethyl(2,2)metacyclophane,~ R S O - 3,4 -Dim& h yl hexa- 1,5 -diem, re -Dimethyl sulphoxide, solvates with transi-Dinitrogen tetrafluoride, reactions of, 144.y8-Dioxovaleric acid, prepn.of, 388.Diphenyl ether, spectrum of, 199.2,2-Diphenylindoxyl, prepn. of, 325.3,3-Diphenyloxindole, prepn. of, 325.Disaccharides, Konigs-Knorr synthesis of,Diterpenes, confign. of, 294.Dithiet, prepn. of, 323.1,2-Dithiolinium cation, identn. of, 333.( f )-Dolichone, isolation of, 329.Donor-acceptor complexes, 81.Drying, for analysis, 439.Durosemiquinone, spectrum of, 206.Echinulin, synthesis of, 327.Echitamidine, spectra of, 351.Electrodes, mercury, uses of, 438.Electrodeposition, 481.Electron distribution, accurate dtmn.of,282.335.of, 508.nanthrene 9-oxide, structure of, 511.chloride, 194.molecular strain in, 509.arrangement of, 238.tion-metal halides, 171.367.503.dtmn., in N-acetylglycine, 504.in diamond, 504.in lithium hydride, 504.in monofluoroacetamide, 504.in cc-quartz, 504.Electron spin resonance (e.s.r.), 45.Electrophoresis, improvements in appar-&Elemme, optical inactivity of, 290.Elimination-addition mechanism, 21 5.Ellipticine, synthesis of, 349.(-f )-Emetine, synthesis of, 347.End point dtmn., amperometric, 459.chronopotentiometric, 472.conductometric, 457.coulometric, 462.differential electrolytic potentiometric,high frequency potentiometric, 472.potentiometric, 466.molecular, levels, 11 3.transfer reactions of, 59.trapped, 62.atus, 447.471.Energy, form of pair-interaction, 88.Energy, potential, curves, 113, 115.Enzymes, different forms of, 419.Enzyme studies, in succhte-glycineEpibaptifoline, synthesis of, 345.( - )-Epicyclocolorenone, synthesis of,.294.2,3-Epoxy-2,3-diphenylindan- 1 -one, 1so-Erbium oxalates, stabilisation of, 152.Erythritol, 1,3-O-benzylidene-, n.m.r. of1,3 : 2,4-di-O-benzylidene-, conformn. of,Escherichia w li., met hionine synthesis h ,Esters, carboxylic, polarisability of, 191.Ethane, spectrum of, 190.Ethane-1,2-dithiol, spectrum of, 195.Evaporated metal films, uses of, 13.Excess functions, measurement of, 94.vibrational, 114.cycle, 388.merism of, 307.reactions of, 340.diacetate, 363.363.406.gas-phase oxidation of, 39.phosphorus, spectra of, 191.Fabianine, composition of, 347.Falcatine, structure of, 348.Flash-filament experiments, 12.Flavasperone, structure of, 341.Flavocarpine, identn.of, 350.Flavopereirine, identn. of, 350.Fluorine-19 resonances, study of, 68.Fluorotriphenylcyclobutadiene, dimer of,Folicanthine, structure of, 349.Formaldehyde, slow oxidation of, 26.Formaldoxime, structure of, 194.Formamide, spectra of, 193.Formyl radicals, spectrum of, 205.Free radicals, 48.Furans, structure of, 327.Furan-2-carboxylic acid, structure of, 509.Furanodecalins, isolation of, 292.Fusidic acid, provisional structure of, 300.Gallium halides, reaction of, 138.Gas-phase oxidation, 18.Gedunin, stereochemistry of, 300.Geigerin acetate, synthesis of, 293.Geissolosimine, structure of, 355.Genetic code, review of, 380.Germanium, prepn.of, 141.509.Germyl cyanide, spectrum of, 207.1,l-Di-iodogermiren, formation of, 322.Gibberellic acid, stereochemistry of, 298.Glass, analysis of, 438.Glassware, resistance to chemical attack,Glauconic acid, structure of, 286.WD-G~UCOS~ monohydrate, structure of,D-G~UCOSB, oxidation of, 361.(+)-Glutinic acid, structure of, 272.Glycine, spectrum of, 194.439.513.N-Carbamoylglycine, spectrum of, 206.Phenylglycine, tramamination of, 245560 INDEX OF SUBJECTSGlycols, dehydration of, 408.Glycosides, 362.Gold, 166.dtmn.of, 437.Goniometer, three-circle X-ray, design of,Gravimetric analysis, 449.Grignard reagents, formation in hydro-Griseofulvin, antibiotic, synthesis of,501.carbon media, 265.318.racemic, formation of, 328.Hsem, biosyn. of, 394.Hafnium, 154.Halides, alkyl, rotational isomerism of,192.transition-metal, reactions with di-methyl sulphoxide, 171.Haplohyllidine, reduction of, 346.“ Hector’s bases,” identn. of, 333.Helminthosporal, constitution of, 294.Heptalenium ion, spectrum of, 315.Heterocyclic compounds, 319.Heteroenzymes, structure of, 419.Hetisine, constitution of, 357.NN’-Hexamethylenebisproprionamide,Hexaphenylbenzene, formation of, 308.Hexaphenylpentalene, synthesis of, 31 5.trans-Hexa- 1,3,5-triene, synthesis of, 273.Holamine, synthesis of, 355.Holsphyllamine, synthesis of, 355.Homocyclic compounds, spectrum of, 195.Hinesol, structure of, 292.Hinokiol, structure of, 296.Hinokione, structure of, 296.Humulene, pure, isolation of, 290.Hunterburnine, structure of, 351.1,3-Hydride shifts, 216.Hydroboronation, 2 5 5.Hydrocarbons, higher, gas-phase oxida-Hydrogen chloride, use as a solvent, 151.Hydrogenation, catalytic, 254.3-Hydroxyflavylium, formation of cationHydroxymethylcytosine nucleoside, struc-trans-Hydroxy-L-proline, spectra of, 202.3-Indazolone, formation of, 331.Indicine, prepn.of, 345.Indium, halides, prepn. of, 138.Indoles, synthesis of, 324.Indolizines, structure of, 327.Indolmycin, structure of, 326.Inorganic complexes, mechanisms of re-Intensities, absolute, of electronic transi-enzymes, isolation of, 396.structure of, 506.prepn.of, 269.tion of, 34.spectra of, 190.of, 310.ture of, 373.reactions of, 325.actions of, 173.tions, 109relative, measurement of, 1 11.Iodine dioxide, structure of, 151.monobromide, spectrum of, 103.monochloride, spectrum of, 103.Periodate, use in oxidation of sugars,Periodic acid, spectrum of, 151.Ion-exchange, metal-amine complexes in,uses of, 447.Ion-pair return, 213.Ion-pairing, study of, 56.Ionization gauge, “ X-ray limit ” of, 8.Iridium, 161.Iridomyrmecin, conformn. of, 289.Iron, 161.361.170.Butadieneiron carbonyls, prepn. of, 181.Cyclo-octatetraeneiron carbonyls, Moss-Ferrous fluorosilicate hexahydrate, dif-bauer spectra of, 168.fraction study of, 505.Ismine, prepn.of, 348.Isoajmaline, confign. of, 352.Isoartocarpin, structure of, 341.Isobisabolene, structure of, 290.Isoenzymes, definition of, 419.Isoiridomyrmecin, conformn. of, 289.Isojervine, structure of, 356.“ Isopilocereine,” structure of, 348.Isopimaric acid, structure of, 296.Isoquinoline, structure of, 337.( f )-Isoretronecanol, synthesis of, 346.Isoselenazole, formation of, 332.Isothiazole, synthesis of, 332.Isotopic tracers, use in radiochemistry, 495.Isoxazoles, halogenation of, 331.Ivalin, constitution of, 292.Jasmine, composition of, oil of, 278.Ketones, reactions of, 244.Konigs-Knorr synthesis of disaccharides,Kurchamine, structure of, 355.Kurchimine, structure of, 355.367.Lathyrine, spectrum of, 194.Lattice theory of mixtures, 92.LeadLeonurine, structure of, 358.Leurosine, structure of, 355.Lsvopimaric acid, conformn.of, 297.Ligand, 2-2’-hydroxyethylpyridine as, 172.Ligand exchange, use in chromatography,(ti’)-( +)-Linalool, confign. of, 289.Lithium aluminium hydride, use of, 256.Trimethylplumbane, structure of, 143.171.Ethyl-lithium, spectrum of, 206.t-Butyl-lithium, structure of, 130.Lumicholesterone, photolysis of, 304.(-f)-L-unacrine, synthesis of, 346.Lutetium oxalate, stabilisation of, 152.Lysine fermentation, 408.structure of, 130.22-Lysine monohydrochloride dihydrate,StNCtUre Of, 573INDEX OF SUBJECTS 5618-Lyxose, conformn. of, 359.Magnesium hydride, prepn.of, 130.Magnetic resonance, of carbon- 13, 7 1.viologen, formation of, 336.of chlorine-35, 70.of fluorine-19, 68.of oxygen-17, 67.of solute nuclei, 68.of solvent nuclei, 64.Maleimide, synthesis of, 324.Manganese, 160.Manganese(1v) fluoride, prepn. of, 160.Tricarbonyl- a-pyrrolylmanganese, form-ation of, 183.Mass spectrometry, 496.Mercury, 167.electrodes, uses of, 438.Mercuric acetate, as oxidising agent forcarbohydrates, 361.Methane, slow oxidation of, 26, 28.Methionine, synthesis of, 406.Methyl formate, spectrum of, 191.Methyl metadithiophosphonate, sym-8-Methylaspartate isomerisation, 403.5-Methylbenzofuroxan, nitration of, 332.trans-5-Methylcyclohex-2-enol, isomerisa-( + )-S-Methyl-L-cysteine sulphoxides, con-Methylcyclohexane, spectrum of, 196.1 ,l’-Methylenedi- (4-hydroxyiminopyridin-ium) halides, isomerisation of, 194.3,4-Methylenehexa-l,5-diene, formation( - ) -N-Methylgelsemicine hydriodide,2-Methylpent-2-ena1, enzyme liberation of,3 -Methyl- 5 - phen ylpenta - 2,4 - dienoic acid,N-Methylthioacetamide, spectrum of, 193.2-Methylthiobenzothiazole, structure of,N-Methylthioformamide, spectrum of, 193.4-Methyl-2,6,7-trioxa- 1 -phospha-Microscopy, field-emission, 10.Mixtures, lattice theory of, 92.Molecular energy levels, 1 13.theory, of solutions, 84.Molecular weight dtmn., differentialMolecule, aromatic, planarity of, 507.Molybdenum, 158.Monofluoroacetamide, planarity of, 506.Monofluorocitric acid, synthesis of, 263.Monosaccharides, 359.Monot erpenes, 2 8 9.Morphine, structure of, 348.Mossambine, spectrum of, 351.Mossbauer spectra, of organic compounds,of cyclo-octatetraeneiron carbonyls, 168.metry of, 511.tion of, 214.fign. of, 514.of, 273.structure of, 511.278.spectrum of, 191.511.bicyclo[ 2,2,2]octane, 172.method, 440.cyclic, planarity of, 507.168.Mycaminose, identn.of, 366.Mycarose, synthesis of, 365.Mycinose, synthesis of, 365.Natural products, review of, 271.Neighbouring-group participation, 217.( f )-Neotenone, isolation of, 329.Neptunium, spectrum of, 154.Nickel, 164.Bis( triphenylphosphine)ethylenenickel,formation of, 179.Nicotinamide apoenzymes, 413.coenzymes, 413.dinucleotides, structure of, 417.dtmn.of, 437.Niobium, 156.Nitration, of aromatic compounds, by“ Nitrene,” isoelectronic, generation of,Nitrenes, use in synthesis, 243.Nitroalkanes, crystalline derivatives of,l-Nitroazetidine, prepn. of, 322.2’-Nitrobiphenyl-2-carboxylic acid, re-5-Nitrobornene, confign. of, 200.Nitrogen, active, reactions of, 143.o-Nitrophenol hemihydrate, potassium2-Nitrosobiphenyl, reduction of, 258.Nitrosyls, gas-phase reaction with halides,molecular-orbital energy-level schemeNoviose, biosyn. of, 360.Nuclear magnetjc resonance in electrolyteNucleation in precipitation, role of, 451.Nucleic acid bases, dimerisation of, 371.Nucleic acids, 371.Friedel-Crafts principle, 2 6 7.241.279.arrangement of, 234.salt of, structure, 507.178.for, 175.solutions, 63.effect of radiation on, 371.genetic code, 380.protein synthesis of, 379.Nucleophilic substitution a t saturated car-Nucleosides, synthesis of, 374.Nucleotides, physical chemistry of, 378.Nupharidine, synthesis of, 344.Obscurine, a- and j3-, structure of, 357.(+)-Occidol, confign. of, 292.Octaphenylcubane, prepn.of, 269.(Estrone, conversion into astriol, 433.Olefin complexes, of transition metals,Olefin-forming eliminations, 222.Olefhic carbon, nucleophilic substitu-tion at, 231.compounds, 272.Olefins, additions to, 224.formation of, 260.gas-phase oxidation of, 35.bon, 207.synthesis of, 376,structure of, 283.179.Oleuropeic acid, synthesis of, 289562 INDEX OF SUBJECTSOrganic chemistry, 187.material, oxidation of, 438.structure, 189.Organometallic compounds, 265.Osmium, 161.Otobain, structure of, 318.Oxidation, gas-phase, 18.hydrogen-oxygen reaction, 22.organic, 26, 28, 32, 34, 35, 37, 38, 39.shock tubes and flames, 19.Oxirans, formation of, 321.Oxygen- 17 resonances, study of, 67.Oxygen atoms, reactions of, with organicPaint, analysis of, modern methods, 437.Pair interaction energy, form of, 88.Palladium, 164.liquid-phase, 258.compounds, 43.Tetraphenylcyclobutadiene-palladium(I1) chloride, prepn.of, 182.Paracyclophanes, prepn. of, 317.Parameters, lattice, accurate measure-Parthenin, correlation of, 294.Patchouli alcohol, synthesis of, 293.trans-Pent - 3-en-2-0~~0, spectrum of, 191.Perchromate ion, basic formula of, 160.Peroxy-compounds, dipole moments of,Phase diagrams, 97.O-Phenylhydroxylamine, synthesis of,4-phenyl- 1,2,4 - triazoline- 3,5 -&one, prepn.Phosphorus, compounds of, 144.ment of, 502.191.308.of, 331.Fluorophosphanes, 146.Phosphanthrene, prepn.of, 342.Phosphazenes, 145.Phosphonitrilic bromides, prepn. of,145.chlorides, prepn. of, 145.dimethylamide tetramer, 61 I.Phosphoranes, olefin formation from,260.Potassium 00-dimethyl phosphorodi-thioate, structure of, 507.Silylphosphines, synthesis of, 140.Triferrocenylphosphine, prepn. of, 146.Picramide, spectrum of, 199.Piloceredine, structure of, 348.Piperazine- 1,4-dibutyric acid, structure of,Pisatin, partial synthesis of, 329.Platinum, 164.511.spectrum of, 203.Dioxygenyl hexafluoroplatinate, identn.of, 165.Pleuromutilin, structure of, 299.Plutonium(rv) complex halides, prspn.of,153.fluoride, identn. of, 153.Podototarin, synthesis of, 297.Polarography, 482.alternating current, 488.cathode ray, 488.Polaroid film, for recording neutronPolyacetylenic compounds, naturallyPolygodial, isolation of, 292.Polymerisation, degree of, of metal oxidePolynucleotides, synthesis of, 376.Polyriboguanylic acid, synthesis of, 378.Porphobilinogen, use of in biosyn., 385.Porphyrins, biosyn. of, 385.diffraction, 502.occurring, 271.alkoxides, 170.formation of, 388.conversion of, 389.reduction of, 325.Coproporphyrin, structure of, 385.Phyriaporphyrin 111, isolation of, 394.Protoporphyrin, conversion of, 385.Protoporphyrin IX, biosyn.of, 394.Potent iometry, 4 6 6.differential electrolytic, 471.high frequency, 472.Praseodymium fluoride, prepn. of, 153.Prephenic acid, corfign. of, 285.Pristimerin, structure of, 302.Properties, equilibrium, of liquid mixtures,Propyl fluoride, spectrum of, 192.Prostglandin F2-1, confign. of, 276.Protein synthesis, review of, 379.Protohaemin IX, inhibitor in biosyn., 387.Pseudouridine, structure of, 375.Pseudovitamin B,, coenzymes, structurePteridine, hydration of, 339.4H-Pyran, formation of, 339.Pyrazoline hydrochloride, planarity of,Pyrazolines, synthesis of, 330.Pyridine, 2-2’-hydroxyethyl-, as ligand,Pyridine hydrochloride, bond linkage in,Pyridines spectra, of, 334.Pyrido[3,2-a]azulene, synthesis of, 316.2-Pyridone7 l-methyl-, structure of, 337.Pyridoxine, synthesis of, 337.1 -2’-Pyridyl- 2 - 2’-pyridylmethylene-2,3-Pyridyne, formation of, 235.3,4-Pyridyne, formation of, 235.reaction as intermediate, 335.Pyrimidines, synthesis of, 338.(+)-Pyrocin, use in synthesis, 281.Pyrroles, synthesis of, 323.Pyrrolines, spectra of, 201.P yruvate-C 0, exchange, 4 1 0.Qualitative analysis, inorganic, 440.Quaternary amino-groups, in enzymeQuinaldine, reduction of, 338.Quinoline, structure of, 337.Quinolizidine, spectrum of, 203.Quinolizines, formation of, 338.73.F,, structure of, 284.of, 401.510.172.510.hydrazine, complexes of, 172.organic, 441, 473.action, 423INDEX O F SUBJECTS 563Radicals, alkyl, gas-phase oxidation of, 39.aromatic, prepn.of, 314.free, e.s.1. of, 48.aromatic, in solution, 8.s.r. of, 50.carbon 7 ~ - , 8.s.r. of, 52.u-, 8.s.r. of, 55.Radioc hemistry, 48 9.Rare earths, 152.Reaction mechanisms, 207.Rearrangements, aromatic, 236.activation methods in, 490.Claisen, 237.benzidine 238.semidine, 238.excess free energies of, 76.separation into two liquid phases, 80.solubilities of, 78.solubility equations of, 76.volume changes on mixing, 8 1.Retamine, structure of, 345.(-J-)-Retronecine, synthesis of, 345.Rhenium, 160.Rhodium, 161.Regular solutions, 73.Rhodium(Ir1) acetylacetonates, spectraDinitrosylrhodium chloride, reaction of,of, 169.178.Ribonucleic acid, reactions of, 374.Royleanone, diterpene quinone, isolationof, 296.Ruthenium, 161.Saccharides, acetylation of, 364.di-, 367.methylation of, 364.oligo-, 367.POly-, 368.Samandaridine, structure of, 356.Samples, analytical dissolution of, 438.Sarpagine, structure of, 352.Saturated carbon, electrophilic substitu-Saxifolin, degradation of, 339.Securinine, structure of, 358.Selenium compounds, prepn.of, 150.Selenophen-2-carboxylic acid, structure of,Semicarbazones, formation of, by acidSempervirine, synthesis of, 350.Sesquiterpenes, 290.Shellolic acid, constitution of, 294.Silicon, multiple bonding of, 138.tion at, 230.nucleophilic substitution at, 207.509.catalysis, 245.halides, reaction of, 140.monoxide, prepn.of, 140.1 , l -Dimethyl-2,3-diphenylsiliren,prepn. of, 322.Disilane, prepn. of, 139.synthesis of, derivatives, 139.Potassium silacyclopentadienide,spectrum of, 333.Silane, conversion into higher silanes,139.Silazides, prepn. of, 139.Silicones, as heat exchangers for analysis,Silver, 166.Skytanthine, prepn. of, 344.Sodium bicarbonate, C-0 distances, studySodium metaperiodate, use as oxidisingSolanum group, synthesis of, 356.Solasodine, synthesis of, 306.Solutions, molecular theory of, 84.Solvent extraction, for dtmn. of radio-439of, 506.agent, 260.regular, 73.isotopes, 492.in analysis, 443.345.(- )-Sophocarpine, prepn. and structure,Sophoramine, prepn. of, 345.Spectra of dkali-metal compounds, 121.of carbonmonoxide andlead telluride,l23of chlorine and iodine, 127.of doubly charged positive ions, 120.effect of fine structure on, 118.effect of isotopes on, 119.effect of predissociation on, 117.of halides, 129.of hydrides, 127.of hydrogen halides, 121.of magnetic rotation, 103.of mercury and rare-gas compounds, 120.of new inter-metallic compounds, 119.of nitric oxide, 124.of nitrogen, 122.of oxides, 128.perturbations of, 116.of phosphorus, monofluoro-, 127.of sulphur: disulphur, 126.Spectroscopic analysis, 475.Spectroscopy, absorption, 478.atomic absorption, 479.of diatomic molecules, 99.emission, 475.flame, 476.fluorimetry, 476.infrared, 480.nuclear magnetic, 480.techniques of, 100.ultraviolet and visible, 478.uses of, for new species, 119.X-ray, methods, 477.Stachenone, structure of, 297.Standards, pH for analysis, 439.Starch and glycogen, 369.Stemmadenine, structure of, 352.Sterigmatocystin, structure of, 329.Steroid hormones, metabolism of, 426.Steroids, 303.spectra of, 200.C18, 429.C,,, 428.CZ1, 427.dtmn.of, by optical analogue methods,in organic molecules, 504.analytical, 439.Structure, analysis of, by computer, 502.503664 INDEX OF SUBJECTSSuccinate-glycine cycle, reactions in, 388.Succinonitrile, conlign. of, 195.Succinyl-Co A, as intermediate in por-Sugars, acetylation of, 364.acetylated amino-, de-O-acetylation of,amino-, reactions of, 366.deoxy-, synthesis of, 365.reducing, methylation of, 364.enzyme studies in, 388.phyrin biosyn., 385.366.Sulphaniloylguanidine, structure of, 195.Sulphides, oxidation to sulphoxides, 260.Sulphonium ylides, use as tmnsfer agents,Sulphur, compounds of, 148.derivatives of, 279.halides synthesis, of, 149.Disulphur monoxide, prepn.of, 149.Tetrasulphur tetranitride, prepn. of,Trisul hur dinitrogen tetroxide, prepn.265.148.of, f48.Tabersonine, structure of, 353.Tantalum, 156.Tartaric acid, spectrum of, 205.Taxines, structure of, 358.Technetium, 160.Tellurium complexes, 150.Terpenes, spectra of, 200.Testosterone, biosyn. of, 429.dtmn. of, 437.synthesis of, 428.secretion of, 433.Tetrachloroquinol, planarity of, 508.Tetracyclines, biosyn. of, 319.Tetramethylene sulphite, cyclic, spectrum“ Tetramin,” spectrum of, 320.Thallium, complexes of, 138.Theorell-Chance, mechanism for enzymeThermal effects in crystals, 504.synthesis of, 288.of, 204.reaction, 421.methods of analysis, 499.parameters in lithium hydride, 504.parameters in a-quartz, 504.scatter, correction for, 504.Thermogravimetric analysis, 499.Themopsine, synthesis of, 345.Thia(Iv)benzenes, prepn.of, 341.Thialen, formation of, 341.Thiamine hydrochloride, planarity of, 514.Thietans, formation of, 321.Thiete 1,l-dioxide, reactions of, 323.Thiirans, formation of, 321.Thiophens, structure of, 329.Thiophen-2-carboxylic acid, structure of,4H-Thiopyran, prepn. of, 339.Thiourea dioxide, planarity of, 507.Thorium chloride, reactions of, 153.Thujone, conlign.of, 290.Thunbergene, see Cembrene, 299.509.Tin, detection of, 142.Titanium, 154.complexes, prepn. of, 155.Hexafluorotitanates, prepn. of, 154.Titrations, chelatometric, 454.functional group dtmn., 457.halogen, 453.non-aqueous, 457.redox, 453.spectrophotometric, 456.rearrangement of, 215.Titrimetric analysis, 452.6-Toluene -p-sulphonyloxyisophorone,Totarol, structure of, 296.Totarolone, structure of, 296.Toxoflavine, synthesis of, 339.Transition elements, 152.quadrupole and magnetic dipole, 108.molecular hydrides of, 185.organometallic compounds, 184.perfluoroalkyl derivatives, 184.Transition-metals, 0.s.r. spectra of, 46.Transitions, electric dipole, 105.Triazolopyrimidine, structure of, 510.Triethylscarpane, formation of, 507.Trime t h ylher queinone B , structure of,1,2,3-Triphenylbenzopentalene, prepn. of,Triphenylethylene, formation of, 312.1,2,5-Triphenylphosphole, reactions of,1,2,3-Triphenylpropene, formation of,Triterpenes, constitution of, 300.1,3,5-Trithian, spectrum of, 204.“ a-Trithioacetaldehyde,” spectrum of,“ a-Trithiobenzaldehyde,” spectrum of,Tropones, synthesis of, 314.“ Tropovinylene spiroborates,” synthesisTropyl derivatives, formation of, 314.Tropylium salts, formation of, 313.Tubercle bacillus, study of acids of, 275.Tuberostemmonine, dehydrogenation of,349.Tungsten, 158.‘‘ Twistane,” synthesis of, 288.Ultra-high vacua, 7.318.315.333.312.structure of, 341.204.204.of, 314.Tungsten-(In) and -(Iv) bromides, 158experimental methods, 8.theoretical approach to, 9.“ getter-ion ’’ pumps for, 9.Uranium chlorides, prepn.of, 154monocarbide, hydrolysis of, 153.quality and safety control of, 437.Ammonium diuranate, composition of,Uranium (IV) oxide, reactions of, 153.Uroporphyrinogen, structure of, 385.Uroporphyrinogen decarboxylase, isola-153.tion of, 393INDEX O F SUBJECTS 566Uroporphyrinogen I synthetase, isolationUroporphyrinogen 111, formation of, 389.Uroporphyrinogen I11 cosynthetase, isola-Valeranone, structure of, 292.Vanadium, 156.of, 391.tion of, 391.tetrabromide, prepn. of, 156.Vanadium(m), oxidation by iron(m),Vector, superposition diagram, symmetryVeralkamine, structure of, 356.Vermiculite, analytical uses of, 439.Vincadifformine, structure of, 353.Vincalencoblastine, structure of, 355.Vincamine, structure of, 354.Vindoline, structure of, 353.Virial coefficient, second, 88.Vitamin B,, planarity of, 514.Vitamin BI2, 400.Vulgarin, constitution of, 292.173.of, 503.Water, dtmn. of, 439.Willardiine, identn. of, 339.Xenon difluoride, prepn. of, 130.hexfluoroplatinate, prepn. of, 130.tetrafluoride, prepn. of, 130.Xylindein, composition of, 318.spectrum of, 341.Yeast alcohol dehydrogenase, r61e of zincYohimbine, synthesis of, 350.in, 423.Zierone, constitution of, 294.Zinc, r61e in enzyme action, 422.Di-L-histidinozinc(11) dihydrate, struc-ture of, 514.Zirconium, 154.Zonemelting, low- temperature applicationiodide, reduction of, 154.of, 171

ISSN:0365-6217    

DOI:10.1039/AR9625900556

出版商:RSC    

年代:1962

数据来源: RSC

摘要:

PRINCIPAL REFERENCES USED I N CHEMICALSOCIETY PUBLICATIONSA LIST of the principal references used in this and other ChemicalSociety publications was given on page 557 of the 1960 issue ofAnnual Reports. A similar list can also be found in each Januaryissue of Current Chemical Pupers, in the Society’s “ Handbook forChemical Society Authors,” and in the brochure ‘‘ Presentation ofPapers. ”Printed in Great Britain by Butler ik Tamer Ltd, Frome and Londo

ISSN:0365-6217    

DOI:10.1039/AR9625900566

出版商:RSC    

年代:1962

数据来源: RSC