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Proceedings of the Chemical Society. August 1959 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue August,
1959,
Page 201-240
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY AUGUST 1959 DELAYED PUBLICATIONS THE delay to the Society’s publications which was the immediate result of the labour dispute in the printing industry is deeply regretted and our best efforts are being made to restore the publications to normal. The present position is as follows Proceedings.-The June issue of Proceedings due for distribution at the end of that month was in the last stages of production when printing stopped. It was distributed during August and was labelled as a joint issue June/July. The present issue (August) will it is hoped not be too long delayed beyond its proper date of August 30th. There will thus be only eleven issues of Proceedings during 1959 but it is hoped to print in them all the material which would normally have appeared in twelve issues.Journal-The effects of the dispute are more serious for the Journal than for the Society’s other publications. The printers succeeded in clearing the June issue from their works before work ceased and this issue was distributed slightly late by the Society’s staff. When the normal holiday in the print- ing industry is consolidated with the period during which the dispute was in progress there is a total of eight weeks during which printing of the Journal was not in progress there is a backlog of two issues. The issue which would normally have been labelled July and distributed at the end of July will be labelled July/August and distributed during September if possible.The dearth of proofs from the printers makes it impossible to resume normal publication immediately thereafter there will be a small issue labelled September/October which will it is hoped be distributed at the normal date for the October Journal i.e. the end of October. Thereafter it is hoped to publish extra large issues monthly but the delay to papers cannot be eliminated before the end of the year at the earliest. There will thus be only ten issues of the Journal during 1959 but these will contain all (or nearly all) the papers falling due for publication in that year. The Society apologises for the incon- venience to readers and authors. Quarterly Reviews.-Although issue No. 2 was intentionally reduced in size it proved impossible to distribute it on time; it should however have been sent to subscribers during August.It is expected that issue No. 3 will be correspondingly larger and will be published at about the normal date. Annual Reports.-The final printing and binding of Annual Reportsfor 1958 has been delayed and it is feared that distribution will not occur until September or October. Current Chemical Papers.-Issue of Current Chemical Papers has proceeded continuously though more slowly. Issues Nos. 6 and 7 have been published with some delay but future distribution should be at the customary times. 20 1 PROCEEDINGS REPORT ON THE ONE HUNDRED AND EIGHTEENTH ANNUAL GENERAL MEETING THE One Hundred and Eighteenth Annual General Meeting was held in the Large Hall Friends House Euston Road London N.W.l at 9.30 a.m.on Wednesday April 8th 1959. The Chair was taken by the President Professor H. J. Emeldus. The notice convening the Meeting having been read by Dr. J. Chatt Senior Honorary Secretary the Report of Council and Accounts for the year ended September 30th 1958 were presented by Dr. Chatt and Mr. M. W. Perrin Honorary Treasurer. Dr. Chatt drew attention to the salient points in the Report of Council which had been circulated to Fellows(Proceedings 1959 pp. 29-36) and remarked upon the continued expansion of the Fellowship; the development of the Society’s publications and pro- gress in other activities with which the Society was concerned. Mr. Perrin pointed out that the Accounts presented for approval covered the first complete year since the change in the Society’s accounting period.Com- parisons with the previous figures which related to nine months only might therefore be misleading. The financial position of both the General Purposes Account and the Publications Account continued to be satisfactory and this justified the steps which had been taken to improve the revenue of the Society by increasing the selling price of pu blications. After discussion the President referred to the support he had received from the Officers and Council and expressed his appreciation of the work of the permanent staff of the Society. He moved that the Report of Council and the Accounts for the year ended September 30th 1958 be adopted by the Meeting.This motion seconded by Professor M.J. S. Dewar was approved unanimously. The President then announced the names of the following new Members of Council elected to fill the vacancies caused by retirement Vice-presidents who have filled the Ofice of President Sir Robert Robinson Vice-presidents who have not filled the Ofice of President Professor F. Bergel Honorary Secretary Professor A. W. Johnson Elected Ordinary Members of Council Constituency I Dr. C. B. Amphlett Dr. H. T. Openshaw Dr. W. A. Waters Constituency 11 Professor C. H. Hassall Constituency IV Professor G. E. Coates Dr. I. J. Faulkner Dr. A. H. Lamberton On the motion of the Honorary Treasurer seconded by Professor A.W. Johnson Messrs. W. B. Keen & Co. Finsbury Circus House London E.C.2 were appointed as Auditors for the year ending September 30th 1959. At the conclusion of the Meeting a vote of thanks to the President Officers and Council and the Local Representatives of the Society was proposed by Dr. F. A. Robinson and was carried with acclamation PRESIDENTIAL ADDRESS* Some Inorganic Polymers By H. J. EMELEUS POLYMERISATION is a phenomenon which is usually associated with organic systems but it is also en- countered very frequently in inorganic chemistry. Thus minerals such as the naturally occurring silicates and borates contain polymeric anions ;and many other purely inorganic substances among which cuprous and palladous chlorides silver thio- cyanate and the complex fluoroaluminates may be mentioned at random have structures which are based on the polymerisation of either neutral mole- cules or anionic units.Processes of cationic or anionic aggregation in solution are also encountered very frequently. The field is indeed so wide that it would be impossible to cover it even in outline in this Address. The section which I have selected for review may best be described as molecular polymerisation. It embraces a range of neutral inorganic molecules which are aggregates of a repeating structural unit. This field is of special importance at the moment for * Delivered at the 118th Anniversary Meeting of the Chemical Society at Friends’ House London on April 8th 1959.AUGUST 1959 it is here that chemists are searching for new com- pounds which are superior to natural or synthetic organic polymers in respect of properties such as thermal stability and resistance to chemical attack. The subject is still in its infancy and has not been systematised in any sense. The examples which will be described are drawn from widely scattered sources in the literature but I hope that they will serve to illustrate progress already made and some possible lines for future development. The simplest type of inorganic polymer is that based on a chain or ring of atoms of one kind. Un- fortunately catenation of elements other than carbon is restricted to a few of the non-metals and the bonds between such elements are not particularly strong.In the case of boron the electron-deficient hydrides represent a special case since although B-B bonds are encountered linkage of boron atoms by hydrogen bridges also occurs. The four halides of the type B2X4 do however have a B-B bond and the chloride B2C14 undergoes spontaneous decomposi- tion above 0” to B&l4 and more complex pr0ducts.l In the compound B4C14 there are four boron atoms arranged tetrahedrally each associated with a chlorine atom an arrangement which is similar to that of the boron atoms in tetraborane.2 The B-Cl bonds are normal but those between the boron atoms are of fractional ~rder.~ This compound is stable up to about 70°,whereas B,Cl decomposes at 0”. Very recently a second species B,CI has been identified.4 There is some evidence that B,CI can be methyl- ated with trimethylaluminium and it is possible that structures of this sort can be further modified so as to enhance their stability.Structures with linked boron atoms also occur in metal b~rides,~ which contain chains layers or three-dimensional net- works extending through the crystal. It is not known however if fragments of these structures can survive controlled attack by reagents such as chlorine. Catenation of silicon atoms occurs to a very limited extent in the saturated silicon hydrides which have been characterised up to Si,H,, and presum- ably also in the poorly defined solid hydrides (e.g. SiHa which are formed in the controlled cracking of the paraffin-like silanes or by hydrolysis of certain silicides.The cracking of silicon tetrachloride in an inert gas at 1100” also gives complex products among which SiloC122 has been characterised. It probably has a chain of linked SiCl groups and can be alkylated though information on the products is very scanty. The iodide Si216 also decomposes thermally to (SiI)n. All such compounds and their derivatives are likely to undergo decomposition on treatment with alkali which readily cleaves the Si-Si bond. In the case of phoshphorus the tetrahedral P molecule with its abnormally low bond angle of 60” occurs in the vapour and also in solid white phos- phorus. Layer structures with covalently linked phosphorus atoms are found in crystalline black phosphorus.Similar structures also exist in the metallic forms of arsenic antimony and bismuth. The layers in black phosphorus have a corrugated appearance and the solid has a flaky texture which so often characterises solids with this structure. There is very little evidence that chains of phos- phorus atoms can persist in its compounds. The diphosphine P,H is the only well-defined hydride other than PH but various amorphous solid hydrides of unknown constitution have been described. Thus the yellow amorphous solid which results when P2H decomposes has the approximate composition P2H. A similar material is formed in the reaction of aluminium phosphide Alp with hydrogen chloride and it is now believed that all of these materials are high polymers with -PH, >PH and 3 P units.6 It is of interest that these compounds are fairly stable in air whereas P2H4 is spontaneously inflammable.This suggests that such polymers could be further improved if means were found to limit the degree of polymerisation and also to introduce suitable sub- stituents. Little attention has been paid so far to sub- halides of phosphorus other than those of the type P,X, or to the production of new type of alkyl derivatives by cracking of phosphorus alkyls. Two unusual phosphorus compounds may be mentioned at this point because they exhibit relative- ly high thermal stability. These are P,(C,H5)4 and P,(CF,)*. The first the so-called phosphorbenzene was prepared in 1877 by the reaction of diphenyl- phosphine with diphenylchlorophosphine It is a yellow solid which melts at 150” and from molecular-weight determinations has the formula (C,H,P),.One of the most interesting reactions is that with sulphur which gives (C,H,-PS), or with excess of sulphur (C,H,.PS2),. The structure has not been determined by physical methods but it is Urey Wartik Moore and Schlesinger J. Amer. Chem. SOC.,1954 76 5293. Atoji and Lipscomb J. Chem. Phys. 1953 21 172. Longuet-Higgins Quart. Rev. 1957 11 121. Lipscomb Adv. Inorg. Chem. Radiochem. 1959 1 118. Cf. Wells “Structural Inorganic Chemistry,” Oxford Univ. Press 1950 p. 594, Van Wazer “Phosphorus and its Compounds,” Interscience Publ. Inc. New York 1958. formulated as a derivative of cyclotetraphosphine P,H,.' Ph*P-P*Ph PhSP-P-Ph II CF,.P-P*CF CFi P-P*cF3 II A very similar compound has recently been described by Mahler and Burg.8 It is made by the reaction of CF,*PI with mercury at room tempera- ture by thermal decomposition of P,(CF,) [to (CF,-P) and (CF,),P] or by the thermal decom- position of (CF,),PH [to (CF,-P) and CHF,].Other related cyclic polymers may also be formed in these reactions. If the structures postulated are accepted we may regard the P ring as stabilised by extra bonding involving the lone electron pair on each phosphorus atom and the 3d-orbitals of ad- jacent phosphorus atoms. This general type of bond- ing is believed to lead to enhanced bond strength in a number of related structures including the phos- phonitrilic halides which I shall discuss later.The only other example of an element with a pro- nounced tendency to catenation is sulphur which in the elementary form contains S rings and in its plastic form chains of linked sulphur atoms. Both the hydrides and the halides of sulphur also include species with sulphur chains of considerable length. Thus Feher and his co-workers have characterised hydrogen polysulphides up to H2S, and higher members of this series certainly exist. Their thermal stability is however low and they are also exceed- ingly sensitive to hydrolysis. Sulphur halides of the type S,C1 are obtained when disulphur dichloride is passed through a so-called hot-cold tube which ensures rapid cooling of unstable reaction products.Compounds such as S,CI, S4C12 and S,C12 are readily identified in the mixed reaction products the sulphur content being considerably in excess of the maximum solubility of sulphur in S,C12 or SC1,. The Raman spectrum of these compounds also differs significantly from that of a solution of sulphur in sulphur chloride. A similar range of sulphur bro- mides also exists though the stability is again low. From the foregoing examples it will be seen that polymeric substances based on a chain or ring of like atoms are not in general very stable and are also rather reactive. The prospect of finding useful poly- mers in this area is accordingly low and one has to turn to structures based on the bonding of two different atoms to obtain the first indication of high stability.Bonds become stronger and not infre-quently chemical reactivity is not particularly high. I shall consider examples drawn mainly from the range of non-metals which has already been dis- cussed. Kuchen and Buchwald Chern. Ber. 1958 91 2296. * Mahler and Burg J. Amer. Chem. Suc. 1957 79 251. Burg and Wagner ibid, 1953 75 3872. PROCEEDINGS Boron forms a large number of polymers when it is linked to other atoms. Reference has been made already to the borates which have polymeric anions based on the B-0-B linkage. Outstanding among the boron-nitrogen compounds is borazole (I) a ring structure in which the B-N bonds are stabilised by v-bonding. It exhibits a certain degree of aromaticity and the hydrogen atoms attached to boron or nitrogen may be replaced by substituents though not often by methods which parallel those used in organic chemistry.The chemistry of this substance and its derivatives has been exhaustively studied but it is remarkable that little progress has been made in the study of the non-volatile products which are formed by intermolecular condensation of com-pounds containing for example the >B-NH groups to give >B-NH-B<. No means has been found for limiting the extent of such condensations. The limiting structure (BN) has however been elucidated boron nitride having a structure similar to that of graphite with alternating boron and nitrogen atoms in the rings. The borazole type of structure should be repeated with aluminium in place of boron and other Group VB elements in place of phosphorus.Little progress has so far been made in the preparation of com-pounds of the first type but phosphorus and arsenic have both been substituted for nitrogen. This may be illustrated by the work of Burg and his collaboratorsQ on the compound (11) which contains a six-membered ring of alternating boron and phosphorus atoms. It is made by heating the adduct of dimethylphosphine and the borine radical Me,HP+BH, to 150" hydrogen being lost. A small amount of a tetramer is also formed. Both the trimer and the tetramer are crystalline and may be sublimed. They are sur-prisingly stable compared with other compounds containing B-H bonds. The trimer is hydrolysed only slowly by aqueous hydrochloric acid at 300" and de- composes thermally at 300-350" losing hydrogen and methane.Burg has explained the stability of this compound as due to B+P n-bonding in which the B-H bonding electrons enter hydrid d-orbitals of phosphorus. The B-P bond is thereby strengthened and the electron density on hydrogen reduced which renders it less susceptible to attack by protonic re- agents. The B-H groups may also be converted into AUGUST B-C1 without loss of stability. Analogous arsenic compounds are less stable.1° Lower stability is also encountered when sulphur is bonded to boron though here again various polymers e.g. (HBS) and (MeSH,), have been described. The silicates are the outstanding example of poly- meric structures based on the Si-0-Si linkage and the silicones which are directly related to them are a pattern of what may in time be done with other systems.By the introduction of suitable organic groups and by limiting the extent of polymerisation the silicones have been made to conform to a wide range of technical requirements while at the same time retaining the strong framework of linked silicon and oxygen atoms which characterises the silicates. The same structural features occur in the silicon oxyhalides which are much less well known. They are for the most part of the type SinOn-lX2n+2 (where X = C1 or Br). Members of this series with n up to 7 have been identified and they are almost certainly of the type (III) with terminal SiCl groups.Two tetramers (SiOCl,) and (SiOBr,) have also been prepared which may have the cyclic structure (IV) but this has not been definitely established. Less is known about the corresponding thio-com- pounds which would in any case be likely to be less stable. Silicon disulphide itself has a structure com- posed of chains of SiS4 tetrahedra with opposite edges shared.ll The chlorine atoms in the oxy- chlorides are reactive and could doubtless be re- placed by other groups than alkyl and aryl as they are in silicones. Replacement by NH or NHR groups might be of special interest because of the possibility of causing cross-linkage by intermolecular elimination of ammonia with formation of an -NH-bridge. So far however all polymers formed from acid halides in this way tend to be rather in- tractable and it would again be very desirable to find ways of restricting the extent of polymerisation.An interesting example of the unexpected in this field is furnished by a study of the reaction of mole- cular nitrogen and silicon tetrachloride in the glow discharge.12 The initial product is the fully chlorinated trisilylamine but this readily loses silicon tetra- chloride and forms polymers with the formula (Si,NC15)z. A cyclic product (V) has been obtained crystalline; oily products are thought to be mixed lo Stone and Burg ibid. 1954,76,386. l1 Zintl and Loosen 2.phjJs.Chem. 1935 A 174 301. l2 Pflugmacher and Dahmen Z. anorg. Chem. 1957,290 la Wannagat und Rademachers ibid.1957 289 66. linear polymers. The simplest of these has structure WI). The chemistry of phosphorus abounds in examples of polymeric materials because of the strong bonds which are formed with elements such as oxygen nitrogen and sulphur. The extensive chemistry of the polyphosphates is based on the P-0-P bond and this is also true of the oxides and oxyhalides. The latter are more complicated than is generally realised and include not only the so-called pyrohalides (e.g. P,O,Cl,) but also more complex compounds such as (VII) and (VIII) to which chain and ring structures have been assigned. As in the case of the silicon oxyhalides the halogen atoms in these mole- cules are reactive and offer considerable scope for further synthetic work.Thiohalides of phosphorus are not well known though the P-S-P bond in the phosphorus sulphides leads to relatively stable structures. An interesting polymeric material has recently been produced by passing phosphorus trifluoride and oxygen through an electrical discharge at -75 '. The initial product is a white solid with the com- position P7010F15 but this loses POF, PF, and P203F4 readily as it is warmed to 0" and leaves a polymer with the formula (PO&), to which the structure (IX) has been assigned.13 This has a rela-tively simple X-ray pattern and is thought not to be 0 X) of high molecular weight. It is also hygroscopic and easily hydrolysed. The most stable and best known phosphorus- containing polymers are the phosphonitrilic halides.The trimer was discovered by Liebig but we owe much of our basic knowledge of these interesting substances to the work of Stokes done some fifty 184. years ago. The usual preparative method is to heat phosphorus pentachloride with a small excess of ammonium chloride in a solvent such as refluxing sym-tetrachloroethane (b.p. 146"). The product after removal of the solvent is a mixture of oils and solids from 70 % to 90 % of which dissolves in light petroleum. This soluble fraction may be separated by distillation and fractional crystallisation into the products shown in the Table. The yields given are however only approximate and vary with the exact experimental conditions. The fraction which is in- soluble in light petroleum varies in consistency from M.p.B.p. (PNCl,) 40% 114" 256" (PNCI,) 15% 123.5" 188"/13mm. (PNCl,) 15% 41" 223-224"/13 mm. (PNCl,) 5% 91" 261-263"/13 mm. (PNCI,) 25% (n = 7 or more) an oil to a plastic solid and has the composition (PNCl,),,PCl,. Its structure is referred to later. The trimer has been shown by electron-diffraction studies and by X-ray crystallography to have a plane six-membered ring of alternating phosphorus and nitrogen atoms with P-N bond length of 1.61 & 0.04 8 and P-CI bonds perpendicular to the ring. This is shorter than the value for a single P-N bond (1 -78 A) found in sodium phosphoramidate. More- over all the P-N bonds are of equal length. The usual formulation with alternating single and double bonds is therefore not a true representation of the structure.It is now considered that the partial double-bond character arises from n-bonding in- volving the lone electron pair of the nitrogen and the d-orbitals of phosphorus.14 Conventionally the trimer may be represented as a resonance hybrid (X) of two KekulC structures. CI2 12 N+J yp*y A -I II cl*P,N"PcI CL P 'N ,Pa (X) The tetramer differs from the trimer in having a puckered ring system in the solid state though spectroscopic evidence indicates that it is flat in solu-tion. The fluorinated tetramer is also different being based on a chair-shaped structure. In other respects however the tetramer is like the trimer. The bond length is 1 a67 8 and the bond order is again between one and two.It seems likely that the higher polymers (up to say n = 12-18) also have ring structures since there is a certain continuity in physical and chemical properties throughout the group. The basis of the aromatic character which is PROCEEDINGS encountered in the phosphonitrilic halides is different from that in benzene and borazole where the n-bonding system is made up of p-orbitals. This was first clearly pointed out by Craig and Paddock.15 In the phosphonitriles there is a p-orbital available on each nitrogen atom but all the p-orbitals of the phosphorus atom are utilised in its four bonds. The Mth electron of phosphorus instead occupies a d-orbital. The resulting n-bond which gives enhanced stability to the ring is then derived from a mixed p-d orbital.These authors have also applied these considerations to explain the variation in stability of the various cyclic structures and also the flexibility of the tetramer. The aromaticity implied in the structures assigned to these compounds is reflected in their chemical properties. The chlorine atoms in (PNCI,) are chem- ically less reactive than those in PCl,. Hydrolysis is relatively slow and yields a variety of phosphinic acids. The ring remains intact in esterification by alcohols and alkoxides and with ammonia and primary or secondary amines reaction follows the normal course which would be expected for an acid halide though complete elimination of halogen is difficult.A hexaphenyl derivative of the trimer P,N,Ph6 has been made by interaction of the trimer with phenylmagnesium bromide in boiling toluene and very recently Searlel has made methyl- phosphonitriles by reaction of trichlorodimethyl-phosphorane Me,PCl, with ammonium chloride. This reaction gives very low yields of cyclic polymers the chief product being a mixture of linear polymers. However the latter have been successfully cyclised by refluxing them in chloroform with triethylamine and ammonium chloride yields of the order of 70% of the trimer (XI) and tetramer (XII) being MQ2 Me,P-N=PMei ",P" I1 I I II ';JY Me2P*N/PMe2 Me,P=N-PMe2 (XI) (XI 0 obtained. These substances are of rather special in- terest since they dissolve in cold water without de- composition and also do not polymerise to a rubber at 350",as do the parent phosphonitrilic halides but decompose instead.Cyclic phosphonitriles containing other halogens may also be made. Thus phosphorus pentabromide with ammonium bromide gives a range of bromo-compounds and with ammonium chloride yields chloro- bromo-derivatives. These halogens may also be replaced by other groups (e.g. -SCN or -N3) l4 Paddock Adv. hrg. Chem. Radiochern. 1959 1 348. l5 Craig Ckm. and Ind. 1958 3; Craig and Paddock Nature 1958 181 1052. Searle Proc. Chem. SOC.,1959 7. AUGUST 1959 and this method must be used to obtain fluoro- derivatives since attempts to prepare these directly give the stable ammonium hexafluorophosphate.The fluorinating agent which has been used with the greatest success is potassium fl~orosulphite:~~ other reagents such as lead fluoride convert the chloro- into fluoro-chloro-compounds. Recent work by Paddock and his co-workersl* has resulted in the isolation of fully fluorinated products up to (PNF& with a purity of >99%. The normal boiling points of these compounds are tabulated. There are indica- tions that this series can be still further extended and (PNF,), n = 3 4 5 6 7 B.p./760 mm. 50.9" 89.7" 120.1" 147.2" 170.7" (PNF,), n = 8 9 10 11 B.p./760 mm. 192.8" 214-4" 230.8" 246-7" the smooth gradation in boiling points suggest that all the compounds are cyclic as the lower members which have been prepared earlier are known to be.In these compounds the P-F bond is less susceptible to hydrolysis as it is in phosphorus trifluoride. Reference must be made here to a compound P,N,CI which was isolated by Stokes and for which Paddock has suggested the cyclic structure (XIII). The existence of such a compound opens up many C'2 "P'" C1.I' ' CI N/ '\N/ '< SJ II I cI,P,N,~N,Pc12 Cl (xrrr) interesting possibilities especially as the ring struc- ture appears to be reasonably stable. The petroleum-insoluble fraction which is left in the original preparation of cyclic phosphonitrilic chlorides almost certainly consists of a mixture of linear polymers. These compounds unlike the cyclic polymers are highly polar and much more reactive and are believed to be of the type PCl,(PNCl,),Cl.Similar products are formed when the cyclic polymers are heated with ammonium chloride at 350". The cyclic polymers also give solid products when they are heated to 250-350". These are gums or are rubbery in consistency and are believed also to be chain-like and it is thought that oxygen plays a part in the polymerisation. These polymers swell re-versibly in organic solvents and also in some cases develop an X-ray fibre diagram on stretching. Un- fortunately the chemical stability is not higher than that of the simpler cyclic products but if this could be improved these materials would be of potential value. See1 and Langer 2.anorg. Chem. 1958 295 316. Paddock personal communication. 207 Before leaving the subject of polymers containing phosphorus and nitrogen we may note that the phos- phonitriles do not by any means exhaust the pos- sibilities of this field.Thus the interaction of phosphorus pentachloride and ammonia gives a compound with the formula (NH,),P-NH, which is almost certainly polymeric; and the trichloride and ammonia also give products of considerable com- plexity. With phosphoryl chloride and ammonia the triamide OP(NH,) may be isolated and this yields the cyclic compound (XIV) by loss of ammonia. The dimer (PhNPCl) (XV) may also be mentioned as a type not so far encountered in the chemistry of the phosphonitriles. H2y y2 CI O=P-NH-P=O P I I I I HN NH PhN' 'NPh \' I Cl "2N (x I v) (X V) Time will not permit more than a brief reference to the large group of polymeric substances formed when sulphur is linked to various other non-metallic atoms.The most familiar example in this field is furnished by the compounds containing sulphur linked to oxygen and the orthorhombic form of sulphur trioxide may be cited as an example. Its crystal is made up of cyclic S,O units. It is however among the compounds containing sulphur and nitrogen that the greatest diversity is encountered. Here we owe much to Professor Becke-Goehring who has not only elucidated the chemistry of tetra- sulphur tetranitride S,N, but has extended the field to include a number of other interesting heterocyclic structures. Tetrasulphur tetranitride (XVI) is best prepared by heating a solution of sulphur chloride (SCI,,) in carbm tetrachloride to 30-51)" in a stream of ammonia.It is a yellow crystalline solid. The oxidation number of sulphur is +3 and hydrolysis S-N-§ Cl I I I HN-+-YH N/s\ N N N S S II 1 I I as ,SCl S-N-S I HN-S-NH N (XVI) (XVI I) (XVI II) gives ammonia and oxyacids of sulphur. The mole- cule has a boat-shaped configuration with alternating sulphur and nitrogen atoms at a distance of 1.62 A corresponding to a bond order between one and two. It is readily reduced by stannous chloride to the tetraimide (XVII) the presence of N-H bonds in which is proved spectroscopically. The hydrogen atoms may also be replaced by organic groups. For example ethylamine and sulphur chloride give S,(NEt),.Chlorination of tetrasulphur tetranitride yields 2,4,6-trichlorothiazine (XVIII). Bromination gives (SNBr), of unknown molecular weight while controlled fluorination in carbon tetrachloride solu- tion with argentic fluorides leaves the ring intact and gives white needles of S4N,F,. When however the reaction temperature is raised the ring breaks and the products include SN2F and SNF. When tetrasulphur tetranitride is heated at low pressures to 300" the ring is broken and a solid with the molecular formula S2N2 is formed which poly- merises to a substance of unknown molecular weight. The latter forms fibre-like crystals with a metallic sheen and has the unexpected property of semi- conduction. The most probable structure (XIX) in- volves a chain of alternating sulphur and nitrogen atoms.Tetrasulphur tetranitride also reacts with ,,"p "* 4N / N\s& N\ sssss (x 1x1 sulphur in carbon disulphur solution forming S,N to which the formula (XX) has been assigned although the structure has not been studied by physical methods. Reference may also be made to heptasulphur imide S,NH which is very readily made by the reaction of sulphur monochloride with ammonia. The presence of an N-H group has been established spectroscopically. It is unexpectedly stable and forms metalk derivatives e.g. S,NNa and (S,N)2Hg can be acetylated or benzoylated and also gives an N-sulphonic acid with sulphur trioxide. Becke-Goehring has also shown that reaction with sulphur dichloride in presence of pyridine yields S(NS,),.PROCEEDINGS The range of possible sulphur-containing products is much wider than the examples given indicate. Thus thionyl chloride also reacts with ammonia in the gas phase to form an imide SO(NH) which polymerises readily to an insoluble material. If on the other hand tetrasulphur tetraimide S4(NH)4 is oxidised with air at 110-120" it is converted directly into the tetramer (SONH), the molecular weight of which has been unambiguously established. There is very much more that could be said about polymeric material formed by the non-metals but the examples given will I hope illustrate some of the directions in which progress has been most marked. With a few exceptions little of real importance from the point of view of technical applications has yet emerged.A few topics have been examined in detail though in no case exhaustively and the role of n-bonding as a factor in enhancing the strength of bonds has been well brought out. We have seen that catenation of a single type of atom is not a very promising route to stable polymers whereas with varied atoms in a chain or ring the possibilities are very much greater. There can be little doubt that the large amount of research now being done on in-organic polymers will before long bring a more systematic approach to the whole subject so that polymers which are at present intractable solids may be tailored to meet specific requirements. It is my belief that this is one of the most exciting fields of current research in inorganic chemistry and that we shall soon witness even greater developments than those which have been reviewed today.REPORT OF THE CO-ORDINATION CHEMISTRY CONFERENCE WHILEwe may hesitate to accept without reservation one report,l of this conference as "Probably the most important thing which happened in Britain in recent weeks-far more important for the country's long-term future than the budget for example-was something that didn't get into the newspapers at all," yet certainly the International Conference on Co- ordination Chemistry held in London from April 5th to llth 1959 was one of the most successful meetings of its kind held so far. It was timed to coincide with the Annual General Meeting of The Chemical Society and was arranged by The Chemical Society with sponsorship from the International Union of Pure and Applied Chemistry.From 4 p.m. on the Sunday when the Conference opened for registration at University College London until the last guest left Thames House late on the following Friday evening there was more than enough of scientific social and spirituous in- terest to satisfy all of the 659 members who registered as well as the 142 accompanying guests. No less than 25 nations were represented at the Conference. The main lectures were held in Friends House in Euston Road N.W.1 but the papers were read in lecture theatres at University College in Gower Street. Various facilities such as the Mixed Staff Common Room and a bar were open to the par- ticipants all under the benevolent eye of the well- The Science Correspondent The Church of England Newspaper April 24th; 1959 p.13. AUGUST1959 preserved effigy of Jeremy Bentham in the Cloisters. After a brief opening on the Monday morning by Professor H. J. Emelkus President of the Chemical Society the first of the General Lectures was given by Professor Ziegler. These general lectures which are discussed briefly below were given at the beginning of each of the morning and afternoon sessions with the exception of Wednesday and Friday afternoons. The remainder of the morning and the afternoon sessions on each day were given over to the presenta- tion of papers. Three parallel sessions were necessary to provida enough time for the delivery of the 100 papers accepted for reading.At the end of each ses- sion about 45 minutes were available for discussion not only of the papers read but also of the remaining 41 contributions. It was arranged that visitors to Great Britain who had one or more papers accepted would be given the opportunity of reading at least one of these. Although it was stressed that the omission of a paper from the list of those to be read was no reflection whatever upon its merit members of the Scientific Committee none of whom read papers were a little nonplussed when congratulated by one guest on the wise selection of the better papers for reading! The seven general lectures were delivered to full assemblies of the Conference.These lectures could be placed into two categories; in one category the lectures gave a survey of some particular aspect of general interest in inorganic chemistry at a level appropriate for those who are not experts in the field and in the other they presented a more detailed exposition of some particular facet of the chemistry of organometallic compounds. The lectures which fitted the first category were The Stability of Metal Complexes by Dr. IF. M. N. H. Irving; Mechanisms of Complex Ion Reactions-Recent Advances by Professor H. Taube; and Recent Developments in the Theory of Metal to Ligand Bonds by Dr. L. E. Orgel. Lectures fitting into the second category were New Aspects of some Organometallic Complex Compounds by Professor K.Ziegler ;Metal Carbonyls and Related Compounds as Catalytic Intermediates in Organic Syntheses by Dr. H. W. Sternberg; n-Complexes of Hydrocarbons with Metals by Professor E. 0. Fischer ; and Complex Acetylides of Transition Metals by Professor R. Nast. Dr. Irving outlined the recent developments that have taken place both in the determination and in the interpretation of stability constants of complex ions in solution. He stressed the exact meaning of the term stability as employed here and in other fields of co-ordination chemistry. In the course of the one lecture he was able in his own inimitable way to cover the whole of this large and expanding field. In the lecture on the mechanism of complex-ion reactions Professor Taube divided his attention between the two main aspects of this subject.In one of these he dealt with the current views on substitution in com- plex ions and in the other he discussed the fascinating field of electron-transfer reactions between complex ions. Dr. Orgel covered the broad and basic subject of the nature of the ligand-metal bond and he reviewed the various types of bonding which occur in metal complexes; the main emphasis of this lecture was concerned with metal-carbon bonds and some interesting speculations were presented con- cerning the nature and structure of some transient intermediates in organometal chemistry. In the second series of lectures certain fields of metal-carbon complex chemistry were dealt with in some detail.Professor Ziegler gave an admirable summary of the metal-carbon compounds which are basic in the synthetic and industrial organic chemical fields and are closely associated with his name Dr. Sternberg in a masterly survey of the rapidly growing field of metal carbonyls paid particular attention to the nature and structure of the intermediates in these reactions. The chemistry of “sandwich” compounds was ably expounded by Professor Fischer who pre- sented a gripping account of the development of the field and of the large variety of ligands which par- ticipate in bonding to metals by using n-type orbitals. It is of great interest to note how rapidly this field has developed since the original discovery of ferrocene in 1951 and how the subject which provided only one paper at the Amsterdam Conference has developed to such an extent as to be now one of the main fields of organometal chemistry.The final lecture was given by Professor Nast; this dealt with the important field of metal-acetylide chemistry; he reviewed the ex- perimental results in a field where the reactivity of the compounds makes the work most exacting. Per- haps the most important impression which one got from these lectures was the large overlap which is now evident between inorganic and organic chem- istry. Clearly a sound knowledge for both branches of chemistry is essential for progress in this field. On Wednesday morning April 8th the President of the Chemical Society Professor H. J.Emelkus delivered the Chemical Society Presidential Address entitled “Some Inorganic Polymers”. This lecture was attended by many members of the Conference. It was specially appropriate for the occasion since he reviewed the types of polymers formed by the light elements such as sulphur nitrogen etc. He stressed the way in which these complexes owe their stability to the probable use of dative d,-bonds. This lecture is published in full in this issue of Proceedings. The general lectures will be printed in full in the report of the Conference which is to be published by PROCEEDINGS the Chemical Society,* together with abstracts of the papers submitted. The 141 papers submitted for reading or discussion covered a very wide range of topics and they fall into a number of categories conveniently classified as follows (a) Thermodynamic Properties (21 %) ; (6) Preparative (15 %) ; (c) Organo-metallics (1 4%) ; (d) Kinetics and Mechanism (13 %); (e) Spectroscopic (1 1 %); (f)Structure (8 %); (g) Miscellaneous (18 %).An examination of the papers in the thermo- dynamics section (a) shows that the measurement of stability constants of metallic complexes is still very popular; however a change in emphasis towards hydrolysis and condensation phenomena involving polynuclear cationic and anionic species was obvious. The general equilibria between aquo-complexes and ligands of varying donor complexity were also studied although few experiments were carried out over the range of temperature necessary to permit the calculation of the thermodynamic quantities other than free-energy changes.An interest in the interpretation of stability constants in terms of ligand-field theory and solvation effects was also evident. The general tendency as apparent from the papers that were read appears to be towards investi- gation of more complicated systems at one tempera- ture rather than the complete investigation over a temperature range of a simpler system. The stability constants were determined mainly by the classical procedures e.g. redox potentials pH measurements and spectrophotometry. Most of the papers describing and characterising new compounds could be placed into one of two sub- categories one dealing with unusual oxidation states and the other with uniisual co-ordination numbers.In the former the main interest was in the characterisa- tion of the low oxidation states of the transition metals and of these the following deserve mention Ti(-1) and Ti(0) ; Re(r1);Fe(1) ;OS(I); Rh(r) ; Rh(I1); and Ir(r). Compounds of unusual co-ordination number and stereochemistry were represented by 7-and 8-co-ordinated fluoro-complexes of molyb-denum tungsten and rhenium and by some sub- stituted carbonyls of molybdenum and tungsten. The data on the tetrahedral structure of some nickel(@ complexes were extended by the description of some new substituted phosphine complexes. The properties of certain compounds of unusual volatility namely anhydrous ferric nitrate and cupric nitrate-perchlorate were also discussed (Addison and Hathaway).Although one of the main aims of the Conference was to emphasise organometallic compounds only one paper in seven fell into this category. However several of these were of considerable interest and importance. One group of papers dealt with the use of metal carbonyls and metal alkyls as catalysts in organic chemistry especially with reference to ethylenic polymerisation. An important contribution was made by Coffield Kozchowski and Closson who discussed the equilibrium Heat R.$zMn (COA R.Mn(CO), Pressuun 0 + co (where R = alkyl or aryl). Papers such as this gave one the feeling that we are definitely getting close to the actual mechanism of the important industrial processes based on the use of metal carbonyls.Several papers dealt with the use of mixed alkyl- aluminium-TiCl catalysts; the elucidation of the mechanism of polymerisation was helped by the paper presented by Eden and Feilchenfeld of Israel who have determined the products of the reaction between triethylaluminium and titanium tetra-chloride. A second group of papers was devoted to the rapidly expanding preparative metal-organic field and new compounds of transition metals e.g. Co Ni Pd Pt were described. It seems likely that a synthesis of our knowledge of the circumstances under which particular metal-organic bonds (e.g. Ni-CH,) can be formed together with the results of work on suitably chosen model carbonyl catalytic systems will soon lead to remarkable advances in this subject.The most popular aspect of kinetic studies still seems to be the investigation of the mechanism of substitution especially in octahedral complexes. Aquation received the most attention especially when involving replacement of chelate groups. It was disappointing however that discussion and con- troversy kept mainly to finer points in the interpreta- tion of the kinetics and that the fundamental points of mechanism were in many cases overlooked. The study of substitution was extended to tetrahedral configurations of the transition elements (Basolo et af. Meriwether ef a!.). Considerable interest was shown in the catalysis of organic reactions by in- organic salts and complexes and attempts were made by Stranks and by Adamson to throw some light on the mechanism of photocatalyses in some exchange reactions and substitutions.It was evident from many of the preparative papers that were presented that magnetic-susceptibility measurements and infrared and ultraviolet spectro- scopy are now becoming the accepted tools of the * Special Publication No. 13; price €2 2s. (or $6.00) per copy (El 5s. to registered members of the Conference). AUGUST 1959 co-ordination chemist. A number of papers were delivered in which the main interest centred on the development and utilisation of these special tech- niques for inorganic chemical problems. In the field of infrared spectroscopy two main lines of approach are being followed.The spectra are being used as a means of elucidating the stereochemistry of com- plex molecules particularly the finer details of the bonding of chelating ligands. Thus attention is being paid to chelate groups which may exist in more than one conformation e.g. chair or boat forms. Similar- ly it is being employed to ascertain the mode of bonding of a chelate having more than one donor atom e.g. an ester. In addition a more fundamental investigation of the infrared spectra of inorganic complexes is becoming evident with the determina- tion of the force constants for the individual metal- ligand bonds in a variety of circumstances. A full co-ordinate analysis has been made of a series of metal-acetylacetone complexes (Nakamoto).Raman spectroscopy is also being used in a manner similar to that for infrared spectroscopy. The ultraviolet absorption spectra of a series of tetrahedral COM-plexes were reported and the use of such spectra as a possible diagnostic tool in studying stereochemistry was also suggested as well as the use of ultraviolet spectra for deciding the mode of bonding of a ligand with two potential donor atoms e.g. SCN-. A cor- relation of some of the factors influencing the n-bonding capacity of ligands was also deduced from a study of ultraviolet absorption spectra. In the papers dealing with magnetism it was evident that the main concern in this field has now moved to detailed studies of the magnetic properties in terms of ligand-field splitting and spin-orbit coupling effects and the correlation between the magnetic and spectroscopic properties.It is interesting that mag- netism has now passed through the stage in which it was applied empirically whereas infrared spectro- scopy is still partly concerned with empirical correla- tions between group frequencies their shifts and the structure of the complex a role occupied by mag- netism only a short while ago. In the section concerned with structure of complexes it was very pleasing to see the steadily increasing number of papers which described the results of the use of X-ray diffraction methods for structure determination. This technique may be looked upon in many ways as the final arbiter in a structural problem.There are two important kinds of information which emerge from these studies the establishment of the basic stereochemistry of the metal complex and a detailed knowledge of the bond lengths and angles. The second point may often be important for a detailed understanding of the re- activity and stability of complexes and is fundamental to the development of ideas of chemical bonding. Of 211 the papers read those dealing with the determination of the structures of some hydride complexes of platinum substituted carbonyl complexes of iron and phosphorus oxychloride addition compounds have clarified many problems in their particular fields. In the case of the substituted carbonyl com- plexes (Mills) some interesting results were presented on metal-metal distances for iron cobalt and nickel compounds in addition to the establishment of the basic structure of these substances.The other papers in this field certainly added to the sum total of knowledge that will allow the step from the analysis of a complex to the formulation of its structure to be taken more readily. As a whole it is pleasing to see that more basic structural data is being accumulated as for obvious reasons this im- portant field has been slow in developing. It is of interest to note certain trends in the development of the subject that emerge from an overall view of the lectures and papers presented. Although valency problems are of major importance there was very little detailed discussion of this sub- ject.It seems clear that although ligand-field theory has made a major contribution to the development of our understanding of the spectra stereochemistry and magnetism of complexes it has been temporarily over-emphasised. It is now fitting into its true per- spective together with other methods of approach; and it seems likely that this period of consolidation will last for some time yet. Advances are needed badly in the quantitative aspects of the nature of the metal-ligand bond especially of metal-carbon bonds. Also a clearer understanding of what we really mean by metal-ligand double bonding and its quantitative correlation with physically observable data is long overdue. Perhaps the most pleasing feature is the steadily increasing application of physical methods to the study of complex com- pounds; it is becoming normal for these to be carried out in addition to the more traditional approach in- volving preparation and analysis only.Finally the more X-ray structure determinations that are ob- tained the better will be our chances of tying together so many of the isolated data procured by other physical methods and getting a better theoretical insight into metal complexes generally. Although one of the main reasons for holding a Conference of this kind is to provide an opportunity for the interchange of ideas a perusal of the list of papers suggests that an important reason for the sub- mission of several of these was to obtain the neces-sary travel grant.Necessary as this may be it is desirable in the reporters’ opinion that a more liberal policy be taken on this matter by some institutions. In addition to the scientific sessions discussed above a wide range of social activities was provided during the Conference. On the Monday evening a conversazione was held in the Rooms of the Royal Society and the Geological Society where an in- teresting collection of scientific exhibits organised by Dr. P. Owston was on display. On the Tuesday evening various theatre parties were arranged. Apart from the Presidential Address there were no other scientific activities on the Wednesday. Members of the Conference were invited to visit Oxford or Cam- bridge during the afternoon and to attend the Anni- versary Dinner of the Chemical Society in the evening at the Connaught Rooms in Kingsway; there were no less than 480 participants at this function.The Overseas guests were entertained in the Fishmongers’ Hall on the Thursday evening and there were in all some 320 guests and hosts present. Finally on the Friday evening the Directors of Imperial Chemical Industries Limited entertained about 550 members of the Conference at Thames House Millbank; this was an outstanding entertainment and the organising committees are profoundly grateful for this hospitality. PROCEEDINGS It was specially pleasing that Imperial Chemical Industries Limited were our hosts on this final even- ing for these Conferences owe a lot to a gathering of some 20 people at the (now) Akers Research Laboratory at Welwyn in 1951.There some 11 papers on co-ordination chemistry were read; and this gathering proved to be the prototype for the future series of conferences on co-ordination com- pounds. The number of papers read has increased remarkably in the intervening eight years. Thus at Copenhagen in 1953 33 papers and lectures were presented whilst in Amsterdam in 1955 there were no less than 65 papers. The figure for Rome in 1957 was 78 and at the present conference 141 papers were submitted. One realises that if this continues a real problem of selection awaits the organisers of the next conference to be held in Detroit in August 1961. However we all look forward to seeing our friends in person again at Detroit and to discussing many of solution.the chemical problems still awaiting J. LEWIS R. S. NYHOLM M. L. TOBE. NEW FUELS By C. H. JOHNSON,C.B.E. D.Sc. Ph.D. (MINISTRY OF SUPPLY) THEadvance of the Rocket culminating while this article was being written in the final defeat of the Earth‘s gravitational pull by the Russian cosmic vehicle has kindled a good deal of specu-lative interest in the fuels which these monsters devour. Most people’s impression of a rocket as a rather elementary form of engine displaying the engaging habit of last minute unco-opera- tiveness is not far wrong even of these newest examples of the pyrotechnist’s art. Its faculty of missing by thousands of miles while scoring a resounding success can only be described as out of this world.The over-eager moon satellite becomes a planet of the sun. There are compelling reasons why the rocket should have been the instrument of Man’s latest escapades. Structurally simple and compact it is the embodiment of Newton’s “reaction” prin- ciple; at the moment of launching the substance to be discarded-the fuel-naturally constitutes the highest practicable proportion of the total mass. Unlike air-breathing engines oxidant as well as fuel* is carried the energy level of each being adjustable through variation of their chem- ical nature or composition. Air can readily be improved upon as an oxidant and its replace- ment in the combustion process makes powered flight feasible in attenuated regions of the at- mosphere or in vacuo surroundings which lead to significant gains in operating efficiency.The period between lighting-up and all-burnt in a large expendable rocket motor seldom exceeds two or three minutes and is often much shorter but within the brief span of burning it surpasses all other prime movers in the rate at which power can be generated. To point these statements a vehicle on the launching platform capable of projecting a one-ton pay-load into outer space would weigh at least 100 tons the fuel account- ing for over 90% of this; the average rate of fuel consumption in flight might exceed half a ton per second equivalent in the case of liquid oxygen-kerosine to 6 x lo6 B.T.U. per sec. or about nine million horse power.In field-free vacuum the force or thrust on a “reaction” motor is governed solely by the rate * In this article the term “fuel” is sometimes used as in this instance in the sense of the reducing partner; sometimes as in the title to mean the propellant as a whole. AUGUST 1959 of ejection of mass (which is controllable) and the velocity of the ejected mass relative to the motor body independent of the latter’s motion. This relative or “effective” efflux velocity c is a key parameter characteristic of the propellant. The force developed in absolute units dyne or poundal per unit rate of propellant consumption (unit rate of ejection of mass) or specific thrust is equal to c. Usually however rocket engineers express force in pounds weight and the specific thrust then becomes c/g with the dimensions of time.This practical unit is called “specific im- pulse” Is, (a misnomer) and is the accepted criterion of propellant performance according to the equation assuming perfect gases out before the end of the short periods of the Periodic System. Heavier elements may of course enter unavoidably; for instance chlorine as the oxygen carrier in perchlorates. RG 1. H He Li Be B C N 0 F Ne Na Mg A1 Si ............ The small piece of the Periodic System shewn in Fig. 1 brings in most of organic chemistry but the scope afforded for new fuels is not notably broadened on that account A heat of combus-tion is the nett result of breaking and making valency bonds and in this respect and as regards the gaseous end products-whatever the identity c = Ispg = {const.(y Y I)2[1 -___ -or recollecting that y = Cp/Cvand C2,-C =R per mole of gaseous exhaust products which brings in C specifically. With any selected propellant the function is seen to approach a maximum value (in respect of conversion of chemical energy into kinetic or thrust energy of the jet) as the pressure of the surrounding at- mosphere pa,approaches zero as in outer space. Practical considerations impose upper and lower limits onp, the gas pressure in the combustion chamber working pressures in actual rockets being of the order of 20 atm. for liquid propel- lants and 1,000lb. in. (about 68 atm.) for solid.These values of pc are commonly but not in- variably taken as standard in theoretical calcula- tions of ISD,and amongst the assumptions which need to be checked when confronted with specific impulse figures p is perhaps the most important. Frequently the reader is left in doubt and possibly with misleading impressions as to the absolute and relative merits of the fuels. The dominant term in equation (1) is (TcCpm-l)+,shewing Ispto be enhanced by high temperature and high heat capacity per unit mass of exhaust gases. The influence of the thermal efficiency term within the square brackets is obviously (p >pa) the more favourable to IS2 the smaller is the heat capacity per mole. Both these basic requirements are satisfied only in molecules of low molecular weight and hence the interest in elements as fuel constituents peters of the reactants-it is rather a case of “plus qa change ...”. Fundamental principles apply equally to new rocket fuels as to old and the implication of Fig. 1 is that room for manoeuvre in the selection of elemental ingredients is strictly limited. Mendeleev could have drawn up nearly as complete a list of likely chemicals for con- sideration as can be done to-day. In the Table specific impulse data of some representative liquid and solid propellants are given calculated for the standard combustion chamber pressures mentioned earlier and at optimum oxidant-fuel ratio in the cases of “two liquid” propellants called bipropellants or bifuels. The figures are illustrative rather than accurate and each could vary by a few units depending on the assump- tions made in calculating them.The exceptionally high specific impulse of certain liquid bipropellants arises from the free- dom to select liquefiable elements from opposite sides of the Periodic System. The unimpressive performance index of the bifuel fluorine-kerosine is bound up with the properties of the carbon fluorides. The attractiveness of liquid hydrogen fuel is clouded by complications resulting from a very low boiling point and to an even greater extent from the uniquely high specific volume (low density) which plagues designers with additional structure weight. PROCEEDINGS The commoner rocket propellants mainly composed of carbon hydrogen oxygen and nitrogen give rise to combustion temperatures of about 2500*-3500”~ and within this range dissociation reactions begin to participate and grow in significance as the temperature climbs.For example HeO = OH + &H2+ 67 kcal. H2= 2H + 104 kcal. CO + H,O = C02 + H2 -9.84 kcal. The influence of dissociation on fuel perform- ance is illustrated in Fig. 2 in which in effect the energy of the end gases from a propellant of empirical formula CHsOa* is plotted against absolute temperature the total dissociation energy being shewn separated from the rest. It will be observed that at 4000’~-an operating level as yet barely achieved in rocketry-almost as much energy has to be diverted to dissociation processes as to all the other degrees of freedom together.Thus elemental constitution enters to an important extent when considering how to obtain the highest specific impulse for a given energy of combustion and elimination of carbon and the water-gas equilibrium would seem to be one direction in which to proceed towards im- proved fuels. On this basis also the presence of nitrogen in carbon-containing fuels might on balance offer some small gain by virtue of the thermal stability of the nitrogen molecule N = 2N + 171 kcal. Before examining further the principles of fuel selection and improvement we should be clear about the distinctions between “liquid” and “solid” rocket motors i.e. those employing liquid and solid fuels respectively.In both types structure weight has to be ruthlessly pruned and this can only be done at the expense of safety margins. In a liquid motor oxidant and fuel are carried in separate tanks whence they are pumped and injected into the combustion chamber in fine streams mixing being artificially contrived and also assisted by turbulence created by chemical reaction. The rate of transfer of energy from the burning gases to the walls of the chamber through convection and radiation can be enormous of the order of 3 B.T.U. in.-2 see. (5 H.P. in.-” and as the result of this heat flux and the disparity between flame temperature and the melting point of the thin-walled casing a liquid motor inevit- ably operates near the brink of catastrophe.It does not have to operate long. Over-heating can be prevented by circulation of liquid (the fuel if the supply is adequate rather than oxidant) with- in the honeycomb walls of the combustion chamber and round the vulnerable throat area of the exit nozzle where the heat flux may be four times greater than that across the chamber walls just before injection. 2a# 3000 44m F OK FIG. 2. Influence of dissociation on fuel performance. (The shaded portions represent dissociation energy.) Unlike fireworks which burn cigarette-wise from the tail end combustion in a large solid motor takes place in a cavity extending the entire length of the charge from the centre outwards- layer by layer-towards the inner wall of the lightweight cylindrical casing.Ideally the flame cannot touch the casing until all the propellant has been consumed; thus by arranging for the charge itself to act as a thermal barrier part of the insulation problem is neatly solved. In both solid and liquid motors the seat of chemical re- action is the gas phase but the fact that combus- tion of a solid charge proceeds only at exposed surfaces is a distinguishing feature of the utmost importance in determining the burning rate. If for any reason insufficient energy returns to the burning surface so-called it ceases to be a source of gaseous reactants and the flame will chuff or die out. By ingenious use of shaped cavities (e.g. * To simplify the presentation the atomic composition has been maintained constant; thus CH,Oo could for example be taken to be oxalic acid crystals (CO,H), 2H10representing zero calorimetric energy or liquid ethane-liquid ozone CIH + 2OS,having a very high energy.AUGUST 1959 a star cross section) or of more than one propel- lant composition in the same charge a sensibly constant area of internal surface can be main- tained despite progressive enlargement of the cavity and hence the rate of burningwithin it remains controlled. In flight a solid motor carries no mechanical pumps no valves to stick or leak and if the development work has been done thoroughly there is little likelihood of propellant turning up in places not intended which is an ever present hazard with liquid fuels. Because of their relative simplicity convenience of handling by non-technical personnel and immediate readiness for action solid motors weighing up to several hundred pounds have been widely adopted for tactical weapons of the sort which are gradually replacing conventional artillery.Only fairly recently has the idea gained currency that solid propellants might also serve in vehicles of long range and it is interesting to recall that some of the power units in America’s Pioneer rocket launched at the moon last December were reported to have been clusters of solid motors. As may be inferred from the Table at least as much solid propellant as liquid would be re-quired for the performance of a specified task and solid charges weighing several tons to several tens of tons would be called for according to the range and pay-load desired and the manner of employing them.Many problems are involved and it is obvious that some of the logistic ad- vantages offered by smaller solid motors will dis- appear with increasing size. Generalisations however are out of place here; such matters need to be sifted in reference to definite stated objectives. To return to the consideration of basic principles there exists a type of rocket propellant called monopropellant or monofuel composed of oxidising and reducing substances in close as- sociation in some instances as parts of the same molecule. They are reasonably stable unless stimulated. A classical example is concentrated aqueous hydrogen peroxide developed by the Germans during the last war for their V missiles and for a submarine engine.Peroxide can also serve as oxidant in bifuel systems but its use as a monofuel depends on catalytic decomposition thus H20,(liq.) -f H,O(steam) + go2+ 13-0 kcal. Organic nitrates and nitro-compounds such as nitromethane also fall into this category. De- composition once initiated by friction electric discharge or impact becomes self-sustaining and in certain circumstances steady burning may change abruptly into detonation reaction travel- ling as a shock wave through the liquid at a speed of four or five miles per second producing the shattering effects of high explosive. Substances vary greatly in this respect which in technical jargon is called “sensitiveness” or when measured on some arbitrary scale the “sensitivity”.The distinction between a propellant and a high ex- plosive lies essentially in the manner of burning and in the character of the pressure coefficient of / Heat of se/f-m&stion ad.&. FIG. 3. Variation of log r (the logarithm of the rate of steady burning with q (the energy of self-cornbustion per gram. of liquid monopropellants). the burning rate rather than in the magnitude of the energy release which is often comparable in the two cases. The point to be noted is that all solid propel- lants are monopropellants according to our definition and the question arises how and how far they can be safely employed. There is no simple answer but to obtain one is of the utmost importance and the purpose of Fig.3 is to give some indication of an experimental approach to the subject in the case of liquid monopropellants. Each of the straight lines refers to a specific chem- ical class-aliphatic mononitrates dinitrates nitro-compounds etc.-shewing the variation of the logarithm of the rate of steady burn- ing r measured under standardised conditions with the energy of self-combustion per gram q. It has been established that sensitivity to the im- pact of a bullet or shell fragment is roughly pro- portional to the product r x q and in Fig. 3 the dotted line r x 4 = const. has been chosen as representative of a monofuel found just sufficient- ly insensitive to be acceptable for application in weapons.On the premise that the time spent in the combustion chamber by an average product molecule varies as the length of the chamber and inversely as the mean flow velocity it can be shewn that the quotient r/q is a rough criterion of combustion efficiency. The dashed line r/q = const. is related to practical experience the constant embracing length and cross sectional area of the chamber droplet density and the ideal gas parameters. Fig. 3 is in effect a guide map the area below the dashed line being representative of mono- fuels difficult to burn in a rocket motor of accept- able dimensions; the area above the dotted line of those too easily detonable for application in weapons. The hatched region enclosed by the dotted and dashed curves is the domain of practical utility where serviceable monofuels may be sought.Clearly then it is no accident that the specific impulse of representative liquid mono- fuels given in the Table are lower than those of the bipropellants in regard to which-when all other obstacles to the use of those of highest energy have been overcome-physical separation of oxidant and fuel may be seen to be an extreme example of countering sensitiveness by inhomo- geneity of composition; by imposing a time lag on the mixing of reactants. It applies willy nilly to most solid propellants. Another sensitiveness- promoting factor is bulk or in technical jargon “confinement,” and this too is obviously a matter requiring close investigation as rockets grow in size.The most formidable obstacles in the way of achieving new fuels are not all chemical or tech- nical. A high energy liquid bipropellant for example can be selected from the list but the really difficult step is to reach a firm decision to go ahead with it. Doubts of many kinds arise. Is it sensible to sponsor the development of an oxidant (e.g. liquid ozone) or a fuel (e.g. liquid acetylene) which is itself an explosive? Is it likely that in the time required to do this a means will have been found which avoids the necessity to accept the practical disadvantages of an awkward though powerful propellant ? The worst dilemma of all is will there be enough of the stuff avail- able? The ability to undertake the development of a large rocket motor is dependent absolutely PROCEEDINGS on the existence of manufacturing capacity for the fuel to amounts measured in thousands of tons or tens of thousands of tons annually.Lacking such capacity the description “fuel” or “propellant” applied to an uncommon chemical is so much idle chatter. The creation of avail- ability on a requisite scale can be a substantial item in terms of human and material resources for there may be no commercial outlets for the product. Chancing an arm may yield dividends in unexpected directions but it is as well that the situation should be seen in this light from the beginning if it be so. As a current example of the costliness of excursions into difficult and unfamiliar chemistry the capital expenditure on two plants erected in the United States for the manufacture of “boron fuels” has been consistently reported in the Press to exceed $80,000,000 in total without reckoning development costs.The liquid products appear to be derived from decaborane B1,,HI4 a solid and to contain carbon as well as boron which presumably depresses the calorific value ;and re- quire to be stored under nitrogen as protection against atmospheric oxygen and moisture. The only liquid boron hydride is pentaborane B,H,. All are prepared from diborane B,H (b.p. -93 ”). Arithmetic suggests that something like two tons of boric oxide smoke will be discharged for every ton of fuel burnt in an engine so all in all it is clear that a good deal more than a gain in fue lpower is involved.In view of what has been written it may be less surprising than on a first impression that a not very significant extension of the choice of liquid fuels has taken place since the end of the last war. By that time the Germans had used on a consider- able scale in their rocket motor programme the oxidants liquid oxygen hydrogen peroxide and hydrogen nitrate (fuming nitric acid) and the fuels methanol ethanol petrol hydrazine (the hydrate chiefly) and aniline amongst others. The fact is that the rocket motor designer finds it difficult to make efficient use of propellants above the level I, 21 250 sec. His future rate of progress will depend on obtaining deeper know- ledge of heat-transfer phenomena and access to structural materials of better thermal and chem- ical resistance.Materials are likewise a major problem in adaptations of nuclear power to rocket propulsion. Turning again to solid propellants some of the AUGUST1959 217 problems met with in attempts to raise their years ago is a case in point. Superseded as a specific impulse have already been touched upon military propellant about the middle of the last and because mechanical devices play no part in century by the smokeless nitrocellulose powders their functioning chemical ingenuity has to com- and a little later by cordite it still finds applica- pensate as far as possible. Inevitably therefore tions for which no better substitute has emerged. performance is a blend of many qualities The latest types of solid rocket propellant (amongst which are the physical and rheological resemble gunpowder to the extent of having a characteristics of the charge) and improvement crystalline oxidant as main constituent say 80 in one or more is liable to be offset by impairment to 90% by weight.Surprisingly few powerful of others. Gunpowder invented thousands of oxidants are solids the best being ammonium TABLE. Theoretical Oxidant Fuel “Specific Impulse’’ (sec.) (a) Liquid bipropellants Hydrogen peroxide Alcohols petroleum fuels 210-250 Hydrogen nitrate I Dinitrogen tetroxide Hydrazine hydrate Oxygen (liq.) Ethanol 240 Kerosine 250 Ammonia (liq.) 250 Oxygen (liq.) Acetylene (liq.) 270 Hydrogen (liq.) 345 Ozone (liq.) Kerosine 275 Hydrogen (liq.) 370 Fluorine (liq.) Kerosine 265 Ammonia (liq.) 290 H ydrazine 295 Hydrogen (liq.) 355 (b) Liquid monopropellants Hydrogen peroxide (90 %) 135 Ethylene oxide 165 H ydrazine 175 Propyl nitrate 170 Ni trome t hane 220 (c) Solid propellants Perchlorates Organic polymers 180-245 j nitrate and perchlorate.The general impression that a solid fuel should contain a large proportion of combined hydrogen is perfectly sound and in order to achieve approximate chemical balance the fuel component seldom accounts for more than 10-20% by weight. A less obvious but essential function of the fuel in this class of pro- pellant is that of cementing the mixture together for a large rocket charge is in need of mechanical strength and flexibility in excess of that obtain- able by mere compression of a powder.This again restricts the choice and underlines the importance of polymeric substances of the hydro- carbon type. The narrowness of selection is palpably evident from Fig 1 being confined to a handful of elements and their hydrides. This is further accentuated by circumstances such as in- stability for example towards water-vapour or incompatibility or lack of cohesive qualities ;by a relatively low yield of gaseous products (metals boron) scarcity and costliness (beryl- lium) oxides that are toxic (BeO) or which melt or vaporise (Li20 B203).Changes of state waste the available energy or to put it another way the relevant heats of oxidation are much less im- pressive when the oxide products are taken to be gaseous instead of solid.So much is required of a solid composition to earn the title of “propellant” that progress in the direction of substantially higher specific impulse is sure to be difficult. For the reasons indicated “No Road” and “Cul de sac” notices are dis- played at several of the turnings but such trifles will not deter the craftsman in what after all is a splendid Black Art. A type of high energy fuel which has received publicity out of all proportion to its promise is the so-called atomic or free-radical fuel par- ticularly well exemplified by the transfer of re- combination energy of the lightest of atoms (H) to the lightest of molecules (H2), the latter acting as “third body” or working fluid in the reaction H + H + H2-+2H2 + 104 kcal.Depending on the initial concentration of atomic hydrogen in molecular hydrogen from say 10 % upwards estimated values of ZsD range from 500 to 1500 seconds which on paper look very encouraging. The actual situation is that not even a 1 % stable concentration of hydrogen atoms has been obtained at liquid helium tem- peratures and in any event there is no clue to a PROCEEDINGS practicable means of controlling the release of energy. As was evident from a Discussion organised by the Faraday Society at Sheffield University in the autumn of 1958 a similar posi- tion prevails in respect of other light atoms and radicals such as CH N NH OH etc.Theoreti- cally at least 5% concentrations would be required to equal or surpass liquid fluorine- liquid hydrogen bipropellant. None is a practical proposition at the present time and in con-sidering any future allocation of resources to this aspect of an otherwise attractive subject two points should be made. First that activation energies of reactions involving atoms or radicals are very small or zero; therefore it is certain that in the form of concentrates they will prove to be capricious explosives-like lead azide only more so; not propellants at all. Second that even successful development-at great cost-would amount to a barely significant closing of the gap between the chemical and nuclear scales of energy.Means of stabilising atoms and free radicals in small amounts are known but it is easy to forget that stabilisation is tantamount to reduction in the level of energy and consequently inimical to their prospects as fuels. Years hence it may be that these entities probably in the form of ions will be playing an essential part in super- propulsion (if the subject is then of more than academic interest) as they appear to have done in expanding the Universe but as rocket fuels in rockets as we know them to-day they have no future. The author of this article was commissioned to write about “new fuels” otherwise it would have been inexcusable not to have mentioned earlier that the recent spectacular achievements of rockets probably owe little or nothing to them.A great deal remains shrouded in mystery but as far as information goes it does not conflict with the impression that everything to date has in all probability been accomplished with “old” fuels ; fuels in the performance class of liquid oxygen- kerosine. The key to the riddle has been the successful engineering of “staging” whereby the structural parts of successive power packets are discarded in flight at all-burnt one after the other. The American rocket Pioneer 111 said to have been in- tended as a moon probe was reported as being made up of four stages the first a liquid motor AUGUST1959 the second and third solid motors. The latter were clusters not single rockets which is another engineering device of particular interest in solid motor development because of the problems created by increasing size of charge.It is self- evident that the shedding of “ironmongery” by a multi-stage rocket proceeding on its way leads to more efficient utilisation of propellant than when all in one piece for in that case the entire structure of the empty burnt-out motor counts as pay-load; which is an appropriate point to intro- duce the second fundamental equation of a reaction motor vj = c x log@ = I, x g x log& .. .. . .(2) v is the final velocity attainable by a given vehicle in the absence of external influences of any kind c the effective velocity of the efflux gases as in equation (l) and p the supremely important design feature the mass-ratio defined as the ratio of the initial mass of the rocket vehicle to its final mass when all-burnt.The maximum velocity v,,, reached in air subject to the Earth’s gravitational field would of course be less than v, and the capability of an actual rocket can be conveniently regarded as a com- bination of velocity terms -Vmaz -vt -(v + Va) v and v being the velocity lost on account of gravity and aerodynamic drag respectively. Bearing in mind that any specified mission can be broken down in similar fashion into a number of component velocities each corresponding to a distinct phase of the journey (the overall value of v being the summation of them)* and also that c is a characteristic of the fuel used it is evident that equation (2) is the formal ex- pression of vehicle capability introducing pay- load structure weight and the quantity and quality of the fuel.In order to bring in staging the effective mass ratio of the xth stage of an n-stage rocket is by definition 219 In Fig. 4 an example is given of a three-stage vehicle for which (pc)l is seen to be 5+9+20 5+9+2 5+9 5 ~ 2.1 (pSh,5+1 2i 2.3 and = 5 whence (Po) N 24. Had the rocket been built as a unit composed of four tons of ironmongery and 30 + 4 ~ thirty tons of propellant p = 4 = 8.5; thus some idea of the gain in performance due to staging is the ratio of the logarithms of 24 and 8.5 or just under 50%. Structure m&ht(S) Stage 3 and pag-/oad Pmpelant weight(P) Stage 2 I:/ ; FIG.4.Example of a three-stage vehicle. The justification for striving after higher specific impulse is clear from equation (2) since v is directly proportional to c which is thus a more potent factor in performance than the logarithmic term containing the structure weight. The dividend to be expected from staging is ob-viously subject to the law of diminishing returns but has proved in practice easier to collect than that from improved I,,. The example given in Fig. 4 is ad hoc but not unrealistic and it would Total mass of all stages above xth + initial mass of xth stage = Total mass of all stages above xth + mass of xth stage at all-burnt and in view of the logarithmic relationship for be hard at the present time to believe that a 50 % simplicity taking c constant for each stage improvement on Z, 2i 250 say to 375 seconds x be)%.... . .. ~(p,) is likely to be brought about in a chemical fuel pe = * The successful planting of an earth satellite requires an idealised velocity of 25 to 35 x los ft. set.-' according to the size and shape of the orbit. To land on the moon say 45 x lo3ft. set.-' including allowance for the rocket-induced deceleration phase of the descent; a lunar round-trip about 55 x lo3ft. set.-'. Very little more than this would do for Venus or Mars provided the journeys were leisurely. suitable for large rocket motors. From equation (2) it is also clear that the limitation on vehicle capability lies in what the engineer can in practice do with the materials of construction and fuels available to him; not in any particular level of fuel performance.Let us look at the position as it is to-day. Ranges of several thousand miles have been registered though not unfailingly by multi-stage ballistic missiles. Sputnik 111 weighing just over 2,900 lbs. including about a ton of instruments has been placed in a fairly close orbit around the earth and a cosmic vehicle of unrevealed mass carrying about one-third of the load of instru- ments of the Sputnik its last stage (possibly a military rocket) weighing 3,238 lbs. when empty of fuel is now circling the sun. It is a reasonable supposition that all this has been done with propellants of up to I, N 250 sec. Half way round the earth say ten thousand miles must be near the extreme limit of useful range for offensive strategic missiles though much smaller distances would be acceptable for many such operations.If instrumented earth satellites of about the size of Sputnik I11 possess any military value-for scientific exploration their potentialities are immense-they could it appears be put in orbit by fifty to a hundred tons of one of the commoner propellants. Obviously much remains to be done to give long-range missiles the reliability and accuracy essential for military purposes but manifestly too current fuels have gone a long way towards their goal. Space travel or even manned earth satellites in remote orbits represents a quite different kettle of fish.The pioneers may not want to be looked upon as expendable and preparations will have to be made in simulated anticipation at all events of their safe return. For this feat to be even a possibility the paraphernalia required for the return trip and to maintain life whilst in transit would raise the weight of the container considerably perhaps to ten tons an order of pay-load seemingly out of reach of the rocket designer with fuels other than liquid bipropel- lants of the highest energy and according to at least one good authority marginal even with them. Already the drain on resources which indul- gence in these adventures will entail is becoming widely if dimly appreciated. For the record a small but essential part of it liquid oxygen and PROCEEDINGS kerosine are priced at a few pounds sterling per ton.Hundreds of thousands of tons of each of these commodities are produced annually in Britain. (It must not be overlooked that ancillary equipment for liquid motors is very expensive.) Liquid fluorine might work out at E2,OOO per ton. Solid propellants in the form of fabricated rocket charges at perhaps &1,500 per ton re-quiring relatively little by way of additional equipment. We are accustomed to an enormous wartime output of propellants but under condi- tions of atomic and thermonuclear warfare this is no longer to be expected in anything like the same degree the heaviest demand as regards long-range missiles being likely to occur during the development phase-in peacetime-as pre-viously emphasised when pointing out the crucial importance of availability.It is very galling that on the threshold of an era of nuclear power and with the vision before us of a contracting Universe we should be obliged to fuss with chemical fuels feebler as they are by several orders of magnitude. Had the energy release from chemical reactions been lower by one order or less multi-staging would not have served to free us from earthly shackles. It is hard to dissociate this subject from gravity but were it not that the prestige of the greatest nations of the world is at stake-apparently-the thought of an intending space traveller perched as it were on some hundreds of tons of liquid fluorine should be enough to make a cat laugh.Half-a-million sterling might not cover the fuel costs. For the time being the quality of elegance amongst others seems to have departed from this field of endeavour. How different the situa- tion sixty years ago when on October 14th 1899 so Mr. H. G. Wells recounts Cavorite was first made ; part-accidental]y as befitted a scientific discovery an inter-Union dispute contributing. This magical paste (Wellsian prescience antici- pating and disposing of the issue “liquid” or “solid”) became on setting opaque to the force of gravity. The consequent journey to the moon and back cost the British taxpayer not a penny for the origin of the small local tornado was never suspected and the parents of Master Tommy Simmons who through meddling placed himself in orbit seem to have rested con- tent.By comparison modern schemes for im- proved methods of super-propulsion look cum- bersome and prodigiously expensive although it AUGUST 1959 221 is mildly reassuring that most of them could only operate or be permitted to operate in that fast- evolving refuse tip the stratosphere or in outer space. From all accounts the nuclear-powered rocket is not just round the corner and while the chemical rocket may not grow a great deal larger the chances that it will pass into limbo during the next decade do not appear bright. Finally in acknowledging the author’s wide- spread indebtedness especially to the fraternity at the Explosives Research and Development Establishment Waltham Abbey whose work has been freely drawn upon it is hoped that what has been written will appear as intended namely an elementary attempt to bring the subject of New Fuels a little into perspective.A subject moreover which does not diminish in interest and importance by recognising that chemically speaking the distant horizon is not limitless nor is the intervening landscape so full of golden promise as has sometimes been made out. Thanks are also due to the Chief Scientist Ministry of Supply who wished authorship on a hapless colleague. LETTER TO THE EDITOR Dear Sir Bond Representation in Formulse During the recent centennial commemoration of KekulC and Couper a number of those who took part suggested1 that the latter chemist was the first to designate the bonds between atoms in chemical formula by lines.2 Actually the honour belongs to my predecessor William Higgins (1 763-1 825).3 In his “A Comparative View of the Phlogistic and Antiphlogistic Theories” published in 1789 he wrote water I-d(I = inflammable air = hydrogen; d = dephlogisticated air = oxygen); nitrous oxide P-a7 (P = phlogisticated air = nitrogen); sulphur dioxide S-d (S = sulphur).He formulated other simple molecules in a similar way. d 6%’ d -Higgins it may be mentioned also had a rudi- mentary idea of reaction mechanisms and of the transition state. The attached diagram from the “Comparative View” (p. 193) shows his interpreta- tion of the interaction of iron (I) and hydrochloric acid.He thought like many of his contemporaries that all acids contained oxygen and he represented a molecule of hydrochloric acid as BdD where B represents the unknown “basis” of the acid. The attraction between B and oxygen had to be strong because the latter had never been obtained from the acid. When iron is placed in hydrochloric acid it attracts oxygen from B which owing to its great affinity for that element simultaneously removes it from water (Id) so that no gas other than hydrogen is evolved. Bd and IdD (calx of iron) then unite to form iron chloride. The numbers refer to arbitrary force constants which he used to illustrate his argument. In some respects Higgins’s ideas were ahead of his time but they made little impression on his con-temporaries.With our present knowledge we are in a better position to appreciate them. I am indebted to Professor J. R. Partington for most helpful advice. Yours faithfully Department of Chemistry T. S. WHEELER. University College May 19th 1959. Dublin. Verkade Proc. Chem. SOC.,1958,208; Green J. Roy. Inst. Chem. 1958 83,522 524; Brown J. Chem. Educ. 1959 36 109. See Alembic Club Reprints No. 21 and Ann. Chim. 1858 53 469. Couper used first dotted and later continuous lines. Partington “A Short History of Chemistry,” MacMillan London 3rd edn. 1957 p. 166; Wheeler Endeavour 1952 11 47; Nature 1955 176 8. PROCEEDINGS COMMUNICATIONS u Denaturation ” of a Synthetic Polyampholyte By M. L. BHASKARA IiAo and $ANTI R.PALIT (INDIAN ASSOCIATION FOR THE CULTIVATION OF SCIENCE 32) CALCUTTA DURING study of synthetic polyampholytes we a observed a co-polymer of aminostyrene and meth- acrylic acid to exhibit behaviour similar to denatura- tied of native proteins. The convenient criterion followed was the insolubilisation of the polyam- pholyte which had a weight-average molecular weight of 3 x lo5 was almost neutral and had carboxy- and amino-groups in almost equal pro- portions about two-thirds of the former being present as sodium salt. The ampholyte solution on acidification to below pH 3 remained clear for a long time and then the whole polymer was suddenly thrown out of solution. The viscosity of the solution meantime remained practically constant and increased only near the point of precipitation evidently because of hetero-geneity.The freshly precipitated polymer was easily redissolved in alkali but became increasingly in- soluble with time until it was eventually insoluble. It appears that this insolubilisation occurs stepwise the first step being reversible; such stepwise denatura- tion2y3 is also often observed with proteins. The time of precipitation was practically inde- pendent of concentration of polyampholyte and decreased with pH. Some experimental results are represented in the Figure. It will be observed that the reciprocal of time of precipitation is almost propor- tional to the acid concentration; increase of tempera- ture decreased the time of precipitation.The reaction can be considered to be slow replace- ment of some bound sodium by hydrogen and pre- cipitation assumed to occur when a definite fraction of the bound sodium is replaced. It is then evident (Figure) that the reaction is unimolecular with respect to ampholyte and bimolecular with respect to hydrogen-ion concentration. Calculated on this basis the energy of activation is 21 kcaI./mole. The mechanism seems to comprise two steps ..CO,Na. .C02-. . + H+ + . .CO,Na. .CO,H. . (1) ..CO,Na.. C02H. . + H+ + ..C02H . .C02H.. (2) where (1) is a rapidly attained equilibrium and is displaced to the left and (2) is a slow reaction. The addition of neutral salts hastens precipitation but probably has little direct effect on the precipitation phenomena; their catalytic action is probably due to the decrease they cause in pH.The analogy with precipitation of proteins extends to the effect of organic solvents e.g. alcohol and acetone which are known to precipitate and de- nature proteins. On addition of alcohol or acetone the polyampholyte is precipitated after a time lag and is slowly insolubilised as with addition of acid. Rise of temperature also hastens precipitation. It is likely that the irreversible insolubilisation is due to inter- molecular salt formation but the precipitation and insolubilisation by addition of organic solvents indicate that solvation also plays a role. 0.02 0-0/ 0 0.5 1.0 1.5 X Polyamplzolyte concentrations 8 0-05 0.028 0 0.007 g.11.t = Time of precipitation in minutes; x = concentration of hydrochloric acid in g.equiv.11. Evaporating the solution and drying the ampholyte renders the residue insoluble in acid and alkali. X-ray examination shows that the denatured ampho- lyte has a crystallinity similar to that of fibrous proteins. The degree of crystallinity of the denatured polymer increases at high temperatures during several hours. A similar treatment increases the degree of crystallinity of some polypeptides4 and isotactic polymer^.^ A copolymer of aininostyrene and maleic acid behaves similarly except that its ampholyte shows an extra range of precipitation near the isoelectric point which lies near pH 6. More work is in progress. (Received April 14th 1959.) Neurath Greenstein htnam and Erickson Chem.Rev. 1944 34 157. Linderstrom-Lang Cold Spring Harbor Symp. 1950 14 117 121. a Kauzamann et al. J. Amer. Chem. SOC.,1953 75 5139 5154 5157 5167. a Bamford Hanby and Happey Proc. ROY.SOC.,1951 A 206 407. Miller Mills Small Turner-Jones and Wood Chem. and Znd. 1958 41 1323. AUGUST1959 223 A Polyampholyte with ‘‘Built-in Dye ” By M. L. BHASKARA R. PALIT RAOand SANTX ASSOCIATION OF (INDIAN FOR THE CULTIVATION SCIENCE,CALCUTTA32) IN the preceding communication we reported the delayed precipitation and subsequent insolubilisa- tion in acid solution of a copolymer of amino-styrene and methacrylic acid. The Bz-amino-group of this polyampholyte can be diazotised and coupled to yield bright azo-dyes which constitute poly- electrolytesi with built-in dye.This communication deals with the insolubilisation and light-absorbing properties of a polymer-dye obtained by coupling the diazotised polyampholyte with 3-hydroxy-naphthalene-2,7-disulphonicacid. The polymer-dye is soluble in acid and in alkali. However if the diazotisation is incomplete leaving a polyampholyte the dye can be precipitated by addition of acid and this precipitation occurs after a time lag as in the case of the parent polyampholyte. Further the precipitate cannot be dissolved in alkali. So we conclude that this insolubilisation is essentially the same process as that of insolubilisation of the parent ampholyte viz. akin to the denaturation of proteins except that insolubilisation after precipita- tion is very rapid in this case.In the dye-polymer a large number of dye units are attached to the polymer chain by non-conjugative bonds which results in many single chromophoric systems; these are expected to be independent of each other in light absorption characteristics.l The carboxylic and sulphonic acid groups of the hypo- thetical monomeric dye units have the usual functions of auxochromes to render the polymer water-soluble and to intensify the colour. Fig. 1 records the optical density of the polymeric dye solution in the visible spectrum. At higher concentrations a new absorption peak appears in the near-ultraviolet region; this is probably an indication of constitu- tional changes in the dye molecule caused by mutual interaction as in metachromacy.2 The spectral characteristics of the polymer-dye solutions are little affected by changes of pH.How- ever the solutions show wide deviation from Beer-Lambert’s law as shown in Fig. 2. The con- tinuous decrease in light absorption with increasing concentration of dye is comparable to the self- quenching of fluorescence. MetachromacyS seems to be a kindred phenomena. Evidently the light-Piper and Brode J. Amer. Chem. SOC.,1935 57 137. Holmes Slain Technology,1926 1 116. a Levine and Schubert J. Amer. Chem. Soc. 1952,74 91. 400 440 480 520 56 Wove length (mp) FIG.1. A 0.016;By0-0632; C,0.1896; D 0.316 g.12. 0 0-1 0.2 0.s Concn.(g/l) FIG.2. Plot against concentration (g.11.) of optical density at 490 mp divided by concentration.absorption behaviour is complicated by the complex dissociation equilibrium of the polyelectrolyte and its micellar size. (Received April 14th 1959.) PROCEEDINGS Echitamine By A. J. BIRCH,H. F. HODSON, and G. F. SMITH (DEPARTMENT OF CHEMISTRY THEUNIVERSITY M.4NCHESTER PUBLICATION by Govindachari and Rajappal of their investigation of echitamine chloride C22H2,0,N,Cl the alkaloid of Alstonia scholaris prompts us to present some of our findings,2 which in 1957 led us to propose3 partial structure (I) for the alkaloid. The main difference between Govindachari and Rajappa's results and ours lies in their report of the absence of C-methyl in echitamine chloride.Kuhn- Roth oxidations carried out in two microanalytical laboratories gave an average of 2.6% (calc. for one C-methyl 3.6%) and we found that ozonolysis of the chloride gave a 25 % yield of acetaldehyde. Basification of aqueous echitamine chloride gave \ N-CH2-C=CHMe H Me CH;CH -CH2Me H Me a quantitative yield of an amorphous base A C22H2,0,N2 of uncertain structure reconverted into echitamine chloride by aqueous hydrochloric acid. In the presence of platinic oxide in ethanol the base A takes up 1 mol. of hydrogen giving in high yield a crystalline tertiary base B C22H2,03N2 double m.p. 154-159" and 185-187" pK 5-5 in 60% aqueous ethanol Amax. 2480 (log E 3-91) and 3090 (log E 2.55) in ethanol changing to 2380 (log E 3-85) and 2970 ,& (log E 3.45) in ethanolic hydrochloric acid.Contrary to the report by the Indian workers,l we found it impossible to hydrogenate echitamine chloride itself in ethan01;~ in glacial acetic acid containing some hydrochloric acid and with Adams catalyst the alkaloid takes up 5-6 mol. of hydrogen slowly and continuously to produce an amorphous base showing no selective ultraviolet absorption. Base B takes up one further mol. of hydrogen in glacial acetic acid over Adams catalyst leading in variable yield (-60%) to a base C C2,H,,0,N2 double m.p. Govindachari and Rajappa Proceedings 1959 134. Hodson Ph.D. Thesis Manchester 1957. 1 3) 115-120" and 160-163" pK 5.5 in 60 % aqueous ethanol whose ultraviolet absorption is almost identical with that of base B.Whereas base B gives a 46% yield of acetaldehyde on ozonolysis base C gives none but gives a mixture of acetic and a-methylbutyric acid by the modified Kuhn-Roth meth~d;~ a quantitative Kuhn-Roth determination with base C gave C-Me 6.2% (calc. for two C-Me 7.8 %). Echitamine chloride is converted by sodium in dry liquid ammonia into a mixture of bases from which fractions showing an ultraviolet spectrum charac- teristic of 2,3-disubstituted indoles can be obtained. All the above results are best interpreted in terms of partial structure (I) for echitamine chloride (11) for base B and (111) for base C. Distillation of base B with zinc dust gave a crystal- line base Cl3HI2N2 m.p. 124-126" identical with base (IV) m.p.124-126" obtained by the addition of methyl- li thium to 1 '-met h y lp yrr010(2' 3'- 3,4) -quinoline,6 followed by oxidation with permangan- ate. This base forms a picrate m.p. 241" with previous sintering and is probably closely related to the non-crystalline base [picrate m.p. 253 O (de-camp.)] described which Govindachari and Raj appal obtained by selenium-dehydrogenation of their tertiary base. We thank Dr. L. J. Webb C.S.I.R.O. (Phyto- chemical Survey) for supplying Alstonia scholaris bark and the Schunck Fund of the University of Manchester for a grant (to H.F.H.). (Received May 8th 1959.) RCsumC des Communications Tome 11 p. 207 XVIth Internat. Congr. Pure Appl. Chem. Paris 1957. Resistance of a quaternary allylamine system to hydrogenolysis is unusual but there are precedents such as mavacurin (Bickel Schmid and Karrer Helv.Chim. Ada 1955 38 649). Garbers Schmid and Karrer ibid. 1954 37 1336. Eiter and Nagy Monatsh. 1949 80 607. AUGUST 1959 225 The Formation of Substituted Ethylenediamines from Reactions of Tertiary Amines with t-Butoxy-radicals By H. B. HENBEST and R. PATTON (THEQUEEN'S OF BELFAST) UNIVERSITY RALEY,RUST,and VAUGHAN~ have shown that di-t-butyl peroxide decomposes thermally by a first- order process the rates of decomposition being very similar in the gas phase and in various solvents. t-Butoxy-radicals are first formed ;these can further decompose to methyl radicals and acetone or can react with other molecules present.2 It has now been found that NN'-dimethyl-NN'- diphenylethylenediamine (I), m.p.and mixed m.p. 47" is formed when the peroxide is decomposed in solution in dimethylaniline. t-Butyl alcohol is also formed and it is suggested that the reaction involves the abstraction of hydrogen from the tertiary amine by alkoxyl radicals thereby generating N-methyl- (Me,C.O.) -f 2MeJ-O. Ph-NMe + Me,C.O. PhMeNCH,. + Me C-OH J. PhMeNCH,CH,-NPhMe (I) anilinometh yl radicals that dimerise. On reaction between the peroxide and di-methylaniline (1 :5 mol. ratio) at 135" the yields of diamine (I) and t-butyl alcohol were respectively 28% and 92% based on initial peroxide and the above equations. A second crystalline not yet identified amine product is formed in smaller amount; the remainder of the amine product is non-crystalline.A similar reaction occurs when the peroxide is decomposed in solution in NN-dimethyl-p-toluidine; NN'-dimethyl-NN'-di-p-tolylethylene diamine m.p. and mixed m.p. 80-Sl" is isolated in 33% yield. The authors gratefully acknowledge financial support from the U.S. Army through its European Research Office (Contract Number DA-91-508-EUC-389). (Received May 13th 1959.) Raley Rust and Vaughan J. Amer. Chem. SOC.,1948 70 1336. Walling "Free Radicals in Solution," Wiley and Sons Inc. New York 1957 p. 443. Dialkylamido-derivatives of Titanium Zirconium and Tantalum By D. C. BRADLEY and I. M. THOMAS (BIRKBECK w.c.1) COLLEGE MALETST.LONDON INsynthesising organometallic compounds contain- ing metal-nitrogen bonds we have explored the scope of reactions involving metal chlorides and lithium dialkylamides as indicated by the general equation (1) -f MCI + xLiNR M(NR,) + xLiCl . . . (1) The metal chloride was added to an ethereal solution of the lithium dialkylamide the ether evaporated and replaced by light petroleum and the system heated at ca. 60" for about 2 hours. After filtration and removal of solvent from the filtrate the new dialkyl- amido-metal compound was distilled off in vacuo. Tetrakisdimethylamidotitanium Ti(NMe2) was ob- tained in 85 % yield as a volatile liquid (b.p. 50"/0.05 mm.) which was readily hydrolysed with liberation of dimethylamine and formation of metal oxide (hydrated).The zirconium analogue Zr(NMe,) was a solid (m.p. 60") which could be distilled (b.p. 75 "lo.1 mm.). Pentakisdimethylamidotantalum Ta(NMe& was a solid which sublimed in vacuo (1OO0/O.05 mm.). The tetrakisdiethylamido-deriva-tives of titanium and zirconium were liquids which distilled at llOo/O-l mm. and 120"/0.1 mm. respec- tively. However in attempting to prepare pentakis- diethylamidotantalum we obtained a volatile product (b.p. 130"/0-1 mm.) which appears to be substantially trisdiethylamidoethylimidotantalurn Ta(NEt)(NEt,),. The quinquevalency of the tantalum in this compound was established by quantitative ethanolysis to tantalum pentaethoxide whilst con- trolled reaction with propan-2-01 (at 25") and then butan-1-01 (at the b.p.) proved the presence of both diethylamido- and ethylimido-groups.It was also clear that the ethylimido-group is more resistant to alcoholysis than the diethylamido-groups and this coupled with the volatility of the compound suggests that the ethylimido-group is bound by a tantalum- nitrogen double bond (Ta-NEt) rather than by bridging (Ta-N-Ta) which would result in poly- merisation. Preliminary experiments showed that aminolysis can occur M(NR,) + xR,NH -f M(NR'& + xR,NH (2) For example tetrakisdiethylamidotitanium was con- verted quantitatively into tetrakispiperidinotitanium Ti(NC5H1,,) (m.p. 60"; b.p. lSOo/O.l mm.) and similarly from the analogous zirconium compound the tetrakispiperidino-derivativeZr(NC5Hl,) (m.p.60"; b.p. 190"/0.2 mm.) was obtained in 62% yield. Nevertheless it appears that steric effects may exert a controlling influence as for example in the reactions involving tetrakisdimethylamidotitanium and 2-methyl- or 2,6-dimethyl-piperidine which gave res- pectively Ti(NMe,)(NC,H,Me) (b.p. 160"/0-1mm.) and Ti(NMe&,(NC,H,Me& (b.p. 120-125"/0~1 mm.) after being heated for 4-5 days at the boiling point of the substituted piperidine. PROCEEDINGS Details of these reactions and others involving other transition metals will be reported later. This research was supported by the Wright Air Develop-ment Center of the Air Research and Development Command U.S.A.F.,through its European Office. (Received May 14th 1959.) Kinetics and Mechanism of Reaction of (-)-4-Methyldiphenylmethyl (-)-l-Phenylallyl and 3a,5 or-CyclocholestandP-yl [14C]Acetatein Acetic Acid By Y.POCKER (DEPARTMENT OF CHEMISTRY UNIWRSITY COLLEGE LONDON) UNDER acidic conditions derivatives of 4-methyldi- phenylmethanol undergo alkyl-oxygen i0nisation.l By heating (-)-4-methyldiphenylmethyl [carboxy-14C]acetate in acetic acid of normal isotopic abund- ance it has now been possible to show that the rates of racemisation and exchange are the same and that perchloric acid is a powerful catalyst which affects equally the racemisation and the exchange.The rate of racemisation becomes proportional to Hammett's acidity function ho.2 The slope of log kl against -Ho is 1.05. These results are taken to indicate that an ionisation mechanism is operative.By heating (-)-l-phenylallyl [14C]acetate in acetic acid of normal isotopic abundance concurrent ex- change racemisation and rearrangement take place. Perchloric acid is a powerful catalyst for all three processes and the rates are proportional to h,. The slope of log k against -H is 1 * 1. The rates of dilu-tion of tracer in the ester mixture and the correspond- ing rates of racemisation are almost equal but are ca. 50% higher than the rate of rearrangement to 3-phenylallyl acetate. These results again suggest an ionisation mechanism. As additional mechanistic evidence one finds:(a) that l-phenylallyl [14C]acetate recovered after interruption of the rearrangement has partially exchanged its acetate group with that of acetic acid solvent and that this exchange plus the isomerisation account for practically all the loss of tracer in the mixture of esters; (b) that 3-phenylallyl acetate recovered after the complete rearrangement of l-phenylallyl acetate has practically no tracer; and (c) that the exchange of acetate between 3-phenyl- ally1 [14C]acetate and acetic acid of normal abund- ance is slower than the rates of both acetate exchange and rearrangement of (-)-1 -phenylallyl [14C]acetate.The simplest interpretation of these results is that the slow step for both racemisation and symmetrical ex- Davies Kenyon Lyons and Rohan,J. 1954 3474. Long and Paul Chem. Rev. 1957,57 993. change is the formation of an intermediate which reacts with an acetic acid molecule at either of its two available positions (3- and I-) to give the rearranged product (3-phenylallyl acetate) of practically normal abundance or to regenerate l-phenylallyl acetate with loss of tracer.One estimates that in the absence of added nucleophilic electrolytes ca. one-third of the intermediate returns after exchange with solvent while two-thirds proceed to exchange with solvent and produce the 3-isomer so that the rates of racemi-sation or exchange are ca. 1-5 times the rate of rearrangement. Similar studies with 3a 5a-cyclocholestan-6~-yl [14C]acetate indicate that the rate of loss of tracer is ca. ten times faster than the rate of rearrangement to the 3/3-isomer. The simplest interpretation of these results is that both exchange and rearrangement proceed through a common intermediate which reacts with acetic acid to regenerate the cyclochol- est-an-6p-yl acetate with loss of tracer ca.nine times faste? than it reacts with acetic acid to produce the rearranged cholestan-3/3-yl acetate. Acetic acid as solvent can by hydrogen-bonding assist ionisation without necessarily being able to sustain the dissociation of two oppositely charged particles which is largely precluded in a medium of dielectric constant 6- 13. Indeed Bjerrum's definition4 would classify a pair of counter-ions at any separa- tion up to 40 A in acetic acid as an ion-pair. The results recorded above are in themselves consistent with a free carbonium-ion intermediate but they do not require it.Their only requirement is that racemi- sation and exchange should proceed through a common intermediate which has a sufficient degree of bond heterolysis to ensure that their respective energy barriers are the same. (Received June 3t-d 1959.) Kosower and Winstein J. Amer. Chem. Soc. 1956,78 4347,4354. Bjerrum Kgl. danske Vidensk. Selskab Mat.-$3. Medd. 1926 7 No. 9; see however Fuoss J. Amer. Chem. Soc. 1958 80 5059. AUGUST 1959 227 Displacement Reactions of Optically Active Phosphorus Compounds By M. GREEN and R. F. HUDSON (QUEEN MILE E.l) MARYCOLLEGE ENDROAD,LONDON THErecent development of convenient methods for resolving phosphorus compounds containing re-placeable groups into their optical isomers1 has opened the way to detailed investigations of the stereochemical changes accompanying substitution.The presence of the P=O group in the compounds so far resolved increases the difficulties of these studies as racemisation readily occurs particularly in prototropic solvents. We have not yet succeeded in developing a cycle of processes which establishes unambiguously the stereochemical course of a particular substitution. In view of the current interest in this and similar problems the following preliminary observations are presented. The reaction of (+)-methyl a-naphthyl methylphosphonate aD20+ 44",with one equivalent of sodium isopropoxide in propan-2-01 gave (-)-isopropyl methyl methylphosphonate xD2O -10.8".Further treatment with sodium isopro- poxide led to racemisation. If similar configurational changes are assumed for these two reactions i.e. for displacements involving similar groups OR- these observations show that both reactions proceed with inversion of configuration. The following series of reactions starting with (+)-S-benzyl 3-phenanthryl- methylphosphinothiolate (I) also show that pre-dominant inversion occurs in some of the displace- ments. The formation of the phosphinate (IV) in two optically active forms shows that inversion must occur in one or all of the processes I1 +111 I1 -+ IVB III -+ IVC. The considerable loss of optical purity is due mainly to the high reactivity of the fluoride (111) which racemises very rapidly in the presence of a trace of ammonium fluoride.Con-sideration of the series of processes I -+IVA I +11 I1 -+ IVB leads to a similar conclusion the loss of optical purity probably occurring mainly in the chlorination stage in this case. The products of these reactions were not isolated but complete conversion was assumed in each stage and all the activity measurements were made in benzene. Q R-P-SBz he (I) + I7O c3 R-f-OMe 0 Me (IVA) + 6i0 I 2 9 8 -R-PCL -R-PF he ile (a) + 55O (m)-28.1 .c3 l3 R-7-OMe R-7-OMe 9 9 Me Me (IVB) -32.7' (IVC) I-23O Reagents 1 CI in C,H at 0". 2 NH,F in acetone. 3 NaOMe in C,H,. Numerals under formula are ctD40. Inversion of configuration suggests that the transi- tion state adopts a bipyramidal (sp3d hybridised) transition state as predicted theoretically with the reacting groups and phosphorus atom collinear.(Received May 28th 1959.) Coyne McEwan and Van der Werf J. Amer. Chem. SOC.,1956,78 3061 ;Aaron and Miller ibid. p. 3538; Green and Hudson Proc. Chem. SOC., 1957 323. Alkyltitanium Trihalides RTiXs By C. E. H. BAWNand J. GLADSTONE (THEUNIVERSITY, LIVERPOOL) A KNOWLEDGE of the reactions of titanium alkyls is of importance to an understanding of the nature of the initiation of Zeigler-type polymerisation. Numer- ous unsuccessful attempts1 to prepare titanium alkyls led to the assumption that a stable bond between titanium and alkyl groups was not possible. Recent patents however by Farbwerke Hoechst A.G.2 describe the preparation of the alkyls RTiX and RR'TiX (X = Halogen preferably chlorine; R and R' = alkyl) by reaction of aluminium alkyls with Cotton Chem.Rev. 1955 55 551. titanium tetrachloride under carefully controlled con- ditions. Independently we have been investigating the formation of metal alkyls by the reaction of lead tetra-alkyls with metallic salts,3 and Mitchell' showed that an alkyltitanium trichloride was formed on reaction of a tetra-alkyl-lead with titanium tetra- chloride at low temperatures. We now report the further use of this reaction for the preparation of the monoalkyltitanium trihalides. Titanium tetrachloride in 2 1 molar excess react a Farbwerke Hoechst A.G. Belgian Patent 553,477.Bawn and Whitby Furuduy SOC.Discuss. 1947 1 228 and unpublished work. F. W. Mitchell Ph.D. Thesis Liverpool 1957. rapidly with tetra-ethyl-lead at -80" in vacuo in heptane or toluene solution with formation of a dark red-brown precipitate. On hydrolysis at -80" with 3 1 (v/v) ethyl alcohol-water and warming of room temperature an almost theoretical yield to ethane was obtained. Only a small amount of ter- valent titanium resulted and the lead-containing pro- duct was shown by analysis to be triethyl-lead chloride in nearly theoretical yield. The reaction can therefore be summarised as Et,Pb + TiCl = Et,PbCl + EtTiC1,. The same general features were observed when the tetraethyl-lead was in excess. If the reactant mixture at -go" was allowed to warm slowly to room temperature some decomposi- tion of the alkyltitanium compound was observed with evolution of ethane and ethyl chloride and formation of tervalent titanium.From this mixture it was possible by vacuum-distillation to isolate a violet solid (yield 40-50%) which was shown by analysis for titanium and chlorine to have the formula C2H,TiCl,. The solid melted at room temperature to a red liquid and was soluble in both aromatic and aliphatic solvents to give clear red solutions. The alkyl in dilute solution was reasonably stable -a 0.005h1-solution in toluene showed 20% decom-position as shown by determination of ter-valent titanium and gas evolution in 5 hours at 60-70". In the pure state the alkyl decomposed within 24 hours at room temperature to give tervalent titanium ethane and n-butane.The titanium alkyl with oxygen readily gave the PROCEEDINGS monoethoxy-derivative:EtTiC1 + &02 =EtOTiCl, which on hydrolysis gave a primary alcohol and quadrivalent titanium. This was confirmed by chem- ical analysis and measurements of oxygen uptake. No reaction with carbon dioxide was observed at room temperature in agreement with the results. obtained by Herman and Nelson5 for phenyltitanium tri-isopropoxide. In similar reaction conditions the analogous ethyltitanium tribromide and methyltitanium tri- chloride may be prepared. Nuclear magnetic resonance spectroscopy shows clearly the presence of" the ethyl group in the trichloride. The ethyltitanium trichloride was catalytically de- composed by tetraethyl-lead and by triethyl-lead chloride and this observation explains why no titanium alkyl could be obtained from reactants con- taining excess of tetraethyl-lead on warming to room temperature.The isolation of the titanium alkyl in the presence of excess of titanium tetrachloride was no doubt due to the strong complex-formation by the triethyl-lead chloride with excess of titanium tetrachloride this complex being insoluble in the reaction media. In the presence of excess of lead alkyl the alkyl- titanium trichloride is a very efficient catalyst for the polymerisation of ethylene at temperatures of -5 ' upwards. The polymer on recrystallisation from decalin had m.p. 127-135".The system was not efficient for the polymerisation of propene at room temperature and atmospheric pressure. (Received May 28th 1959.) Herman and Nelson J. Amer. Chem. Soc. 1953 75 3877. The Conversion of a 14a-into a 14/3-Hydroxy-group in the Androstane Series By FRANZSONDHEWIER BURSTEIN and SUMNJZR (DANIEL SIEFF RESEARCH INSTITUTE ?kJ? WEIZMANN INSTITUTE OF SCIENCE REHOVOTH, ISRAEL) NEARLY all the naturally occurring cardioactive steroidal lactones have a 14~-hydroxy-substituent but only one method for bringing about 14p-hydroxylation has been described so far.l We now report an easy synthesis of androstan- 14/3-01 deriva- tives which involves the conversion of a 14a- into the corresponding 14~-hydroxy-compounds. The former are available in one step from simple andro- stane derivatives by both chemical2 and microbio- logical means.3 3p-Acetoxy- 14~- hydroxyandrostan- 17- one (I), readily prepared2 from dehydroepiandrosterone acetate was dehydrated with potassium hydrogen sulphate in refluxing acetic anhydride to 3-acetoxy- androst-14-en-17-one2(11) in 70% yield.This with perbenzoic acid in chloroform gave a 70 % of yield of the epoxide (111) m.p. 159-160" [a] + 105" (all rotations in chloroform) attack being as expected from the same side as it is known to be for hydrogen.2 Refluxing the epoxide with sodium carbonate in aqueous t-butyl alcohol for 1 hour resulted in smooth rearrangement and gave 75 % of 3p-acetoxy- 14/3- hydroxyandrost-15-en-17-0ne(IV) m.p.153-1 55"+ [a] + 120" Amax. 213 mp (E 13,500) (in ethanol) Plattner Ruzicka Heusser et al. Helv. Chim. Acra 1946 29 942; 1947 30 385 395. St. Andrk MacPhillamy Nelson Shabica and Scholz J. Amer. Chem. SOC.,1952 74 5506. Eppsteh ibid. 1958 80 3382. AUGUST1959 229 Ample analogy for this type of rearrangement of py-epoxy-ketones exist^.^ For comparison 3~-hydroxy-14~-androst-15-en-17-one (V) [the 14- deoxy-analogue of (IV) prepared from the ketone (11) by treatment with potassium hydroxide in refluxing aqueous t- butyl alcohol5] showed Amax. AcO 230 mp (E 7200). The anomalous ultraviolet spectra of d15-17-ketones of this type will be discussed in the full paper. Finally hydrogenation of the ketone (IV) in ethanol over palladium-charcoal gave 80% of 3/3-acetoxy- 14p- hydroxyandrostan- 17-one (VI) m.p.181-182" [a] + 13". The structure of this substance (and consequently of the preceding ones) follows from the fact that it differs from the starting material (I) is unchanged on treatment with acetic anhydride and pyridine and is converted into the unsaturated compound (11) by potassium hydrogen sulphate in boiling acetic anhydride. (v) Ac We are grateful to the U.S. National Institutes of Health for a research grant (No. H-2476) and to Syntex S.A. Mexico City for a gift of the steroid starting material. (Received June 2nd 1 958.) Cf. Djerassi Batres Velasco and Rosenkranz ibid. 1952 74 1712. Cf.Johnson and Johns ibid. 1957 79 2005. A New Synthesis of Dichlorocarbene By W.M. WAGNER AMSTERDAM (SHELLINTERNATIONALE MAATSCHAPPY ~KONINKLLJI~E/SHELL-LABORATORIUM RESEARCH N.V.)] PREVIOUS syntheses of dichlorocarbene involve the reaction of compounds CCI,X (X = H or C0,R) with a base (e.g. ButO-) in non-protonic media:lS2 ccf,x + ButO--t eel + Butox . . (,) CCI,-+ CCI + CI-. . . (2) Proton donors (YH) interfere with this process by reaction with CCl CCI; + YH+ CHCI + Y-. . . (3) The known thermal decarboxylation of sodium trichloroacetate in protonic solvent^,^ which is also believed to proceed via the CCl; anion ccI,-co,-+ccI,+ co . . . (4) followed by reaction 3 may therefore be expected to yield CCI (reaction 2) if a non-protonic solvent is employed. Refluxing a 15% solution of sodium trichloro- acetate in 1 ,Zdimethoxyethane gave a nearly quanti- tative yield of sodium chloride; the progress of the reaction may conveniently be followed by titration of chloride ion in representative aliquot parts.When the decarboxylation is carried out in the presence of CC1,-acceptors the expected addition products are formed; they were identified by comparison of physical constants and infrared spectra of authentic ~amp1es.l~~ Thus 40 g. of sodium trichloroacetate 70 ml. of 1,2-dirnethoxyethane and 105 g. of cyclohexene after 22 hours' refluxing gave 23-1 g. (65% based on the acetate) of pure 7,7-dichloronorcarane. A smaller excess of acceptor still gave reasonable yields; for instance from 40 g. of acetate 50 ml. of glycol ether and 40 g.of cyclohexene refluxed for 7 hours 47 % of the adduct was obtained. When 40 g. of acetate 75 ml. of the ether and 100 g. of cycloheptatriene were stirred at 80" for 10 hours the yield was 17-5 g. (46.5%) of pure 8,8-di- chlorobicyclo[5,1,O]octa-2,4-diene. An attractive feature of the present method may well be the possibility to maintain essentially neutral conditions throughout the reaction. (Received June Sth 1959.) Doering and Hoffmann J. Amer. Chem. SOC.,1954,76 6162. a Parham and Loew J. Org. Chem. 1958,23 1705. Verhoek J. Amer. Chem. SOC.,1934,56 571. * ter Borg and Bickel Proc. Chem. SOC.,1958 283. PROCEEDINGS ~~ ~~~~~~ ~~ New Elastomers Containing Fluorine By D. A. BARR,R. N. HASZELDINE, and C.J. WILLIS (THEUNIVERSITY AND CAMBRIDGE THEMANCHESTER OF SCIENCE MANCHESTER, COLLEGE AND TECHNOLOGY 1) ITwas shown earlier1 that the reaction of trifluoro- nitrosomethane with tetrafluoroethylene gave quantitatively two products an oxazetidine (I) and a 1 :1 copolymer (XI). The N 0 group acts like C:C in copolymerisation with the olefin and the copoly- mer is strictly 1 :1. The copolymer reported as a result of the early experiments ranged from viscous oil to a gel with a molecular weight much above 7000; further investigation has shown that use of carefully purified monomers a reactant ratio close Olefn Oxazetidine -CF :CFCl CF,.N.O.CFCl*CF CF :CCl CF,*N*O*CCl,*dF, - peduoromethylcyclohexane and other fluorocarbon solvents.Viscosity measurements indicate a mole-cular weight for the elastomer of 150,000-200,000. Other co-monomers may be used. Chlorotrifluoro- ethylene is similar to tetrafluoroethylene. Trifluoro- ethylene differs in that an elastomer can be obtained without rigorous purification of reactants; the hydrogen in the molecule (111) enables cross-linking to be effected by peroxides amines etc. and imparts greater solubility in conventional solvents such as Polymer [.N(CF,)*O*CF,CFCl*] [*N(CF3)*O*CF,*CCl,-] CHF:CF CF3*N*OCHF*CF2 [.N(CF3)*O°CF,*CHF.] plus [*N(CF,)*O*CHF*CF,.] , CF3CF:CF CF,*N*OCF(CFa*CF2 [*N(CFJ*O*CF,CF(CF3).] 90% to 1 :1 and temperatures of 0" or below enables an elastomer to be obtained directly and quantitatively.The white opaque elastomer the first to be reported with the -N-0-C-C- backbone has good thermal stability at 200" in presence of air and is apparently unaffected over long periods at 180". At higher temperatures pyrolysis sets in to give the compounds CF,-N CF2 and carbonyl fluoride as noted ear1ier.l A feature of particular interest with this new elastomer is its flexibility at -30° and it is evident that rotation of the chain about the N-0 bond and the size of the trifluoromethyl side-chain effectively prevent crystallisation (cf. polytetrafluoroethylene which is highly crystalline). The elastomer is insoluble in all common solvents as was the shorter-chain material but is soluble in 90 % acetone. Other fluoro-olefins e.g.,CF2:CCl, C3FB have been copolymerised with the nitroso-compound.The structure of the products from some of these unsymmetrical olefins has been determined as in the annexed Table. It will be noted that like the polymer the oxazeti- dine (obtained either concurrently or under different conditions of temperature and pressure) has exclu- sively or predominantly one structure but that the direction of addition of the NO group to the olefin is different from that in the polymer. The elastomers referred to above represent a new structural class and their solvent resistance and low- temperature characteristics should make them useful in a number of applications. (Received May 28th 1959.) Barr and Haszeldine J. 1955 1881; 1956 3416; Nature 1955 175 991.AUGUST 1959 23 1 Molecular Structure of a Macrocyclic Polyacetylene By W. K. GRANT and J. C. SPEAKMAN DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) THEcrystalline hydrocarbon prepared by the oxida- density to be corrected showing there to be four tive coupling of o-diethynylbenzene was originally molecules present. Thereafter the interpretation of suspected1 of having a triangular molecule of the main features of the hol diffraction pattern formula C3,,H12.X-Ray measurements of the unit- proved straightforward leading us to the preliminary cell dimensions2 gave some support to this formula- electron-density projection reproduced here which tion in so far as they led with the assumption of two conclusively confirms structure (I) with its bowed diacetylenic chains.This map is an idealised one since it is based on reflexions having even values of (;th + 2) only and thus possesses enhanced symmetry. Though these _-._ . . .... t z ..-molecules per cell to a density in reasonable agree- even reflexions are generally much the more intense ment with the then accepted experimental value. odd ones also occur especially at high orders. This However we found it impossible to reconcile the tri- implies that exact identity recurs for instance only angular molecule with the details of the diffraction at every second molecule along the x-direction pattern. Further chemical evidence3 has recently (. .A,B,A,B,A. .). However the difference between established that the hydrocarbon has a C, molecule the aspects presented by molecules A and B must be with formula (I).To accommodate three such mole- slight since the "averaged" molecule shown here is cules in the cell would be difficult ;but the availability so neatly defined. of better crystals has enabled an error in the original Further work is in progress. (Received,June 9th 1959.) Eglinton and Galbraith Proc. Chem.,Soc. 1957 350. a Viz.,a = 28-3 b = 3.87 c = 11.5 A orthorhombic. Behr Eglinton and Raphael Chem. and Ind. 1959 699. A New Route to Heterocyclic Phosphorus Compounds By I. G. M. CAMPBELL and J. K. WAY (THEUNIVERSITY, SOUTHAMPTON) INTRAMOLECULAR cyclisation of suitably substituted Freedman3 were unable to obtain the phospha- arsonic or arsinic acids has been widely used as a fluorene derivative by cyclodehydration of 2-bi-method of preparing heterocyclic arsenic com-phenylylphosphonic acid and had recourse to a pounds,l and to a smaller extent the same process specific reduction of di-o-bromophenylphosphinic is useful in the antimony series.2 So far however acid in order to close the five-membered ring.Only cyclic phosphorus compounds have not been ob- two other compounds of this type are known tained by this method. For example Doak and 9-phenyl-9-phosphafluorene obtained by interaction Aeschlimann Lees McCleland and Nicklin J. 1925 66; Campbell and Poller J. 1956 1195. * Morgan and Davies Proc. Roy. Soc. 1933 A 143 38; Campbell and Morrill J. 1955,1662. Doak and Freedman J. Org. Chem. 1956,21,238. of triphenylphosphine with phenylsodium and its oxide (11; R = H) which was formed by the reaction of phenylphosphonous chloride with 2,2'-dilithiobi- phenyl.* We now report the successful cyclisation of two phosphinic acids by the annexed route.2-Biphenylyl- phenylphosphinic acid (I; R = H) m.p. 180-181" (Found C 73.4; H 5.2. C,,H,,O,Prequires C 73.5; H 5.1 %) was obtained in 20% yield by interaction of 2-biphenylylmagnesium bromide with phenyl- phosphonous chloride followed by oxidation and the nitro-acid (I;R = NO,) m.p. 234-235" (Found C 63.3; H 4-1. C,,H,,O,NP requires C 63.7; H 4.2 %) was obtained in 25 % yield by the diazonium salt method. The acid (I; R = H) was unaffected by acetic anhydride containing 1 % of sulphuric acid at 90° or by polyphosphoric acid at 160" conditions which bring about cyclisation of the corresponding stibinic and arsinic acids respectively.Trifluoroacetic an- hydride failed to cyclise the phosphinic acid and con- centrated sulphuric acid at 100" apparently sul- phonated it. The acid chloride a viscous oil formed the anilide m.p. 202-204" and the ethyl ester m.p. 116" but did not undergo intramolecular cyclisation PROCEEDINGS under Friedel-Crafts conditions in carbon disulphide or benzene with aluminium chloride as catalyst. However cyclisation occurred when the acid was heated with excess of phosphorus pentachloride in nitrobenzene at 1 80°,and subsequent treatment with water gave 9-phenyl-9-phosphafluorene 9-oxide (II; R = H) m.p.167-168" (Found C 78-0; H 4.8. Calc. for C,~HI@P c,78.2; f-I 4-7%) in 30 % yield along with 50% of the unchanged acid. The acid (I; R = NO,) was cyclised in the same conditions though more slowly ;60% was regained and 2-nitro- 9-phenyl-9-phosphafluorene9-oxide m.p. 203 ",was obtained in 20% yield (Found C 67.0; H 4.1 . C,&f,,O,NP requires C 67.3 ; H 3.8 %). In addition to chemical evidence comparison of the infrared spectrum of the phosphinic acid (I; R = H) with that of the oxide (11; R = H) gives further proof of cyclisation. Three broad absorption bands at 1540-1750 2260-2450 and 2500-2700 cm.-l are present in the spectrum of the phosphinic acid. Absorption of this type in this region has been ascribed to the group X :0(OH),6where X = P As S or Se.The two higher-frequency bands are absent from the spectrum of the oxide but the 1540-1750 cm.? band is still present and has a sharp peak at 1595 cm.-l. The corresponding band in the nitro- oxide (II;R = NO,) is less broad (1550-1720 cm.-l) with a peak at 1590 crn.-l (Nujol mull). We thank Mews. Albright and Wilson Ltd. for a generous gift of phenylphosphonous chloride and the D.S.I.R. for a maintenance grant to J.K.W. (Received,June 5th 1959.) Wittin and Geissler. Annalen 1953 580. 44. Doak-and Freedman J. Amer. Chem. SOC.,1952 74 2884. Braunholtz Hall Mann and Sheppard J. 1959 868. Synthesis of Biflavonyls By F. C. CHEN C. T. CHANG,*M. HUNG,Y. C. LIN,and S. T. CHOONG (RESEARCH TAIWAN INSTITUTE OF CHEMISTRY ,NATIONAL UNIVERSITY TAIWAN) BAKER and his collaborators1 recently assigned a 3',8"-or 3',6"-biflavonoid structure (I) to ginkgetin isoginkgetin and sciadopitysin.This prompted us to report our recent result on the synthesis of bi- flavonyls. The only synthetic biflavonoid reported in the literature so fas as we are aware is that obtained by Mahesh and Seshadri as a by-product of the oxida- tion of acetoxyflavanone with Fenton's reagent in acid medium by dehydrogenative coupling in the 3-position. Since 1949 we have been studying the R Ginkgetin Me lsoginkgetin H Sciadopitysin Me R' Me Me Me R" H Me Me * Present address Princeton University Princeton USA. a Mahesh and Seshadri J. 1955 2503. Baker Finch Ollis and Robinson Proc. Claern. Soc. 1959 91. AUGUST1959 233 Monoffavone 3-Br-6 M.p.126" Biflavon yl 3,3"-7 M.p. 285-287 O 6-I-a 190-191 6,6"- 305-307 6-I-4'-OMe-a 183-1 84 4',4' "-(MeO) ,-6,6"- 3 1 5-320 7-1-3 168-1 69 7,7"- 3 39-34 1 7-14-0 Me-3 205-206 4',4'"-( MeO) 2-7,7 "- 340-345 187-1 88 8,8"- 312-320 8-Br-9 178-1 79 8-C1-lo 3'4-4,11 4'-1-4,11 167-168 14 1-1 42 167-1 68 39 3',3'"-4',4'"- 9 308-3 10 320-322 synthesis of halogenoflav~noids,~ hoping to prepare binuclear compounds by the Ullmann reaction. Al-most all the monohalogenoflavones and related com- pounds* have been prepared and the Ullmann reac- tion on iodo- and bromo-flavones has been employed to prepare the symmetrical biflavonyls,6 which are shown in the annexed Table. Further studies on the Chen and Chang J. 1958 146.unsymmetrical biff avonyls are being carried out. The authors are grateful to Professor T. S. Wheeler who read the typescript President S. L. Chien and Professor Y. Sebe for their encouragement and Mr. T. Ueng Mr. C. Y.Chen Miss L. S. Wang and Mr. C. T. Wang for experimental assistance. (Received June 5th 1959.) Chen and Yang J. Taiwan Pharm. ASSOC.,1951,3 39. Chen Chang Ueng Wang Choong and Kung J. Formosan Sci. 1958,12 141. Diesbach and Kramer Helv. Chim. Acta 1945 28 1399. 'I Chen and Liu J. Taiwan Pharm. ASSOC., 1953,5 53. Chen Chang and Chen J. Formosan Sci. 1958 12 151. Chen Lin Ueng and Chen ibid. 1958 12 144. lo Ruheman Ber. 1921 54 912. l1 Chen Yang Chang and Lin J. Formosan Sci. 1954 8 19. NEWS AND ANNOUNCEMENTS Anniversary Meetings 1961.-The Anniversary Meetings of the Society will be held in Liverpool during the period April 11-14th 1961.Full details will be announced in due course. The programme will include a Symposium on the Chemistry of Boron Compounds and a Symposium dealing with selected topics in the Chemistry of Natural Products. Corday-Morgan Medal and Prize for 1958.-This Award consisting of a Silver Medal and a monetary Prize of 200 Guineas is made annually to the chemist of either sex and of British Nationality who in the judgment of the Council of the Chemical Society has published during the year in question the most meritorious contribution to experimental chemistry and who has not at the date of publica- tion attained the age of thirty-six years.Copies of the rules governing the Award may be obtained from the General Secretary of the Society. Applications or recommendations in respect of the Award for the year 1958 must be received not later than December 31st 1959 and applications for the Award for 1959 are due before the end of 1960. Dexter Award in the History of Chemistry.-The Dexter Award in the History of Chemistry recently awarded by the Division of History of Chemistry of the American Chemical Society to Professor John Read will be presented before the Scientific Meeting in the Society's Rooms in Burlington House on October 15th next by Dr. S. M. Edelstein Secretary of the Division of History of Chemistry and Mr. Evans representing the Dexter Chemical Corpora- tion.The Research Fund.-The Research Fund of the Chemical Society provides grants for the assistance of research in all branches of Chemistry. About seven hundred pounds per annum is available for this purpose. Applications for grants will be con- sidered in November next and should be submitted on the appropriate form not later than Saturday November 14th 1959. Applications from Fellows will receive prior consideration. Reports on grants outstanding from previous years should be made by November 1st. Forms of application together with the regulations governing the award of grants may be obtained from the General Secretary. Local Representative.-Dr. A. S. Jones has been appointed Local Representative for Birmingham in succession to Dr.D. H. Whifen who has resigned. Birthday Honours List.-Awards to Fellows announced in the Birthday Honours List include Dr. A. C. Monkhouse lately Deputy Director Warren Spring Laboratory Department of Scientific and Industrial Research (C.B.E.); Mr. E. W. S. Press Director Chemical Inspection Ministry of Supply (C.B.E.); and Dr. J. A. B. Smith Director Hannah Dairy Research Institute (C.B.E.). International Congresses and Symposia.-The Ninth Canadian High Polymer Forum will be held at the Guild Inn Toronto Canada on October 26-28th 1959. The Programme Chairman is Dr. L. A. McLeod Polymer Corporation Ltd. Sarnia Canada. An International Congress and Exhibition on Laboratory Measurement and Automation Tech- niques in Chemistry (ILMAC) will be held in Basle Switzerland on November 10-1 5th 1959.En- quiries should be addressed to ILMAC 61 Clara- strasse Basle. A Symposium on Radioactive Isotopes in Clinical Medicine and Research organised by the 2nd Medical University Clinic will be held in Bad Gastein Austria on January 7-10th 1960. Enquiries should be addressed to Dr. Rudolf Hofer 2nd Medical University Clinic 13 Garnisongasse Vienna IX,Austria. An International Symposium on the Metallurgy of Plutonium sponsored by the SociCtC Franqaise de Metallurgie and the French Atomic Energy Com- mission will be held in Grenoble France on April 19-22nd 1960. Further information may be ob- tained from the SociCt6 Franqaise de MCtallurgie 25 rue de Clichy Paris.The Second International Congress of Catalysis will take place in Paris on July 4-9th 1960. Details can be obtained from the Secretariat General du Congres Paris &ole SupCrieure de Physique et de Chimie 10 rue Vauquelin Paris 5 or from Dr. F. G. Ciapetta Secretary The International Congress of Catalysis Inc. Grace Research and Development Division Washington Research Centre Clarksville Maryland U.S.A. The Eighth International Symposium on Combus- tion will be held at the California Institute of Tech- nology Pasadena California on August 29th to September 2nd 1960 under the auspices of The Combustion Institute. Further details may be ob- tained from The Combustion Institute Union Trust Building Pittsburgh 19 Pennsylvania.The Eighteenth International Congress of Pure and Applied Chemistry will be held in Canada on August 6-12th 1961. The Congress will be preceded on August 2-5th by the Twenty-first Conference of the Union. Imperial Chemical Industries Limited.-The Board of Imperial Chemical Industries Limited announce PROCEEDINGS that Sir Alexander Fleck K.B.E. F.R.S. who will attain the age of 70 in November 1959 has intimated his intention of relinquishing his position as Chair- man of the Board and of resigning from the Board of the company on February 29th 1960. Sir Alexander Fleck will have been actively associated with the company and its predecessors for over 44 years. He was appointed a Director of Im- perial Chemical Industries Limited on June 8th 1944 and was elected a Deputy Chairman in December 1950.He succeeded Mr. John Rogers O.B.E. LL.D. as Chairman on the latter’s resigna- tion in June 1953. The Board have unanimously agreed to elect Mr. Stanley Paul Chambers C.B. C.I.E. as Chairman of the Board to succeed Sir Alexander Fleck with effect on and from March lst 1960. Mr. Chambers who is 55 years of age has been with Imperial Chemical Industries Limited since July 1947 when he was appointed to the Board. He was elected a Deputy Chairman in July 1952. Persolml.-Dr. D. W.Adamson has been appointed an alternate director of Cooper McDougall & Robertson Ltd. Professor J. S. Anderson Professor of Inorganic and Physical Chemistry at the University of Melbourne has been appointed as Director of the National Chemical Laboratory and is expected to take up his duties in October.He will succeed Dr. D. D. Pratt who is to retire. Dr. W.L. F. Armarego has been appointed Senior Demonstrator in Organic Chemistry at the University of Melbourne. Dr. P. G. Ashmore has been appointed to an Official Fellowship and Tutorship for advanced students at Churchill College Cambridge. Mu. A. L. Bacharach has been elected President of the Nutrition Society. Professor D. H. R. Barton Professor of Organic Chemistry of the Imperial College of Science and Technology London has accepted the invitation of the Royal Australian Chemical Institute to attend the meeting of the International Union of Pure and Applied Chemistry in Australia in September 1960 and to visit all branches before the symposium.Dr. A. H. Beckett Reader in Pharmaceutical Chemistry at Chelsea College of Science and Tech- nology has been appointed Head of the School of Pharmacy at the College as from September 1st. The title of Professor of Analytical Chemistry in the University of Birmingham has been conferred on Dr. R. Belcher from August 1st. Professor F. Bergel will leave this country at the end of September for a four months’ stay in the United States where he has been invited as a visiting worker and lecturer to the Children’s Cancer Re- search Foundation Boston Mass. and appointed a AUGUST 1959 visiting lecturer to the Department of Biological Chemistry Harvard Medical School.Dr. D. A. Blackadder has been appointed to a Lectureship in the Chemistry Department of St. Salvator’s College University of St. Andrews. Dr. D. C. Bradley has been appointed to the Chair of Inorganic Chemistry in the University of Western Ontario as from September next. Dr. D. M. Brown has been appointed to a University Lectureship in Organic Chemistry at Cambridge. Mr. M. F. Carroll has retired from the post of Chief Research Chemist to A. Boake Roberts & Co. Ltd. He is retained as consultant by the Company. Mr. P. Casapieri has been appointed Lever Research Fellow in the Department of Chemistry of the University College of Rhodesia and Nyasaland. Dr. J. W. Cook Vice-Chancellor of the University of Exeter has been appointed a member of the Board of Scientific and Industrial Studies of the College of Technologists National Council for Technological Awards.Dr. C. J. Danby Lecturer in Chemistry at Worcester College Oxford has been appointed to a Fellowship and Lectureship at the College. Mr. D. S. Daniel has been appointed Research Fellow in the Department of Chemistry University .of Birmingham. Dr. P. B. D. de la Mare is lecturing and visiting in the United States and in New Zealand from July 2nd until October 30th. Professor M. B. Donald Professor of Chemical Engineering at University College has been ap- pointed a Co-optative Governor of the Borough Polytechnic. Dr. E. A. V. Ebsworth has been appointed to a University Demonstratorship in Inorganic Chem- istry at Cambridge and has been pre-elected into an 4Official Fellowship (Class D) of Christ’s College with effect from October 1st.Dr. V. C. Ewing Pressed Steel Research Fellow Oxford University has been appointed Lecturer in Chemistry at the University College of North Staffordshire from October 1st. Dr. F. N. Fustier Senior Lecturer in Pharmacology at the University of Otago New Zealand is spending sabbatical leave in England the United States and Australia. Sir Alexander Fleck has made a trust deed in favour of the University of Glasgow and the Durham Division of the University of Durham. The income from the fund is to be applied at Glasgow to make Alexander Fleck Awards to forward research in Chemistry and at Durham to make Isabel Fleck awards to forward research in History.Mr. C. S. Garland who retired as President of the National Union of Manufacturers last year has been appointed Chairman of the National Union of Manufacturers Advisory Service. Mr. E. D. Gilbert has resigned his position of Chief Development Chemist Newton Chambers & Co. Ltd. Sheffield to open a consulting practice in Southampton specialising in industrial colloids particularly emulsions and self-emulsifiable oils ; industrial hygiene; corrosion and protective coatings. Dr. W. P. Grove has been appointed Director of the Atomic Energy Authority’s new radio-isotopes production and marketing organisation at the Radiochemical Centre Amersham. The Earl of Halsbury is to become a Director of Sondes Place Research Institute and has joined the Board of Head Wrightson Processes a subsidiary of Head Wrightson & Co.Dr. G. B. Hargreaves of Birmingham University has accepted an appointment as a Research Demon- strator at the University of Washington as from August 1st. Mr. M. D. Johnson has been appointed to an Imperial Chemical Industries Fellowship in Chem- istry at the University of Hull with effect from October 1st. Mr. H. T. Islip retired from the Civil Service in July after 40 years’ service with the Plant and Animal Products Department Imperial Institute and its successors the Colonial Products Laboratory and the Tropical Products Institute. Dr. A. L. Kapoor of the National Chemical Laboratory Poona has been appointed an Imperial Chemical Industries Fellow in Chemistry at Univer- sity College Dublin.Dr. Kapoor who was trained at the lnjab University has studied at Zurich and at Wayne State University Detroit. Dr. A. R. Katritzky has been appointed to an Official Fellowship at Churchill College Cambridge. Dr. Alexander King has been made an Honorary Fellow of the Institute of Information Scientists. This is the first Honorary Fellowship to be conferred by the Institute which has completed its first year of active operation. Professor G. B. Kistiakowsky (Honorary Fellow) Professor of Chemistry at Harvard University has been appointed as President Eisenhower’s Special Assistant for Science and Technology in succession to Dr.J. R. KiNian Jr. who has retired in order to resume his appointment as President of the Massa- chusetts Institute of Technology. Dr. R. Lessing has been appointed Vice-chairman of the Chadwick Trust in succession to Sir Allen Daley who has become Chairman in place of the late Mr. E. M. Rich. Dr. A. G. Maddock University Lecturer in In- organic Chemistry at the University of Cambridge has been elected to a Non-Stipendiary Fellowship of St. Catharine’s College Cambridge from July 1st. PROCEEDINGS Professor G. F. Marrian will retire from the Chair of Chemistry in relation to Medicine at the Univer- sity of Edinburgh on September 30th. Dr.F. H. McDowaZl Chief Chemist to the Dairy Research Institute New Zealand has been appointed Deputy Director.Dr. N. J. L. Megson has been appointed Director of Materials Research and Development (Air) at the Ministry of Supply in succession to Dr. H. Sutton who will shortly be retiring from public service. Dr. Megson joined the Ministry of Supply in 1939 and in 1951 was appointed Superintendent of the Chem- i3try Department at the Royal Aircraft Establish- ment Farnborough. Dr. J. N. Murrell has been appointed Lecturer in Chemistry at the University of Sheffield. Dr. R. T. Parker has been appointed Head of Aluminium Laboratories Limited Banbury and Geneva offices in place of Mr. R. D. Hamer. Professor Ram Chand Paul of Karnatak Univer- sity Dharwar India has been appointed Professor of Inorganic Chemistry and Head of the Department of Chemistry at Panjab University.Dr. P. L. Pauson Reader in Organic Chemistry at the University of Sheffield has been appointed to the Chair of Chemistry at the Royal College of Science and Technology Glasgow. Dr. F. H. Peakin an Assistant Purchases Con- troller of Imperial Chemical Industries Limited has been appointed Manager of the German branch of Imperial Chemical Industries (Export) Limited and expects to take up duties in Frankfurt/Main in the autumn. Dr. B. R. Penfold of the Chemistry Department University of Canterbury New Zealand who was recently promoted to a Senior Lectureship has been awarded a National Academy of Sciences Post- Doctoral Research Fellowship which he will take up at the University of Minnesota to work with Professor Pepinsky.Dr. S. V. Perry University Lecturer in Biochem- istry in Cambridge University has been appointed to the Chair of Biochemistry in the University of Birmingham from September 1st. Mr. S. B. Phillips has retired from his position as Chief Chemist of Cadbury Brothers Ltd. after 47 years’ service. Dr. J. H. Purnell has been appointed to a Univer- sity Lectureship in Physical Chemistry at Cambridge. Dr. C. B. Reese has been appointed to a University Demonstratorship in Organic Chemistry and to an Official Fellowship at Clare College Cambridge. Mr. L. Simmens has been appointed Chief Chemist of Mars Ltd. Slough Trading Estate in succession to Dr. A. A. Houghton who has been promoted to the central office staff of Food Manu- facturers Inc.to co-ordinate product research be- tween the different companies in the Group both in the United Kingdom and the United States. Dr. E. J. Smith has relinquished his post as Lecturer in Physics at University College London to become Chief Scientist in the Chemistry Depart- ment of Fisons Ltd. at Levington Research Station Ipswich. Dr. R. L. Smith has resigned from his post with Norman Evans & Rais Ltd. to take up an appoint- ment as Chemical Development Manager with The Permut it Company Lt d. Dr. J. Sykes has been appointed Lecturer in Biochemistry in the University of Sheffield. Dr. B. A. Thrush has been appointed to a Univer- sity Assistant Directorship of Research in Physical Chemistry at Cambridge.Sir Alexander Todd has been elected as Second Warden of the Salters’ Company. Dr. D. Traill Research Director of the Nobel Division of Imperial Chemical Industries Limited has been elected an Assessor on the University Court of the University of St. Andrews. Dr.J. H. Turnbull of the University of Birmingham has been appointed by the War Office to the post of Associate Professor at the Royal Military College of Science at Shrivenham. Mr. G. F. Underhay a Director of the Bowater Research and Development Co. Ltd. and of Bowater’s United Kingdom Pulp and Paper Mills Ltd. has been appointed Chairman of the Paper Industry Standards Committee. Dr. A. M. Ward Principal of the Sir John Cass College has been appointed Chairman of the Applied Chemistry Subject Panel National Council for Technological Awards in succession to Dr.J. W. Cook. Mr. D. E. Webster has been appointed to an Assistant Lectureship in Chemistry at the University of Hull with effect from October 1st. Dr. D.H. Whiffen has accepted an appointment as Senior Principal Scientific Officer in the Basic Physics Division of the National Physical Labora- tory Teddington. Dr. J. H. Wilkinson is retiring from his post as Senior Lecturer in Chemistry at Suiiderland Tech- nical College at the end of the summer term. Mr. A. H. Wilson has been elected to an Honorary Fellowship of Emmanuel College Cambridge. He was formerly a Fellow of the College. Election of New Fellows.-6 1 Candidates whose names were published in the Proceedings for May have been elected to the Fellowship.Death of Honorary Fellow.-We regret to announce the death (9.6.59) of Professor Dr. AdoZf Windaus (Gottingen) who was elected an Honorary Feilow of the Society in November 1933. AUGUST 1959 Deaths of Fellows.-The deaths of the following Fellows are announced with regret Dr. Roy Gladwin Collinson (5.6.59) of the Reed Paper Group Packag- ing Research and Development Division; Mr. Charles Gilling (26.6.59) of Perranporth; Mr. Dadabhoy Maneckshaw Karkhanavala (1.5.59) of Bombay; Dr. Samuel Judd Lewis (24.4.59) Consult- ing Chemist of High Hol born ;Professor K. Linder-strorn-lang (25.5.59) of the Carlsberg Laboratories Copenhagen ; Dr. James Hill Millar (1 4.6.59) of Dublin; Mr.Michael Angelo O’Callaghan (1 1.6.59) of Oporto ; Mr. Frederick Leigh Okell (9.5.59) formerly Editor of “The Analyst”; Dr. Clarence Arthur Seyler (24.7.59) of the British Coal Utilisa- tion Research Association; Mu. Thomas Marvel Sharp (10.6.59) of the Wellcome Laboratories of Tropical Medicine; and Mr. John Leslie Wild (9.6.59) of Duttson and Knight Ltd. Bristol. FORTHCOMING SCIENTIFIC MEETINGS (Details of Meetings for the period October 1959 to January 1960 will be published in the next issue of the Proceedings.) London Thursday October 15th 1959 at 7.30 p.m. Niels Bjerrum Memorial Lecture. To be given by Professor E. A. Guggenheim M.A. Sc.D. F.R.S. in the Rooms of the Society Burlington House London W.1. Birmingham Friday October 23rd 1959 at 4.30 p.m. Lecture “Some Recent Developments in the Por- phyrin Field,” by Professor G. W. KeMer Ph.D. Sc.D. Joint Meeting with Birmingham University Chemical Society to be held in the Large Chemistry Lecture Theatre The University. Cambridge Monday October 12th 1959 at 5 p.m. Lecture “Diterpene Synthesis,” by Dr. J. A. Barltrop M.A. To be given in the Chemical Laboratories Lensfield Road. Friday October 30th at 8.30 p.m. Lecture “Developments in the Chemistry of Bacterial Walls,” by Professor J. Baddiley Ph.D. D.Sc. Joint Meeting with the University Chemical Society to be held in the Chemical Laboratories Lensfield Road. Exeter Friday October 23rd 1959 at 5 p.m. Lecture “Some Photochemical Re-arrangements,” by Professor D.H. R. Barton F.R.S. To be given in the Washington Singer Laboratories Prince of Wales Road. Liverpool Thursday October 29th 1959 at 5 p.m. Lecture “The Growth of Fluorocarbon Chemistry,” by Professor R. N. Haszeldine D.Sc. Ph.D. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Department of Inorganic and Physical Chemistry The University. Northern Ireland Tuesday October 27th 1959 at 7.45 p.m. Lecture “Some Properties of Heteroaromatic Amines,” by Dr. K. Schofield. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Department of Chemistry Queen’s University Belfast. North Wales Thursday October 29th 1959 at 5.45 p.m.Lecture “Recent Developments in the Study of Ionic Solutions,” by Professor K. W. Sykes M.A. D.Phi1. Joint Meeting with the University College of North Wales Chemical Society to be held in the Department of Chemistry University College of North Wales Bangor. Southampton Friday October 16th 1959 at 5 p.m. Lecture “Applications of Chemistry in the Inter- pretation of Infrared Spectra,” by Dr. L. J. Bellamy. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry to be held in the Chemistry Department The University. South Wales Monday October 26th 1959 at 5.30 p.m. Lecture “Recent Developments with Crystallo-graphy of Vitamin BIZ,” by Dr. D. M. Hodgkin F.R.S. To be given in the Chemistry Department University College Cardiff.Tees-side Monday September 28th 1959 at 8 p.m. Lecture “Pharmacology of Polymethylenes,” by Dr. R. Ing F.R.S. To be given at the Constantine Technical College Middles broug h . PROCEEDINGS OBITUARY NOTICES WALTER GRAHAM 1918-1 958 WITH the sudden death of Walter Graham at Glasgow on September 1lth 1958 chemists lose a valued colleague and a truly remarkable man. Graham was sadly crippled from birth but his fine mind and an indomitable spirit brought him a life which was rich in achievement and in friendship. His all too brief professional career was concerned with the alleviation of human suffering and to this end he strove to equip himself cheerfully accepting responsibilities and working wholeheartedly in their discharge.Walter only son of George and Elizabeth Graham was born at Greenock on July 22nd 1918 and was educated at Dumbarton Academy and Glasgow University. In 1940 he graduated B.Sc. with 1st Class Honours in chemistry and was awarded the Mackay Smith prize as the outstanding chemistry student of his year. At Glasgow under J. W. Cook he began research on the structure of colchicine an alkaloid of some significance for the study of cancer. This was followed by an investigation of hydropyrenes and later under the auspices of the Medical Research Council by researches on antimalarials in which he was associated with F. H. Curd and F. L. Rose. He took his Ph.D. at Glasgow in 1944 and joined Organon Laboratories Ltd.the Dutch firm with which he spent the remainder of his career. The im- mediate consequence was his transfer to London where he worked for a time in the Chester Beatty Institute of the Royal Cancer Hospital. Then for a further period of research and specialist training he went to his firm’s headquarters in Holland and com- pleted the circuit by a return to the Glasgow district taking up his post with the Organon Laboratories at Newhouse where he had charge of research and development. He was a Fellow of the Royal Institute of Chemistry and at the time of his death was an active member of the Local Committee of the Chemical Society. But it is Walter Graham the person who claimed the admiration and affection of those who knew him.For them the twinkling eye that spoke the gaiety within the pawky humour-essentially Scottish in style-or some other trait quickened in universal liking will recall the man in warm remembrance. His many friends in many places will join in sympathy with the parents who survive him and in whom he was fortunate. J. D. LOUDON. MOHAMED ZAFARULLAH 1923-1 958 BORNon January lst 1923 at Shadiwal near Gujrat (formerly Punjab now West Pakistan) Mohamed Zafarullah received his early education at Islamia High School Gujar Khan. After matriculation he joined Zamindara College Gujrat where he passed the intermediate science examination and won a Government merit scholarship. He graduated from the Panjab University in 1946 in the Honours School of Chemistry.Zafarullah obtained the M.Sc. (Tech.) degree in 1947 being first in the University. Then he was engaged in teaching Physical Chemistry first as a demonstrator then as a Junior lecturer and there- after to his death as a senior lecturer. In the summer of 1951 he proceeded to the Massachussetts Institute of Technology U.S.A. and received specialised training in spectroscopic and instrumental methods of analysis. In 1954 he joined King’s College London and had the privilege of working under Professor Sir Eric Rideal in the field of heterogeneous catalysis. He returned to Pakistan in the summer of 1957 after obtaining Ph.D. Degree. After 1947 he was engaged in teaching of physical chemistry to the Honours and M.Sc.classes includ- ing guiding the research of post-graduate students. He was in charge of the section of physical chemistry of this Institute during all these years. It is an irony of fate that after receiving specialised training in the various fields when he was going to embark upon a research career he died at a young age of about 36. Zafarullah had been a very pleasant colleague. He was held in very high esteem among the academic staff of this University as well as by the student com- munity. His integrity as a teacher honesty of pur- pose straightforwardness and sincerity will be long remembered by his colleagues. He died on October 24th 1958 after a protracted illness at Lahore. M.I. D. CHUGHTAI. AUGUST1959 239 HENRY EDGAR WATT 1877-1959 HENRYEDGARWATT born on July 12th 1877 passed peacefully away at his home in Edinburgh on February 8th 1959.He had lived his life with grace and with graciousness. He studied chemistry at King’s College Newcastle on Tyne and in 1900he graduated B.Sc. with distinc- tion as the Freire Marreco medallist. In 1904 he was awarded the M.Sc. and in 1908 the degree of D.Sc. was conferred on him for his work on the Senecio alkaloids. After a brief spell with Burroughs Wellcome he joined the staff of the Imperial College of Technology under Professor Wyndham R. Dunstan and here his life-long interest in alkaloid chemistry commenced. He studied the Senecio species and isolated seneci- foline and senecifolidine (J.1909,95,466; Bull. Imp. Inst. 191 1 9 346). After minor work on Orchella weed he worked on the evaluation of Indian opium (Science Progr. 1909 14 279) and later contributed to Thorpe’s Dictionary. In 1909 Dr. Watt joined T. & H. Smith Ltd. in Edinburgh to initiate the manufacture of the Strychnos alkaloids and later to take charge of manufacture of the opium alkaloids. He retired from this post in 1947. Dr. Watt was of a reserved nature but his skill knowledge and judgment were always at the disposal of any who sought it while his fundamental under- standing and integrity of purpose helped and inspired all who associated with him. He gave willingly of his time and his services to the Edinburgh and the East of Scotland Sections of the Chartered Societies and in particular that of the Society of Chemical Industry of which he was a past Chairman.Dr. Watt is survived by his wife and two daughters. G. W. WALKER. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Adams Kenneth Allen Harry M.Sc. Department of Chemistry University of Saskatchewan Saskatoon Canada. Aguiar Adam M. M.A. Ph.D. 275 Renner Avenue Newark New Jersey U.S.A. Alsop Derek John B.Sc. 298 Hagley Road Edgbaston Birmingham 17.Althouse Victor Edward B.Sc. Department of Chem- istry Stanford University California U.S.A. Ang Kok Peng Ph.D. A.R.I.C. Chemistry Department University of Malaya Singapore. Anselme Jean-Pierre Louis Marie B.Sc. 47-33 39th Place Sunnyside L.I.C. 4 New York U.S.A. Bancroft David Malcolm BSc. 12 Mill Hayes Road Burslem Stoke-on-Trent Staffs. Bhattacharya Rama M.Sc. Ph.D. Chemistry Depart- ment University College Gower Street London w.c.1. Birt Trevor John B.Sc. 575 Holly Lane Erdington Birmingham 24. Buncel Erwin Ph.D. A.R.I.C. Chemistry Department McMaster University Hamilton Ontario Canada. Buxton George V. B.Sc. Washington Singer Labora- tories Perry Road Exeter. Chari Mandyam Osuri Alasingra B.Sc.43 Anson Road London N.7. Cheema M. Zafarullah Khan B.Pharm. Dr.rer.nat. Christophstrasse 7 I. Tubingen Germany. Connor Henry BSc. 120 Beaufort Park London N.W.ll. Cook Elmer William M.S. Ph.D. Cyanamid of Great Britain Bush House Aldwych W.C.2. Cowan Dwaine O. B.S. Chemistry Department, Stanford University California U.S.A. Davies Jeremy Michael B.Sc. 112 Shirley Avenue Reading Berks. De Maine Paul Alexander Desmond Ph.D. Chemistry Department New York State College for Teachers New York State University Albany N.Y. U.S.A. Dreyer David B.S. 3211 Franklin Avenue Seattle 2 Washington U.S.A. Edwards John A. Ph.D. Calle Goethe 144-5 Mexico 5 D.F. Ellwood Derek Clifford B.Sc. 31 Regent Street Stotfold Beds. Enzell Curt Rickard.Herserudsvagen 2d Lidingo, Sweden. Francis Martin James Ogilvie. 21 Cadogan Street London S.W.3. Franck Burchard Dr.rer.nat. Am Pfingstanger 45 Gottingen (20b) West Germany. Franklin Norman Collins. 337 Bricknell Avenue Hull Yorks. Froemsdorf Donald H. Ph.D. 22 Monee Road Park Forest Illinois U.S.A. Gesser Hyman Ph.D. Department of Chemistry Uni- versity of Manitoba Winnipeg Manitoba Canada. Gill Alan. 26 Tickhill Square Denaby Main nr. Doncaster Yorks. Glover George Ebner B.S 54 Summit Avenue, Philadelphia 18 Pennsylvania U.S.A. Hacket Nicholas Bonham. 23 Hopetoun Avenue, Vaucluse Sydney New South Wales Australia. Hanack Michael Dr.rer.nat. Pharm.-chemisches Institut der Universitat Wilhelmstrasse 27 Tubingen Ger- many.Haynes Bernard B.Sc. 24 Priory Close Bebington Wirral Cheshire. Hertl William B.S. King’s College Cambridge. Higgins David John. 4 The Oval Warley Smethwick 41 Staffs. Hill John Anthony B.Sc. 48 Bodnant Avenue Leicester. Hinton Roy Cyril B.A. Pembroke College Cambridge. Hopton John Douglas. 66 Haywood Road Bromley Kent. Hosein David Azural A.M.I.E. 79 Eglinton Road Plumstead S.E.18. Hoyle William M.Sc. A.R.I.C. A.R.T.C.S. 125 Har- borne Road Edgbaston Birmingham 15. Hurst Jeffrey John B.Sc. 92 Chaplin Road Longton Stoke-on-Trent Staffs. Iber Peter Keim B.A. Chemistry Department The Johns Hopkins University 34th Charles Streets, Baltimore 18 Maryland U.S.A. Insley Michael John BSc. 585 Burton Road Midway Burton-on-Trent Staffs.Irons Laurence Ian B.Sc. A.R.C.S. 20 Dipton Avenue Benwell Newcastle upon Tyne 4. Izsak Dennis. 2/5 Ormond Gardens Coogee Sydney N.S. W. Australia. Jones Malcolm Norcliffe BSc. 20 Elmsleigh Road Heald Green Cheshire. Julian Keith. Balliol College Oxford. Kelly Ronald B.Sc. 6B Churchmead Road Willesden N.W.lO. Knowles Jeremy Randall B.A. Beechwood Iffley Turn Oxford. Kuhn Nicholas John. 25 Victoria Road Oxford. Lenthen Paul Myer. 10 Boronia Road Bellevue Hill Sydney N.S.W. Australia. Lister John Henry Ph.D. A.R.I.C. 8 Barkworth Close Broadley Avenue Anlaby nr. Hull Yorks. Maass Douglas Hugo M.Sc. 230 Chislehurst Road Petts Wood Kent. McCamish Malcolm B.Sc. St. John’s College St. Lucia Brisbane Queensland Australia.McCoy Errol Frederick B.Sc. 7 Melrose Street Mosman N.S.W. Australia. McCullough John James B.Sc. 59 Wellesley Avenue Belfast Northern Ireland. Mansfield John Rickard. 30 Reynolds Road Shirley Southampton. Matthews. William Edgar. 30 Rossett Green Lane, Harrogate Yorks. -Melillo Joseph T. B.S. 2333 Arthur Avenue New York 58 N.Y. U.S.A. Miles. Harry Todd. Jr. Ph.D. National Institutes of Health Bethesda -Maryland U .S .A. Millar Keith Raymond M.Sc. 6 Blewman Street, Heretaunga Wellington New Zealand. Moore James Alexander M.S. Ph.D. Chemistry Department University of Delaware Newark Dela- ware U.S.A. MUSSO Hans Dr.rer.nat. Stettinerstrasse 23 Gottingen Germany. Phipps Peter Beverley Powell. 16 Fairgreen Cockfosters Road Cockfosters Barnet Herts.Piatak David Michael B.S. Department of Chemistry University of Maine Orono Maine U.S.A. Pidcock Alan B.Sc. 22 Sapling Road Swinton, Manchester. Podilchuk Ilia B.Sc. 9 Fanshawe Terrace Hooe nr. Plymouth Devon. Powell Paul. 103 High Street Hampton Middlesex. Prasad Raj Nandan M.Sc. Ph.D. 114 South Forest Avenue Ann Arbor Michigan U.S.A. Quarmby Christopher. 69 Woodhouse Lane Brighouse Yorks. Rice Dennis Frederick B.Sc. 8 Dhu Varren Crescent Belfast. Robinson Brian Poole B.Sc. Chemistry Department University of Saskatchewan Saskatoon Canada. Rogers David Eric. Glendenning Hayes Road Mid- somer Norton nr. Bath Somerset. Ross David B.A. Ph.D. Priory Farm Waverley Farnham Surrey. Schmutzler Reinhard. Schellingstrasse 26 Stuttgart (14a) Germany.Sewell Grace B.Sc. 18 Buckland Crescent London N.W.3. Shean David Horace Sutton. 8 Clare Road Leytonstone E.11. Shone Geoffrey Graham B.Sc. 77 St. Saviour’s Road Reading Berks. Singh Phirtu M.S. Department of Chemistry University of Colorado Boulder Colorado U.S.A. Smith James David. 5 Rawcliffe Street Blackpool Lancs. Smith Thomas Albert B.Sc.Longfield Stallington Road Blythe Bridge Stoke-on-Trent. Spencer Glenn Howard Jr. Ph.D. Department of Chemistry Harvard University Cambridge 38, Massachusetts U .S.A. Steel Kenneth David. 154 Kingsgrove Road Kingsgrove Sydney N.S.W. Australia. Strickson John Alfred B.Sc. 37 Parkside Little Thurrock Grays Essex. Tertzakian Gerard B.Sc. Department of Chemistry University of Saskatchewan Saskatoon Canada.Tomlinson Harry. 19 Berwick Avenue Heckmondwike Yorks. Uff Barrie Cookson B.Sc. Manor House Northfield Birmingham 3 1. Walmsley Stuart Herbert B.Sc. 73 Whitegate Drive Blackpool Lancs. Welch Vernon Albert B.Sc. Department of Biochemistry, South Parks Road Oxford. Wharton Peter S. M.A. Ph.D. 360 Riverside Drive Apt. llc New York 25 N.Y. U.S.A. Wheelock James Verner. Scoby House Enniscorthy Co. Wexford Ireland. Whitear Anthony Leslie B.Sc. 11 Park Road Wanstead E.12. Whitfield Richard Charles. 89 Millway Mill Hill, N.W.7. Willcott Mark Robert M.A. Sterling Chemistry Labora- tory Yale University New Haven Connecticut, U.S.A. Williams Roger Douglas B.Sc. 69 Cadogan Gardens South Woodford E.18. Wood Kenneth Roger. 29 Stubley Road Heckmondwike Yorks. Wyldes Norman. 84 Mill Lane Ellesmere Port Wirral Cheshire. Yadav Jai Singh Pal Ph.D. Imperial Forestry Institute South Parks Road Oxford. Yazgi Alfred. 5 Petit Beaulieu Lausanne Switzerland.
ISSN:0369-8718
DOI:10.1039/PS9590000201
出版商:RSC
年代:1959
数据来源: RSC
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