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Proceedings of the Chemical Society. January 1962 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue January,
1962,
Page 1-36
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Proceedings of The Chemical Society 1962 LONDON THE CHEMICAL SOCIETY PROCEEDINGS OF THE CHEMICAL SOCIETY JANUARY 1962 SIMONSEN LECTURE* Some Pathways in Biosynthesis By A. J. BIRCH (THEUNIVERSITY 13) MANCHESTER THEassociation of the name of Sir John Simonsen with this lecture gives me particular pleasure. It is also appropriate since some of our own contributions to this subject grew out of work on dehydroan-gustione and related compounds which was initiated by him. I am speaking to you today as an organic chemist with no biochemical training in an attempt to demonstrate how the organic chemist can make his own special contribution to the subject of bio- synthesis particularly through his intimate know- ledge of reaction mechanisms.The earlier work particularly on alkaloids pioneered by organic chemists such as Sir Robert Robinson was based on structure-analysis of the molecular skeletons of substances derived from biological sources. It attempted to relate simpler to more complex mole- cules by using the principles of chemical reaction theory to suggest how the units became linked to- gether. This approach did not deny the importance of enzymes but it was insisted that reactions should ultimately be explicable in terms of fundamental reaction theories. The approach suffered from a number of drawbacks; in particular it could only give a vague indication of the sequence of stages involved. In more recent years advances in biochemical techniques and the uses of radioactive isotopes have made possible such elegant biochemical work as that of Davis and Sprinson and other collaborators2 on shikimic acid (I) as a biochemical precursor of aro- H02COT2*COaC02H ___c HO AH (I) .Anthranrlrc acid indole. p -aminobenzoic acrd etc. @= Phosphate ester YIMNH3W matic compounds [e.g. phenylalanine (II)] and of Bl~h,~ and their Lynen,* Cornforth and P~pjak,~ collaborators on the origin of the biochemically * Delivered before The Society on May 4th 1961 at Burlington House London W.l. For a summary see Robinson “The Structural Relations of Natural Products,” Oxford 1955. See e.g. Davis “Amino-Acid Metabolism,” John Hopkins Baltimore 1955 799; Ah. Enzymol.1955 16 247; Sprinson Adv. Carbohydrate Chem. 1960 15,235. Eg. Bloch “Vitamins and Hormones,” Academic Press New York 1958 p. 119; Chaykin Law Phillips Tchen, and Bloch Proc. Nat. Acad. Sci. U.S.A. 1958 998. Eg.,Lynen Eggerer Henning and Kessel Angew. Chem. 1958,70 738. E.g. Cornforth J. Lipid Res. 1960 1 3; Popjak and Cornforth Adv. Enzymol. 190,22 281. 3 PROCEEDINGS active isoprene units [the isopentenyl pyrophosphates (HI)and (IV)] and their conversion into polyter- penoids and steroids. I have not the time to discuss these and equally interesting work on fatty acids amino-acids carbohydrates etc. with which we have not been ourselves concerned. 2 MKO. COA -MeCO.Cl-$CO* CTA +-Me COCOA ?H QH Me$.CH,.CHiOH Me .$*CH2*CO*CoA CH2C0 H CH2C02H ..@=PY-te ester Cx=Coenzyme-A ester Our own work was initiated (1951) in an attempt to extrapolate by structure-analytical methods the work of the biochemists to systems which had not been investigated by biochemical means. Xn particular we attempted to extrapolatee the known biochemical importance of acetic acid as a building unit in fatty acids and steroids to phenolic and enolic systems. The reason for choosing the latter was the expecta- tion that oxygen atoms remaining in the system could be used as markers to indicate the positions of some of the carboxyl-carbon atoms of acetic acid units. Collie7 had put forward a similar hypothesis in 1907 based on the condensation and cyclisation of synthetic /%polyketones but we were initially un- aware of it and it unfortunately exercised no further influence.Its complete neglect can be seen by examining authoritative reviews of the subjects which it could chiefly have influenced e.g. the bio- synthesis of mould products* and of flavonoids,g where it is not even mentioned. The only discussion I have been able to find which does more than give a passing referencelo to Collie’s work is in a text- bookll where it was developed with excessive en- thusiasm in obviously inapplicable directions. An apparently independent treatment of the subject by Birch and Donovan Austral. J. Chem. 1953 6 360. Collie J. 1907 91,1806; Proc. Chem.-Soc.,-1907 230. ~ ~ Robinson of which we were unaware was not pub- lished until 1955,12 by which time we had already provided considerable experimental support for our hypothesis.13J4J5 Our hypothesis was originally based on a con-sideration of what might happen if in the course of biosynthesis of a fatty acid through the head-to-tail linkage of acetic acid units the /?-oxygen atoms which were the residues of the acetic acid carboxyl group were not serially reduced out.Collie’s approach had a different but equally chemical basis. He studied7 the cyclisations and condensations of synthetic /?-polyketones and was struck by the resemblance of some of the products to certain natural products; he therefore postulated similar processes in Nature. A /%polyketo-acid chain (probably as its co-enzyme-A ester) can be conceived to cyclise in two ways by known types of mechanism (aldol con- densation Claisen condensation) to give aromatic or related systems.A straight-forward example is the production of orsellinic acid (V) or acetylphloro- glucinol (VI) from 3,5,7-trioxo-octanoic acid. More complex reactions can occur with longer chains. / I..................... ”.................... I HT) This reaction immediately suggested6 the solution to the puzzle of the almost invariable co-occurrences of the pinosylvin-type (WI) and flavonoid-type com- pounds (e.g. VIII) in pines. The basic carbon skele ton of each could be constructed from the same precursor if the chain could start from cinnamic acid (presumably as the coenzyme-A ester) and if the two possible types of ring closure then operated.This work also suggestede the final solution to the prob- lem of biosynthesis of the flavonoid and anthocyanin pigments later confirmedle by tracer experiments. Further uses were made of the hypothesis as a kind of “isoprene rule” and it was demonstrated that it could predict the correct structures for eleuther- Raistrick Proc. Roy. Soc. 1949 A 199 141; 1950 B 136,481 ; Asahina and Shibata “Chemistry of Lichen Sub- stances,” Japan SOC. Promotion Sci. Tokyo 1948,212. * Geissman and Hinreiner Bot. Rev. 1952 18 77. loRobinson J. Roy. SOC.Arts. 1948,% 795. l1 Stewart “Recent Advances in Organic Chemistry,” Longmans Green London 1924. l2 Ref. 1 p. 3. lS Birch and Donovan Austral. J. Chem. 1953 6 373. l4 Birch and Donovan Chem.and Ind. 1954 1047; Austral J. Chern. 1955 8 529. l6 Birch. Massy-Westropp and Moye Chem. and Ind. 1955 683; Austral. J. Chem. 1955 8 539. l6 Renik and Urban Naturwiss. 1957,44,13; Underhill Watkin and Neish Canad.J. Biochem. 1957,35,219,229; Geissman and Swain Chem. and Ind. 1957 984; Shibata and Yamazaki Chem. and Pharm. Bull. Japan 1958 6 42; Grisebach,2.Naturforsch. 1957 12 227. JANUARY1962 inol?’ nalgiovensin,l* flaviolin,19 a-and /?-sori- genin,2O and mellein.21 The first striking confirmation of its correctness was the demonstrationfs that [l-lT]acetic acid was incorporated by Penicillium grismfulvum into 6-methylsalicylic acid to give the distribution of label shown in (IX). It has since been shown by tracer methods that a number of diverse structures arise by this route PhCH=CHCO*CoA \ Ph CH = CH.CO.CH,.CO.CH,.COCH~CO./ . Ph.CH=CH o”.” HO\ OH 4 M&O,H -h;le Y including griseofulvin (X)22, alternariol and citromycetin(xu>.= Initiation of the Chain.-It was necessary from the beginning6 to assume that any acid found in Nature (presumably as its coenzyme-A ester) might con- ceivably initiate a chain by adding to the methyl end of an acetyl-coenzyme-A unit. Among such acids readily recognisable by structure-analysis are fatty acids of varying lengths (C2,C4,C, C, C16,C,,),’5 branched-chain acids presumably related to amino- acids (such as isobutyric a-methylbutyric and iso- valeric acid) cinnamic acid (as noted above) nicotinic acid and possibly others such as glutamic acid.Chain-building.-The number of acetic acid units which can be recognised varies from one to eight or more but with the exception of “propionic acid” (see below) there is no clear evidence that other acids can be involved in chain-building as distinct from initiation. It is not inconceivable that other acids notably straight-chain fatty acids could be incor- porated in some cases. We noted25 that the labelling of the first acetic acid unit (Me end) incorporated into a chain by feeding [laC]acetic acid sometimes showed a label up to 8% higher than the other units. This provides some evidence that an intermediate chain exists; in a concerted assembly of units all units should have the same activity.It was however puzzling until recent elegant work on fatty acid bio- synthesis2s showed that the unit actually involved in chain-building is malonyl-coenzyme-A formed by carboxylation of acetyl-coenzyme-A. We have now shown2’ that addition of malonic and [1-lqC]acetic acid to Penicillium griseofulvum results in dilution of label in the carboxyl group of 6-methylsalicylic acid compared with the C-Me. Bu’bck and Smalleym have obtained the expected labelling by using [2-14C]malonic ester (first unit unlabelled) and the same deduction can be drawn from the important results of Bentley and Kei129 on the incorporation of [14C]malonic acid into penicillic acid itself derived from “acetate” via orsellinic acid. From the incor- poration of [14C]propionic acid into erythr~mycin~~ l7 Birch and Donovan Austral.J. Chem. 1953,6,360;see also Birch Fortschr. Chem. org. Naturstofe 1957,14 186. Birch and Massy-Westropp J. 1957 2215. laBirch and Donovan Chem. and Ind. 1954 1047; Austral. J. Chem. 1955,8 529. 2o Haber Nikuni Schmid and Yagi Helv. Chim. Acta 1957,39 1654. s1 Blair and Newbold J. 1955,2871;Birch and Donovan Chem. and Ind. 1954 1047. Birch Massy-Westropp Rickards and Smith J. 1958,360; Hockenhull and Faulds Chem. and Znd. 1955,1390. 2a Thomas Biochem. J. 1961,78 748. 24 Birch Fitton Pride Ryan Smith and Whalley J. 1958 4576. 2s Birch and Smith Chem. SOC.Spec. Publ. 1958,No. 12,1. 26 Homing Martin Karmen and Vagelos Biochem. biuphys. Res. Comm. 1960,3 106. 27 Birch Cassera and Rickards Chem.and Znd. in the press. Bu’Lock and Smalley Proc. Chem. SOC.,1961,209. 28 Bentley and Keil Proc. Chem. Suc. 1961,11 1. ao Vanek Majer Babicky Liebster Veres and Dolezilova IVth Internat. Congr. Biochem. Vienna 1958 Sect. 10-91 135; Corcoran Kaneda and Butte J. Bid. Chem. 1960,235 PC29; Grisebach Achenbach and Grisebach Nuturwiss. 1960,47 206. and methyrny~in~~ it can be dzduced that as sug- this substance (as rnethylmalonyl-coenzyme-A) can act as a chain-building unit. As noted below this route is not distinguishable by structure-analysis from the apparently commoner C-methylation but is biochemically distinct. Propionic acid probably as propionyl-coenzyme-A can initiate a chain also.% For fully acetic acid-derived substances* such as orsellinic acid (V) and methylsalicylic acid (XIII) the processes from present information appear to be those given in the scheme leading to these substances.,CO*H + 3H,C \\ COCA By using [14C,180]acetic acid Gatenbeck and Mosbach= showed for orsellinic acid and islandicin that the I80:l4Cratio is unchanged for “acetate” oxygen attached to the nucleus but the carboxyl group of orsellinic acid has been diluted by l60to the extent of 50%. This is precisely what is to be expected on the above picture the l60being intro- duced by hydrolysis of the coenzyme-A (thiol) ester. The reversible carboxylation to malonyl-coenzyme-A will not result in dilution of the l80 label. There is no doubt from this work that the “acetic acid” is incorporated as units and the oxygen atoms were originally in the carboxyl groups.The majority of polyketides can be built up (on paper) from one chain. However in some cases two must be involved (e.g. rubropunctatin XIV); and in other cases e.g. citromycetin (=I) the branched chain could be produced either by linking two straight chains or possibly by fission of a ring-system produced from one chain. The discovery of PROCEEDINGS the slightly different origin of the first unit in a chain should permit this point to be investigated experi- mentally. No attempts have succeeded in showing incor- poration into methylsalicylic acid of intermediates containing more than one acetic acid unit% (aceto- acetic acid or its ethyl ester 3,5-dioxohexanoic acid or its ethyl ester).The picture which best fits the results so far is that of direct assembly of the activated units starting with .an acyl-coenzyme-A with successive additions of malonyl-coenzyme-A units on an enzyme surface to give a /3-polyketo- ester of coenzyme-A as originally postulated6 on the basis of the reactivities necessary for the ring closures. This bound chain can probably revert rapidly to the original units unless a relatively irreversible step such as cyclisation intervenes. Ex- perimental progress will probably come through examination of the enzymes involved but so far only minimal amounts of synthesis of 6-methylsalicylic acid have been achieved in non-living systems.% Removal and Introduction of Oxygen.-To explain the production of 6-methylsalicylic acid (XIII) with oxygen missing from an expected position (compare orsellinic acid V)6 we were reluctant to assume direct removal from a phenolic ring although this might occur in a few cases e.g.by the route of oxidation to a quinonoid compound and reduction of this by a hydride ion rather than by an electron-donating system; a case in point would be volucri~porin~~ (XV). foH \ Q . tO-C,H,,-n * A generic name for such substances derived by folding a p-polyketone ring seems desirable and we suggest “polyketide” (cf. ref. 7). sL Birch Pride Rickards Thomson Dutcher Perlman and Djerassi Chem. and Znd. 1960 1245. Gerzon XGIVth Internat. Congr. Pure and Applied Chem.Zurich 1955; Woodward Angew. Chem. 1957,69 50. s3 Ollis and Sutherland Proc. Chem. Soc. 1960 347. 34 Gatenbeck and Mosbach Acta Chem. Scand. 1959,13 1561. a6 Birch Cassera and Thompson unpublished work. s6 Divekar Read Vining and Haskins Canud. J. Chem. 1959 37. 1970; Read and Vining Chem. and Ind. 1959, 1547. JANUARY 1962 A more acceptable general route for polyketides is the reduction of a carbonyl group in a polyketo- intermediate with aromatisation resulting finally from dehydration! A biochemical analogy is the conversion of acetoacetic acid into hydroxybutyric acid and thence into crotonic acid. The same result could be achieved by reduction at a cyclised but non- aromatic stage. If reduction occurs before cyclisation it is evident that reduction of carbonyl groups in- volved directly or as activating groups in ring- closure cannot be postulated.The gene Y in Dahlia variabih which results in pigments containing a resorcinol rather than a phloroglucinol ring probably controls the operation of such a carbonyl-reducing system.37 The likelihood that such routes are correct is increased by the natural occurrence of compounds such as flavoskyrin (XVI). This or more probably the anthrone precursor could aromatise to chryso- phanol as shown. (XVIII) The biochemical introduction of oxygen into organic molecules is a well-known process and in particular operates in phenolic compounds with introduction of ortho- or para-oxygen. A number of oxidative cleavage reactions of rings are also becom- ing apparent and it is known that penicillic acid (XVIII) comes from the benzoic acid (XVII)= and that patulin (xnc) is derived from methylsalicylic acid (XIII).39 Introduction of C1and C Units.-Considerations of structure-analysis led us to propose4o that pro- cesses of direct biochemical attachment of C and Clin(isoprenoid) units must take place on carbon,in addition to the well-known reactions on oxygen nitrogen and sulphur.The biochemical precursors were thought to be methionine (or other members of the C pool) and the terpene precursors respectively. These assumptions were confirmed by tracer experi- ments. HOdqH Me Me HO Me MeMe OH O(w Citrinin (XX) comes from acetic acid and three C units23 derivable from [Me-14C]methionine; terra- mycin (=) contains two N-Me and one C-Me all three derived from methionine with the same efficien~y.~~ Tracer experiments with [14C]methionine in the production of mycophenolic acid42 provided the first experimental proof of biological C-methyla- tion.Other compounds with such “introduced” C-methyl groups include s~lerotiorin~~ (XXIII)where such introduction occurs in an open chain as it does in the side-chain of eburicoic acidg3 and ergoster~l.~~ 37 Birch XVIIth Internat. Congr. Pure Applied Chem. 1959 Plenary Lectures Butterworths London 1961 p. 73. Birch Blance and Smith J. 1958,4582; Mosbach Acta Chem. Scand. 1960,14,457. ss Raistrick and Simonart Biochem. J. 1933 27 628; Tanenbaum and Basset Biochem.Biophys. Acta 1958 28 21, 247; J. Biol. Chem. 1959,234 1861 ;Bu’Lock and Ryan Proc. Chem. Soc. 1958,222. 40 Birch Elliott and Penfold Austral. J. Chem. 1954,7 169; 1956 9 95. Snell Birch and Thomson J. Amer. Chem. SOC.,1960,82,2402. 42 Birch English Massy-Westropp Slaytor and Smith J. 1958 365; Chem. andInd. 1957 204. 49 Dauben Ban and Richards J. Amer. Chem. SOC.,1957,79,968 1000. Alexander Gold and Schwenk J. Amer. Chem. SOC.,1957 79,2967,4554. The C-methylation of phenolic rings through reaction with a methyl cation is not surprising and has laboratory analogies; reaction with an isolated double bond is surprising. The closest analogy for the latter is the alkylation step involved in terpene synthesis which involves Me& =CHCH2+produced from the isopentenyl pyr~phosphate.~ It is however curious if alkylation of a double bond does occur that the methyl group introduced into a polyketide invariably appears on a carbon-derived from methyl of acetic acid even when a considerable proportion of the “acetate” oxygen has been reductively re- moved.This suggests that the more usual process is alkylation of a phenol or /%polyketone intermediate. As noted above the overall result of this process is in many cases structurally the same as that of direct introduction of a “propionate” unit but the processes are not equivalent (see e.g. Thomas&). The fact that orsellinic acid (V)can act as a precursor of mycophenolic acidas (XXII) is a further convincing demonstration of this.The mould tropolones ap- parently arise from four acetic acid and one C1unit,” but the intermediates are not yet known; they couId be related to benzenoid compounds of the types just considered. C-Methylation from methionine has also been shown to occur in some branched-chain sugars from antibiotics noviosea (XXIV) and cladino~e~~ (in XXV)being examples. Fairly obvious terpene units occur in the skeletons of a number of mould products. Among the com- pounds into which the direct incorporation of terpene units has been proved by experiments with [l%]-mevalonolactone are fuscinsO (XXVI) auroglaucinsl (XXVII) echinu1id2 (XXVIII) elymoclavine (XXIX; R = OH) and agroclaviness (XXIX; R = H) and mycelianamides4 (XXX).An interesting feature of the biosynthesis of such “mixed” com- pounds is that addition of labelled mevalonic acid to a culture introduced labelling only into the terpenoid portion of the molecule whereas labelled acetic acid introduces labelled carbon atoms into both the ter- penoid and the acetate-derived portions. Examina- tion of mycophenolic acid produced after varying periods of time by re-flooding the mycelium of Penicillium brevi-compactum showed the [14C]acetic acid is introduced initially most rapidly into the 4b Thomas Proc. Chem. SOC.,1959 88. ‘* Birch. Fryer. Ryan. and Smith. untmblished work. PROCEEDINGS acetate-derived ring system but the label in the ter- penoid chain builds up rapidly and eventually con- siderably preponderates.& The positions labelled in the terpenoid chain are those to be expected from the previous work on the incorporation of acetic acid into terpene units.The results indicate that molecules of this type are probably built up in the form of separate fairly large pieces which are then joined together and possibly later modified. Further aspects of this subject are considered below. (XXVI) 8 (xxvll)= * OH Biosynthetic Intermediates.-Theories and experi- ments of the type outlined above often successfully define the ultimate precursors and the positions of their incorporation in the molecule. They are not so successful in defining sequences of reactions al- though they give a good general idea of the processes involved.For compounds derived by direct cyclisa- tion of poly-p-keto-acid chains the first relatively irreversible intermediates are probably cyclic corn- pounds all other intermediates probably being enzyme-bound and reverting readily to the original 47 Richardsgnd Fkrretti Biocneh. Bhphys. Res. Comrn. 1960,2 107; Bentley ibid. 1960,3,215. 48 Birch Cameron Holloway and Rickards Tetrahedron Leffers 1960 No. 25,26. ID Vanek personal communication. so Birch Ryan and Smith unpublished work. I1Birch Schofield and Smith Chem. and Ind. 1958 1321. Birch Chem. Weekblad 1960,44 56; Birch Blance David and Smith J. 1961 3128. 6a Birch Blance Smith Smith and Winter unpublished work. 64 Birch English Massy-Westropp and Smith J. 1958 369. 66 Birch and Cassera unpublished work; cf.ref. 52. JANUARY1962 activated units. In such cases there is more meaning to an enquiry in terms of the sequence of reactions involved than in terms of intermediate substances. Presumably in a complex case there is at least a sequence of reactions such as ring closures dehydra- tions and aromatisations even if no intermediate compounds can be detected in the sense of relatively stable substances which are released or passed from one enzyme system to another. Evidence that enzymically bound chains of some sort exist comes from the fact that what is obviously the same large basic unit can be elaborated in different ways. A con-vincing example is provided by comparison of fusarubin (XXXI) fulvic acid (XXXU) and citro- rnycetin (XII) which could clearly come from the same branched skeleton (XXXUI).o*; U 111 111 (xxxii) The all-or-nothing effects of mutating Penicillium islandicum on the production of anthraquinonoid (acetate-derived) compoundsm appears to show that no irreversible partial intermediates exist ;and unless the biosynthetic process produces complete mole- cules by an irreversible step such as cyclisation any portion of the molecule elaborated merely dissociates into its components. With the discovery of the im- portance of malonyl-coenzyme-A containing a carboxyl group an attractive hypothesis is that the units are attached to orientated active centres on the enzyme by salt formation esterification or other appropriate reaction (see scheme; HSR =coenzyme-A) in a sequence of reactions proceeding to the right.Ring-closure by aldol condensation in particular could then produce cyclic non-aromatic inter-mediates (e.g. XXXN) which might be relatively stable. In fact several compounds of the dihydro- hydroxybenzene type have been isolated for example (XXXVI)s7which is clearly produced by reduction dehydration and decarboxylation of a precursor cxxxv).The dehydration of compound (XXxrV) probably occurs readily but it may nevertheless require an enzyme; furthermore the cyclisation may also be readily reversible since attempted dehydra- tion of the condensation products of ketones and f acetoacetic esters normally leads in the laboratory to substantial reversal of the condensation.The irreversible stage necessary to produce a stable pro- duct may well be a dehydration of this type. In the formation of phloroglucinol derivatives the ring closure itself may well be the irreversible stage since aromatisation would then merely require enolisation which would be expected to occur spontaneously. (xxx vI) \ Once a relatively stable intermediate is produced it is then technically much easier to pursue the quest4Qn of other relatively stable intermediates. To illustrate the subject further it is worthwhile to look at several of the best-investigated cases. Griseofulvin. This substance (X) produced by a strain of Penicillium griseofulvum is evidently from inspection formed from seven acetic acid units6 and this has been confirmed by tracer The methoxyl-methyl groups come as expected from the C1pool and the chlorine must be introduced by substitution at some stage.The obvious intermediate M Ehrensvard XVnth Internat. Congr.Pure Applied Chem. 1959 Plenary Lectures Butterworths London 1961. 57 Dalton and Lamberton AusrraZ. J. Chern. 1958 11,46. PROCEEDINGS produced by two cyclisations of one chain would be the benzophenone (XXXVII and following sugges- tions of Barton and Cohenm on the free-radical cyclisations of phenols by oxidation Scott and his collaborators59 obtained dehydrogriseofulvin (XXXVIII) by ferricyanide oxidation of this benzo- phenone (XxXvrI). That this is probably a genuine intermediate is shown by the fact that P.griseofulvum can convert it into griseofulvin.Other stages in the sequence have been determined by workers at Glaxo Limited,6O partly by feeding aminopterin (which can act as a methylation or oxidation inhibitor) which afforded the dimethyl ether (XXxrX) as the Grst 000 I t H02C ’1 (+3Me€=) *Me6 \ n t n Me0 f?M?O (CO (XXxvlI)+ Isolated detectable precursor. They conclude that the stages involved are as shown from (XXXIX) onwards. We are tempted to speculate further by another very important result obtained by these workers that under more drastic conditions with aminopterin no griseofulvin is produced at all; 6-methylsalicylic acid results instead. Unless aminopterin has some hither- to unknown biological activity in this case the inference is that methylation is necessary to consum- mate production of the molecular skeleton.If this is so then a possible sequence of reactions is as annexed and it can be inferred that the phloro- glucinol ring closure does not take place in the absence of methylation as shown the acetate units of the remaining chain then dissociating and the ring- carbonyl group being reduced. Predictions can be made on this basis for example that the tetra- hydroxybenzophenone is never formed and that the 6-methyl ether (XVII) of orsellinic acid may well be incorporated if a mechanism exists for its biological activation. It is interesting that the last compound is knowna to be the biochemical precursor of penicillic acid (XVIII).Mycophenolic acid.-This interesting substance (XL) from Penicillium brevi-compactum could by inspection arise from the series of changes shown although no prediction could be made about the exact sequence involved. Much of this scheme has been proved by tracer incorporations. The aromatic and lactone rings arise from acetic acid in the ex- pected way as shown by degradations of the pro- ducts obtained by incorporation of both [I-l4C]- and [2-14C]-acetic acid?’ It is not certain that the aro-matic precursor has a C3 side-chain (e.g. XLI) although such substances occur in strains of the organism. [5-14C]Orsellinic acid is incorporated with some randomisation of label apparently owing to degradation to [2-1*C]acetic but the incor- poration is poor; this might be an alternative bio- synthetic route.The result does at leqst show that direct alkylation of an aromatic ring can occur. The 0-and C-methyl groups are introduced from methi~nine,~~ and addition of [2-14C]- or [4-14C]-mevalonolactone to the fermentation liquors gives respectively one or two labels in the expected posi- tions of the terpenoid side chain with no label present elsewhere.B1,62 Moreover acetone is pro-duced in equimolar proportion and when [2-14C]- mevalonolactone is the source the acetone contains the same molar activity as the side chain of the mycophenolic acid. Therefore the chain was intro- duced as a geranyl unit originally and the =CMe2 cleaved to acetone and carboxyl as indicated.61 Riboflavin.The dimethylbenzene ring of riboflavin Barton and Cohen “Festschrift Arthur Stoll,” Birkhauser Basle 1957 p. 117. 6D Day Nabney and Scott Proc. Chern. Soc. 1960,285. 6o modes Boothroyd Moria Gonagle and Somerfield persona1 communication; cf. McMaster Scott and Tripett J. 1960,4628. Birch and Cassera unpublished work. Birch and Ryan unpublished work. JANUARY 1962 (XLIV; R = ribityl) appeared to us to present a new problem of aromatic biosynthesis and after con- sideration of possible precursors available and of chemical reactivities we suggested63 that it could arise from two molecules of biacetyl by aldol condensa- tion. As with all such hypotheses an “equivalent” (see ref. 1) or activated biacetyl molecule could be envisaged.In fact an aldol-type dimer (XLII) could be obtained and was condensed with the base (XLIII; R = Me) to give lumiflavin (XLTV; R = Me); later Cresswell and WoodS4 condensed a trimer with ribitylaminoaminouracil (XLIII; R = ribityl) to give riboflavin (XLIV; R = ribityl). P+ Me 2C=CH-CH,-CH,C= CH-CH A \ 101’f I Mevalonic acid t HOwC%-COMe 6MeC0,H,//Me+ Me+’ ‘ [03 \ Met h ion1ne 5 Me-CO2H Me2C:0 0 i Me Biochemical work led to similar conclusions. Masuda had isolated several other substances from the organism Eremothecium ashbyii which produces riboflavin and showed the substance “G’ to have structure (XLV) and “V” structure (XLVI).65He also showed that substance “G’ could be converted both chemically and biologically into riboflavin.Compounds “G” and “V” can be obtained by the action of biacetyl and pyruvic acid respectively on the base (XLIII; R = ribityl). Masuda took these results to imply that the biacetyl molecules add successively to this base compound “G” (XLV) being an actual intermediate. Although this is not implausible we felt that reactivity considerations should favour reaction through a non-aromatic intermediate which would be some kind of deriva- tive of the dimer (XLII). This possibility can be reconciled with the above results if the addition of biacetyl is at least partially reversible as shown in the chart. This probability is increased by the forma- tion of substance “V” from “G” which we believe to be a displacement by pyruvic acid rather than an oxidation.Recent work by PlauP showed that two molecules of substance “G” (XLV) are converted enzymically into one of riboflavin. This result and the others above. can be reconciled with reactivity considerations by a route such as that shown from (XLV) to (XLIV). txull) \ I It has not been possible in this Lecture even to mention many of the substances which we have investigated such as the fully terpenoid compounds gibberellic acid and rosenonolactone the antibiotic novobiocin the ergot-type alkaloids and a number of other mould products derived partly or wholly from acetic or shikimic acid. Structure Determination.-I should like to consider finally the question whether it is possible to reverse the traditional relationship between structure and biosynthesis investigating the latter first and using the results to illuminate the structure.The successful use of the hypothesis with flaviolin 69 Birch and Moye J. 1957 412 2622. 64 Cresswell and Wood J. 1960. 4768. Experimental support for displacement has now been provided by Rowan, Wood and Hemmerich A oc. Chem. Soc. 1961,260. 66 Masuda Chem. and Pharm. Bull. (Japan) 1957 6 28 136; 1958 6,447. Plaut J. Biol. Chem. 1960,235 PC41; cf. Goodwin and Treble Biochem. J. 1958,70 14. eleutherinol etc. as a kind of “isoprene-rule” has been mentioned already. To apply the approach some evidence of origin in these cases from acetic acid was necessary and was derived from partial structures. Similar evidence can however be ob-tained from tracer experiments.No general rules can be given because each case is unique but several examples can be quoted. There is good chemical which in general we have confirmed that the formula of phomazarin is either (XLVII) or (XLVJII). The structure suggests that some acetic acid units at least are involved and incorporation experiments with both [I -lac]- and [2-14C]-acetic acid indicate that there are probably eight of them.6s In particular the carboxyl group is labelled from [2-14C 1-and unlabelled from [l-14C]- acetic acid. If alternate /%labelling occurs proceeding from the fatty side chain only formula (XLVIII) can accommodate these facts (* =14C from *MeCO,H). This result does not prove the correctness of the formula but it certainly suggests that any synthetic work on degradation products should be based first upon it.A more conclusive case is echinulin. When this work was begun the formula so far as it had been determined by chemical was (XLIX). Incorporation of both [1-14C]acetic acid and [2-14C]mevalonolactone showed the presence of three isoprene units two terminating in Me,C=. The formula could thus be expanded to (L) with the dioxopiperazine ring attached to one of the double bonds. Incorporation of 11-laclalanine showed that the dioxopiperazine ring arose in fact from this unit. This formulation was independently reached on chemical grounds,70 and it has now been shown that in fact the formula (LI) contains an extra -CH2- in the 3-position to which is attached the dioxo-piperazine ring.The CZsrather than c28 formula PROCEEDINGS had been suggested to us independently by the quantitative tracer results. The substance is clearly derived therefore by introduction of three isoprene units into tryptophan and formation of the ring with alanine. The lund of approach should be particularly useful with fully terpenoid compounds. The anti- biotic ple~romutilin~l is the glycollic ester of a substance C20H,,03 shown by infrared spectra to contain a vinyl group. This evidence suggests a di- terpenoid skeleton. We have confirmed this con- clusion by incorporation of [l-14C]acetic acid and ozonolysis one-eighth of the molar activity appear- ing as formaldehyde ;mevalonolactone is also incor- porated as expected.72 Tn such cases (and others) it is possible in theory at least to limit the number of possible positions for substituents (OH =0,etc.) by determining whether the carbon atom to which they are attached is labelled or not using if possible the substance derived from more than one precursor since the distribution of labels in the primitive terpene chain is known.Some progress has been made in this field,” which is largely dependent on devising methods of examining the radioactivities of the atoms in question. Other applications can also be foreseen for example by use of [14C,180]acetic acid it should be possible for an unknown structure derived from 67 Kogl Wessem and Eisbach Rec. Trav.chim. 1945,64,23. 68 Birch Fryer Thomson and Smith Nature 1961,190,44; Birch Butler and Rickards unpublished work. 69 Quilico Cardani and Piozzi Gaztette 1955 85 3; Cardani Gasnati Piozzi and Quilico Tetrahedron Letters 191509 No:161. Quilico personal communication. 71 Anchel J. Biol. Chem. 1952 199 133. 72 Birch Cameron Holzapfel and Rickards unpublished work. JANUARY 1962 this source to determine how many oxygen atoms are relics of carboxyl groups and how many are “introduced” l60 thus limiting the possible posi- tions in both cases. This kind of approach must necessarily be used in conjunction with the chemical work which it should greatly assist particularly in the field of antibiotics. I have tried to show how the organic chemist by considerations of structure and mechanism can extrapolate the results of the biochemist into new or more complex fields.1 have tried to indicate the limitations of the chemical approach but to suggest that it can form a basis for further biochemical work and particularly with the acetic acid and related theories to show how whole fields of natural pro- ducts can be reduced from structural chaos to ordered array. I believe that this pattern of inter- action between chemist and biochemist will recur repeatedly in molecular biology and that the chem- ist will in particular be required ultimately to elucidate the detailed chemical mechanisms first of coenzyme action and then of enzyme action. I should like to thank my many enthusiastic col- laborators especially Dr.Herchel Smith and Dr. R. W. Rickards who have contributed much hard work and many new ideas. THE ETHEL BEHRENS BEQUEST THECOUNCILis pleased to announce the establish- ment of a new trust fund which owes its existence to a bequest made to the Society by the late Miss Ethel Behrens. The fund will be employed to assist under- graduate Fellows to attend Meetings and Symposia organised by the Society. Miss Ethel Behrens was the daughter of the late Henry Behrens of 34 Gloucester Square London. She died in London on March 14th 1960 in her -0th year. From her earliest youth she was fascinated .)y colour and later this developed into an interest in the history of pigments and in the study of their extraction from natural sources and their synthesis.She travelled widely in Britain and on the Continent in order to visit laboratories and factories where dyes and pigments were developed or manufactured; France she visited so frequently that she regarded it as her second home. She was elected a Fellow of the Society in 1947 and for a number of years was a familiar figure at all its lectures and social events. She was also a member of the Society of Chemical Industry The Oil and Colour Chemists Association and other scientific bodies. In her will Miss Behrens directed that her bequest should be devoted to the payment of travelling expenses and the Council has decided to establish a fund to be known as the “Ethel Behrens Fund’’ from which grants will be made to enable undergraduate Fellows of the Society to attend the Anniversary Meetings and Symposia arranged in conjunction with them.The first awards will be made in con-nexion with the Anniversary Meetings in 1963 and a detailed announcement will be made in due course. Miss Behrens was keenly interested in youth and particularly in young students of chemistry and it is believed that the scheme proposed by the Council would be the one that she would have wished more than any other. THE ROYAL INSTITUTE OF CHEMISTRY MONOGRAPHS FOR TEACHERS No. 1 Principles of Electrolysis by C. W. Davies (3s. 6d.). No. 2 Principles of Oxidation and Reduction by A. G. Sharpe (3s. 6d.).No. 3 :Principles of the Extraction of Metals by D. J. G. Ives (6s.Od.).No. 4 Principles of Metallic Corrosion by J. P. Chilton (6s. Od.). No. 5 Principles of Chemical Equilibrium by P. G. Ashmore (4s. 6d.). P. J. HAWS,and W. C.A. HARDS(EWELL TECHNICAL Reviewed by 0.J. CHILTON COUNTY COLLEGE, SURREY) THEestablishment of the Royal Institute of Chem- istry Fund for the Development of Education in Chemistry has made it possible to publish this series of monographs on selected well-defined topics. The aim of the series is to aid teachers of chemistry at G.C.E. “A” level and above and to a smaller extent to help more advanced students. Apart from those teachers concerned solely with “A” level this aim is largely achieved-certainly those teaching students to Higher National Certificate Degree or G.R.I.C.standard will find the series interesting and very useful in the preparation of lecture notes but generally the treatment is rather beyond the scope of chemistry required in schools. Since each monograph endeavours to treat its own subject independently of the rest of the series there is inevitably some overlap but this is not without advantage for each mono- graph may be studied without reference to others in the set. For students commencing a serious study of electrochemistry it is encouraging to have the I.U.P.A.C. system clearly defined and a table of standard electrode potentials given as in C. W. Davies’s “Principles of Electrolysis,” especially in view of the confusion existing in the sign conven- tions of electrochemistry.Sections I and I1 of this booklet are a good introduction to the topic through the general principles and electrolytic conduction. Section III introduces electrode reactions and elec- trode potentials leading to the concepts of decom- position voltage and overpotential and even with- out a knowledge of thermodynamics it is possible to appreciate this section. Well chosen examples of electrolysis are discussed in Section IV and it is a pleasure to see simplified mechanisms suggested for the lead accumulator and the Hall-Heroult process rather than the usual involved and improbable mechanisms encountered in many text-books. A. G. Sharpe’s “Principles of Oxidation and Reduction” is one of the monographs which should find a place in school teaching particularly because Dr.Sharpe treats oxidation and reduction from the electron-transfer standpoint and illustrates this with many examples throughout the text. These are mainly limited to inorganic systems The omission of organic examples may be justified in the quantita- tive treatment of oxidation-reduction but more reference should have been made to organic chem- istry when dealing with the electronic theory of these processes. It is regrettable that whilst on the one hand the Royal Institute strive to introduce oxida- tion numbers into the teaching of chemistry it is hardly mentioned in their own monograph on oxida- tion and reduction. Surely this was the opportunity to bring the case for the oxidation number approach to the attention of teachers.On page 1 a qualitative picture of the redox series is given and this early introduction enables the quantitative aspects of later sections to be appreciated more easily. Very little is mentioned about the choice of redox indicators. The sign convention used is again that recommended by the J.U.P.A.C. and a table of standard redox potentials is given for forty- five systems. Some slight discrepancies are noted between the values given here and those in the first monograph Davies (No. 1) Cu2+,Cu+ E” = $0.16 v Sharpe (No. 2) Cu2++e=Cu+ E” = +0.15 v In conclusion Section IV dealing with oxidation PROCEEDINGS and reduction in gaseous and solid states and in non- aqueous media suffers from being rather too con- densed but it should stimulate further reading.The extraction of metals is probably among the first aspects studied in inorganic chemistry but too often such studies are unrelated to the physical prin- ciples involved. In Monograph No. 3 on the “Prin- ciples of the Extraction of Metals,” D. J. G. Ives believes that a course on this subject is introduced with great benefit only after an adequate background of physical chemistry has been established. Provided the reader already has some grasp of chemical thermodynamics this book is interesting and does its job admirably. However the thermodynamics given in Sections I and I1 is barely sufficient. A second-year degree student would have enough background to be able to make good use of this monograph and teachers of inorganic chemistry for courses above “A” level standard will find the work of value.In dealing with the thermodynamics of pyro- metallurgical processes the provision of Ellingham diagrams plus good examples of their use is appreci- ated since such diagrams are difficult to locate in the readily available literature. Another useful feature is a table summarising the methods used in evaluating dG as a function of temperature. Unfortunately so much space is devoted to the pyrometallurgical pro- cesses that the theoretical background to electro- chemical and hydrometallurgical processes is badly neglected. The sections entitled “The Choice of Extraction Methods and Some Typical Processes” are very condensed and do not add anything to the work found in standard text books although a col- lated summary is valuable.Students of metallurgy should find this booklet helpful in relating their studies to the purer chemical aspects of the extrac- tion of metals. Once again a divergence must be noted between the values and the representations used in the four monographs published Davies (No. 1) Ni2+ Ni E” = -0.25 v Sharpe (No. 2) Ni2++ 2e = Ni E” = -0.25 v Ives (No. 3) Ni NiZt E” == -0.23 v Chilton (No. 4) Ni2+/Ni E” = -0.25 v This difference in representation of the same process is confusing and it is a pity that all the authors could not standardise on a common system in this series of monographs. Sharpe’s clear repre- sentation is to be preferred and it is noted that the method used by Ives does not follow I.U.P.A.C.rules. The fascinating and important topic of the cor- rosion of metals is often regarded as rather too metallurgical and so is neglected in pure chemistry JANUARY 1962 courses. However J. P. Chilton’s “Principles of Metallic Corrosion” (No. 4) establishes quite clearly the need for a study of chemistry to include metallic corrosion. Section I considers the corrosive action of gases (air and oxygen) and deals with the laws governing the rate of oxidation of metals and the mechanism of oxide film growth. Wet corrosion or corrosion in aqueous solution is covered in Section 11 and naturally occupies the majority of the monograph covering electrochem- istry and corrosion corrosion cells aeration dis- solution of metals in acids alkalies and neutral solu- tions.The concluding Sections (HI and IV) are devoted to prevention of corrosion and further aspects such as stress effects and corrosion fatigue. Fifteen effective lecture demonstrations are described by Dr. Chilton each of which may be per- formed quite easily with simple materials. Further these experiments range over the whole topic of cor- rosion and would provide a very suitable accompani- ment to a series of lectures drawn from the text. Owing to the specialised nature of the subject matter this book is obviously more suitable for studies at or beyond second-year degree level. Teachers at all levels however will find many interesting features in this well written monograph.The introduction to “Principles of Chemical Equilibrium” by P. G. Ashmore follows a sound approach by considering free energy in relation to the equilibrium equation. Section I deals with energy changes and conditions for equilibrium and is mainly concerned with the thermodynamic study of energy changes. The conditions for equilibrium and spontaneous change are clearly stated in terms of free energy with several well-chosen examples. Section 11 Chemical Equilibrium in Real and Ideal Systems discusses the derivation and functions of equilibrium constants for some very useful systems although heterogeneous reactions receive little attention. Some of the material contained in the Appendices could with advantage be included in this section.In the third Section Dr. Ashmore gives a very clear critical survey of the various methods for the determination of equilibrium constants. A minor misprint occurs on page 35 where the number of equilibrium moles of hydrogen should read (1 -cc). It would have been helpful in teaching had some demonstrations been described although teachers at the G.C.E. “A” level will find useful ideas in this monograph but generally the standard is well above this level. The series has a great deal to recommend it although it does not fulfil one of its aims which was specifically to help teachers at G.C.E. Advanced level. It is a good thing for such a series to have a common set of symbols nomenclature and con- vention.The Royal Institute of Chemistry should seriously consider including in each monograph a list of symbols which they recommend. CHRISTMAS COMPETITION 1961 THIS Competition inspired by the second edition of J. E. Gowan and T. S. Wheeler’s “Name Index of Organic Reactions,” invited brief definitions of the nature and scope of any three of the following Eve’s method; Picasso replication ; Adam’s reaction; Miss Arden’s colour test ;* Cain’s reagent; Busoni transposition ; Borgia solution; Methuselisat ion. Nineteen entries plus one not for competition were received. Many were long in absence of a direct limit and we ask competitors to accept our assurance that ruthless selection does not imply lack of appreciation. Eve’s method This proved unexpectedly difficult in spite of several appeals to malic acid.On another tack P.J.C.S. interpreted the method as “subterfuga- tion,” and N.M.C. combined two allusions neatly in “See Fig. overleaf” (regrettably not provided). Adam’s reaction provoked much ingenuity. “Surprise and sin” (M. Halva) was a surprise answer; “reluctant acceptance by a primary agent of a malic acid derivative” (D.B.) a more straight-forward one. F.W.C. ingeniously invented “fem- mealdehydes,” and I.A.W. had a neat chemical study in “a reaction of a Primary One which leads to a fall in exposed surface area with consequent shielding against attack by the elements; catalysed by malic denudase and promoted by ser-pentene.” G.H.H. gave full references in entries too long for full quota- tion which included Adam’s reaction as a “major step in a reaction series initiated by a homogeneous reaction-with-rearrangement1” and involving “photo- sensitisation2 eventuated by applied absorption?’ We expected coupling of Eve’s method with Adam’s reaction but this did not often occur.However J.C.S. suggested that “the product from Eve’s method (4. Y. 1 provided its specific activity exceeds * Tt was possibly unfair to some readers outside the United Kingdom not to have explained that Elizabeth Arden is a leading British women’s beauty specialist. Gen. ii 7 (B.c. 4004). Gen. iii 7. Gen. iii 6. PROCEEDINGS 12 millihelens (Dr. Faustus 1588) excites suitably polar molecules to an activated state”; M.J.S.D.gave an ingenious reaction mechanism with an “un- usual unimolecular initiation M = M + F” and continuing “M + F = MF MF = M + F*” etc.; and M. Tussaud described Eve’s method as “pomiferation recorded (often in footnotes) as X X X and designed to effect the reaction ?+8=Q8+0+00+... with a useful variation involving a saccharine Pa (described in modern nomenclature as a lolly pop);” to this was coupled Adam’s reaction-“a back-reaction termed dissolution 93 = 9s; + &;.” For Cain’s reagent the neatest suggestion was simply “Stickstuff” (N.M.C.). “Sugar-Team,” from Prague gave a very useful recipe “Dark brown powder (composition not given) evolving black smoke at a temperature 36.541”~ (25 g 31/-). Especially convenient for younger scientists.If some- body is exagerating his own results the smoke is falling down; if he is telling truth the smoke is rising up (very seldom observed until today).” (Cain seems in part to have anticipated and improved on Sir Walter Rayleigh.) Leaving this family but sticking to crime our entrants had fun with Borgia solution though its composition seemed uncertain steel + hemlock Bella Donna corrosive sublimate + sugar of lead dilute alcoholic strychnine hydrocyanide and tri- valent arsenic were all claimed. I.A.W. chose the mathematical interpretation of “solution” in his “liquidation of Pope’s Agents”; F.W.C. gave us “cleavage at the pope-tide link”; and J.E.H. described its purpose as “removing unwanted blemishes-unfortunately often the lady’s lovers”.According to A.G.L. “it has been recommended as a means of maintaining first-order kinetics in systems of unstable equilibrium”; it is also useful for “elimination of interfering functional groups” (M.J.S.D.) and “elimination of free radicals by means of scavengers” (G.B.B.). Miss Arden had a large fan-mail. J.N.F. says simply “Mary SHAKES and PEERS”. From others we hear that it “gauges the reactions of keytones under conditions of varying pressure unfortunately rarely performed under laboratory conditions” (D.B.) and “tests the reactivity of natural products in the male sex hormone series yielding ring com- pounds often with diamond-like structures (see Bachelor’s Reduction)” (D.W.) ; and M.Tussaud assures us that the following is a TV jingle to the tune of Three Blind Mice Beauty and the Beats Biebrich Scarlet Our top starlet Palladium streaks in her Ponceau hair While Eosin lips fluoresce and dare. The I.C.T. men from Blackley stare At Biebrich Ann. (envoi) But Annie got’er man. The Busoni transposition was a tougher nut. G.A.L. related it to the Boosey-Hawke rearrange- ment and D.W. gave its synonym as “chromatic substitution of C-groups by B-groups” ; both gave clever technical expositions unfortunately too long to quote. But we have room for G.B.B.3 “adapta- tion reaction for ketones RR’CO -+ kenotes” and M.J.S.D.’s “first applied to the Benzene Ring for the Aromatic Sextet.” Picasso replication was equally hard to do well but we liked “use of an oxidised Schiffs Base to induce ‘I’ strain” (G.B.B.) and “a method for syn t hesisin g distorted molecules” (D.W.\.Many interpretations of methuselisation included a half-life of 4.845 x 102 yr. but we shall mention the more recondite “A method applied particularly to gums in unlabelled flasks; an extension of micawberisations and the maiiana process” (G.A.L.) ; “exhaustive methylation discovered in US. at EZizabeth College” (N.M.C) ; our Prague friends’ “Every reaction when a mixture is to be refluxed for 500 years; for details see this Journal Nov. 2461 and later on” gave us great pleasure and was brief. Irresistible is an entry from P.O.L. of Copenhagen “A method used by a subordinate (methuselisa- tor) when he is not too interested in performing the investigation (methuselisate) proposed by his superior (methuselisant); the motive for meth-uselisation can be that the methuselisator (1) is lazy (2) thinks that he has more important things to do or (3) thinks the methuselisate is silly.Methuseli- sation may fail because (1) the methuselisator is a bad methuselisator (2) the methuselisant takes a strong interest in the methuselisate or (3) there are too many methuselisates to avoid them all.” Before adjudicating we must thank G.A.L. for “misreading” a question and giving us “Cahn’s reagent :a red caustic liquid employed in reductions; some authors* think it of only marginal utility,” and M.P.B. for “Michael extraction an author-reaction induced by catalytic quantities of blue pencil.” M.P.B.was in a close run for the prize for the best set of three and we reproduce two of his “Borgia solution A combination of two solutions ‘Prolyx B. Autolycus “Publish and Be Damned” (unabridged) Upper Common Room Binders United Oxbridge U.P. JANUARY 1962 (cf. Fehling’s) (A) hemlock and (B) steel is used fallen into disuse. Time preferably in years is according to the Machiatrelli Principle to purge the treated with giberellic acid and eonised by the B.R. body politic. It is awkward to apply and often leaves process which extends the periodic intervals to stains on the hands. For large-scale use it has been inordinate length. replaced by fluidisation (liquidation).“Miss Arden’s colour test The application of “Busoni transposition A low-probability re-colours as a catalyst for the combination of organic arrangement of the symphonic nucleus involving the complexes. Has been known to yield explosive replacement of a string quartet (‘the a-particle of reactions in parents when applied at a too early music’) by four strange particles with disturbance stage. of the energy levels and consequent high-intensity “Eve’s method An application of the so-called emission of unusual wave form (see Stravinsky ‘Le Miss Arden’s colour test (q.v.) originally utilising Scare du Printemps’).” malic acid esters and serpentine as initiator. Now The prize we allot to J.R.D. for his astringent generally modified for low-intensity illumination.definitions strictly to pattern Can give fast reactions at elevated temperatures lead- “Methuselisation A long-established process ing to ring closure and a single bond.’’ COMMUNCATIONS The number of Communications offered for publication continues to increase and the space available is limited. In order that as many as possible may be accepted the Publication Committee urges authors to be brief. Text diagrams formulae equations and tables must be restricted to what is essential to an understanding of the main discovery; physical properties must not be given for normal intermediates in a synthesis or degradation ; minor points and side-issues must be excluded. Rotational-Vibrational Energy Transfer By T. L. COTTRELL and A. J. MATHESON (DEPARTMENT THEUNIVERSITY, OF CHEMISTRY EDINBURGH) WE previously reported1 that the vibrational to lengthen the relaxation time while the decrease in relaxation time of tetradeuteromethane at 298OK was the lowest vibration frequency tends to shorten the longer than that of methane and suggested that the relaxation time.Calculation of translational-vibra- value observed for methane might be too low. We tional energy transfer probabilities by standard have now made further measurements on these two methods shows that the latter effect predominates. compounds using samples purified in a modified But the decrease in the classical velocity of rotation Clusius-Riccoboni2 low-temperature fractionation of the peripheral atoms in going from methane to column.The values of the overall vibrational relaxa- tetradeuteromethane is much greater than the corres- tion times observed were methane 2.0 x sec.ponding decrease in the translational velocity. Thus and tetradeuteromethane 3-9 x lo-‘? sec. The if vibrational energy transfer in collisions were former result is only slightly longer than other caused by the interaction of a rotating molecule with reported value^,^ while the latter agrees with our the lowest bending vibration the lower peripheral previous value. This confirms that the vibrational velocity of tetradeuteromethane would more than relaxation time of tetradeuteromethane is longer counterbalance the effect of its lower vibration fre- than that of methane. quency leading to a longer relaxation time in tetra- The usual theories of translational-vibrational deuteromethane than in methane as observed.This energy transfer predict the opposite result. There are suggestion that energy transfer in collisions can be two opposing effects in going from methane to tetra- caused by rapidly rotating molecules could also deuteromethane the increase in mass causes a explain why methane has a much shorter relaxation decrease in the average relative velocity which tends time than expected from the Lambert-Salter plot.* (Received November 20th 1961.) Cottrell and Matheson Proc. Chem. Soc. 1961 114. Clusius and Riccoboni 2.phys. Chem. 1938 B 38 81. CottreU and McCoubrey “Molecular Energy Transfer in Gases,” Butterworths Scientific Publns. London 1961. Lambert and Salter Proc. Roy. SOC.,1959 A 253 277.PROCEEDINGS Novel Reactions in the Synthesis of New Organosulphur Compounds By B. SAVILLE (THENATURAL PRODUCERS’ ASSOCIATION, RUBBER RESEARCH WELWYN HERTS.) GARDENCITY RECENTLY~ it was shown that thiouronium cations (I) may undergo nucleophilic substitution by solvent or added reagent (X-) according to the stoicheio- metry X-+ R-S*C(:NH,+)NH,+ X-R + S:C(NHJ2 (1) and that reactions of this class probably occur via the SJ mechanism when R is potentially a well- stabilised carbonium ion. Practical use has now been made of this in the synthesis of new organosulphur compounds im-portant in the study of the reactions of 2-methylpent- 2-ene with sulphurating reagents. Thus when S-l,3-dimethylbut-2-enylthiouronium bromide2 (as I; R = CHMeCH:CMe,) (0.5 mole) was heated at 70”for 15 min.with sodium thiosulphate (0-75mole) in 1 :2 methanol-water (300 ml.) the thiouronium cation was completely decomposed’ ,the pH dropped to 3 and only a trace of sulphur was deposited. It is assumed therefore that the reaction Sz032-+ RS*C(:NH,+)NH + RS-SOs-+ S:C(NHJ had largely occurred uncomplicated by serious corn-Saville. Proc. Chem. SOC.,1961 214. Saville;J. submitted for publication. peting solvolysisl of the thiouronium cation. After extraction of covalent impurities by chloroform and petroleum the resulting aqueous solution when treated with sodium sulphide (0-25mole),3 gave bis- 1,3-dimethylbut-2-enyI trisulphide (62%) according to the reaction S2-+ 2RS-S03-+ RS-S-SR + 2S032-.The product was 98 % trisulphide and contained 2% of the corresponding di~ulphide.~ When the alkenylthiolsulphate solution as pre pared above was treated with propane-2-thiol (0-375 mole) and sodium hydroxide (0.375 mole) in 50 % aqueous ethanol (200 ml.) at room temperature there was immediately obtained lY3-dimethylbut-2- enyl isopropyl disulphide (65 %) PriS-+ RS.SOS-+ PriSaSR + SOs,-Only minute traces of the symmetrical disulphides were found in the alkenyl alkyl disulphide. Mr. M. B. Evans is thanked for performing gas-liquid chromatographic analyses. (Received October 30th 1961.) Milligan Saville and Swan J. 1961 4850. * Evans Higgins Saville and Watson J.,submitted for publication. Nucleophilic Displacements by Thioanions on Trisulphides By M.B. EVANSand B. SAVILLE (THENATURAL PRODUCERS’ ASSOCIATION, RUBBER RESEARCH WELWYN CITY,HERTS.) GARDEN Fossf has interpreted many of the reactions of polythjonates and polysulphides with nucleophiles (e.g. SO,” CN-) in terms of displacements of the terminal potentially-anionic groups from central sulphur atoms y-e SXPX -Y-sx + x-**....(I) This seems reasonable particularly where X-is a well-stabilised entity (e.g. S*S03- as in Pent+ thionate) and is less nucleophilic than Y-towards sulphur. However in general it is necessary to con- sider whether an alternative displacement is possible, i.e. For example application of Foss’s mechanism (1) to the alkylthio-anion (RS-)reacting with a simple dialkyl trisulphide (RS-S-SR)leads one to expect establishment of thiol-trisulphide interchange equi- libria involving displacements of thio-anions having stabilities similar to those of the attacking entities R’S-+ RS-S*SR + RS-S-SR’ + RS-...(3) ~5-+ RS.S.SR’ + R’S.S.SR’ + RS-. . . (4) we now suggest primary displacement on a terminal sulphur atom as a likely alternative to schemes (3) or (4) since in this case a perthio-anion (RS-S-) would be released -y-0 &-)( y-x + ’S-x ........a /+ R’S-~SR-S-SR R’S~SR+ RS-S-...(5) \ 1 Foss el. norske Videnskab. Selskabs Forh. 1943,16 No. 20 72. JANUARY 1962 and on reasonable theoretical grounds RSW should be better than RS- as a leaving-group from sulphur. Unequivocal evidence has now been obtained for reaction (5) with R = R' = Et.On examining di- ethyl trisulphide (0.2~) in ethanethiol in the presence of piperidine (0.4~) by quantitative gas-liquid chromatography it was found that contrary to equa- tions (3) and (4) which predict no net observable change in the system one rapidly (3 min. at 25") obtained two moles of diethyl disulphide and one of piperidinium hydrosulphide per mole of trisulphide in accordance with the stoicheiometry EtS-S-SEt + 2Et*SH+ 2EtS.SEt + H,S which is derived rationally from displacement (5) (R = R' = Et) followed by EtS-? SETS-EtSeSEt + S2-In the absence of base no detectable decomposition of the trisulphide could be observed during several hours. Reaction of bis- 1,3-dimethylbut-2-enyl trisulphide2 with propane-2-thiol catalysed by piperidine yielded approximately one mole each of 1,3-dimethylbut-2- enyl isopropyl disulphide di-isopropyl disulphide * Saville preceding communication.and 1,3-dimethylbut-2-ene-l-thiol,per mole of initial trisulphide RS.S.SR-t RSSPri + PriSSPri + R-SH(+H,S). This stoicheiometry which is easily explained on the basis of initial displacements according to scheme (5) is inconsistent with (3) and (4). However in the early stages of this reaction a very small quantity of di-isopropyl trisulphide was detected showing that the thiol-trisulphide interchange (3) and (4) is a minor competitor with (5). The above products are not the result of further thiol-disulphide inter-changes which are very much slower than the tri- sulphide reactions now under discussion.These reactions written formally above in terms of free ionic entities proceed easily in non-polar solvents (e.g. heptane) and may be better expressed as occurring in cyclic assemblies which present a non-polar periphery to the solvent and allow little overall charge separation in the transition state \/ ,N H uH -364, S I (Received October 30th 1961.) The Reaction of Tropine with Benzoyl Chloride and Alkali A Novel Hydrogen Transfer Reaction By BARBARA and J. D. HOBSON J. CALVERT (CHEMISTRY DEPARTMENT BIRMINGHAM) THEUNIVERSITY STANDARD procedure for the benzoylation of tropine (I) involving treatment with benzoyl chloride alone has long been known1to give the hydrochloride of the corresponding ester (11) in high yield.However observing that coloured products are often formed in basic media. we examined the mixture resulting from the reaction of an excess of benzoyl chloride and aqueous sodium hydroxide with tropine and have isolated 2,4-di benzylidenetropinone (IV) in yields of up to 45% (based on tropine) depending on conditions and the quantities of benzoyl chloride used. The origin of this compound was revealed on closer investigation of the products obtained after a limited reaction time when significant amounts of tropinone (111) and benzaldehyde were found to be present. The dienone (IV) m.p. 152* is rep~rted~,~ to be the only unsaturated ketone formed by acid- or base-catalysed condensation of tropinone with benzalde- Barrowcliff and Tutin J.1909 1966. * Willstatter Ber. 1897 30,731 2716. Davies Jones and Pinder J. 1960 3504 hyde but small quantities of a second isomer m.p. 103O having an almost identical ultraviolet spectrum b Ph*CO( -OH' vu '0 (IV) --. Ph-CO N were also obtained in the present case. This appeared to be a less stable geometrical isomer probably formed during isolation by the action of light and it was quantitatively converted into the higher-melting compound by hot acetic acid. An equilibrium mixture of the two was obtained by irradiation of a benzene solution of either pure isomer with ultraviolet light. The formation of tropinone (III)and benzaldehyde from tropine (I) under the conditions indicated may be the consequence of hydrogen transfer and we favour an intramolecular mechanism involving the intermediate N-benzoylammonium cation (V).An intermolecular transfer either to an acylammonium cation or to benzoyl chloride itself seems unlikely since no similar reaction was observed with either +-tropine (VI) or N-benzoylnortropine (VII). Al-Klages and Zange Annulen 1957,607 35. PROCEEDINGS though the cation (V) can have only a brief existence in aqueous alkali the powerful electrophilic pro- perties of trialkyl-N-benzoylammoniumsalts,4 and the favourable proximity of the hydrogen atom in the conformation shown evidently combine to facilitate the hydrogen transfer. Alkaline conditions are pre- sumably necessary not only to assist the removal of the proton from the hydroxyi group but also to prevent the latter from being permanently masked by ester ifica t ion.We thank Professor M. Stacey F.R.S. for encouragement and the D.S.I.R. for a maintenance Pnt (to B.J.C.). (Received November 23rd 1961 .) Co-ordination of Germanium Tetrafluoride with Nitrogen Phosphorus Oxygen and Sulphur Donors By R. C. AGGARWAL and M. ONYSZCHUK (DEPARTMENT 2 CANADA) OF cHJSMISTRY MCGILLUNIVERSITY MONTREAL OUR preliminary experiments reveal that germanium tetrafluoride is a powerful electron-acceptor capable of forming stable co-ordination compounds with nitrogen phosphorus oxygen and sulphur donor molecules. This property of germanium tetrafluoride results from the ability of germanium to increase its covalency from four to six by using its vacant 4d-orbitals in bonding.Previously described complexes of germanium tetrafluoride with nitrogen donors are GeF,,Me,N,' GeF,,2Me3N,l GeF4,2C,H5N,2 and GeF4,2Me,NPh.2 Although nitriles were reported not to form isolable complexes,2 we have found that aceto- nitrile resembles trimethylamine in forming 1:1 and 1:2 complexes. However ammonia pyrollidine piperidine and hydrazine give 1 :2 adducts only and ethylenediamine functions as a bidentate ligand when it forms a 1:1 compound. These new com- plexes are white non-volatile solids insoluble in hydrocarbon solvents and remarkably stable ther- mally. By contrast phosphine and trimethylphos- phine produce 1:1 compounds only; these are white solids which sublime with some decomposition at 25 ".Muetterties reported that germanium tetrafluoride forms stable 1 :2 complexes with oxygen donors such as dimethyl sulphoxide dimethylformamide and acetoxime but he could not isolate by precipitation from organic solvents complexes containing ketones or ethers. Using the tensimetric titration technique we have found that acetone dimethyl ether ethylene Fergusson Grant Hickford and Wilkins J. 1959 99. Muetterties J. Amer. Chem. Suc. 1960 82 1082. oxide tetrahydrofuran tetrahydropyran and methanol produce 1 :2 complexes and that the bi- dentate ligand dioxan yields a 1 :1 compound. These complexes are stable at 25" except GeF,,2Me2C0 and GeF4,2[CH2],0 which decompose at 25" and -78" respectively.Complexes of germanium tetrafluoride with sulphur donors have not previously been reported. Our results show that hydrogen sulphide methane- thiol dimethyl sulphide tetrahydrothiophen and tetrahydrothiopyran each form 1:1 and 1 :2 com- plexes. Of these only GeF,,H,S GeF,,MeSH and GeF4,2MeSH are unstable at 25". The stable com- plexes melt below loo" except GeF,,2H2S which does not melt below 300". The compositions of all new complexes were first indicated by pressure4omposition isotherms and then confirmed by quantitative synthesis and analysis for germanium and fluorine. While the 1:2 com- plexes are probably monomeric with octahedral bonding of germanium and either cis-or trans-arrangement of ligands the 1 :1 complexes are prob- ably polymeric fluorine-bridged structures with octa- hedral configuration about germanium.We are now investigating their structures by nuclear magnetic resonance X-ray diffraction and infrared spectral methods. We thank the Defence Research Board of Canada for financial assistance. (Received November 7th 1961.) JANUARY 1962 An Unusual Reaction Product from Diphenylketen and Ethoxyacetylene By D. H. R. BARTON R. C. PETIXRSON, J. N. GARDNER and 0. A. STAMM (IMPERIAL LONDON, COLLEGE S.W.7) DURING his extensive investigations on the chemistry of ethynyl ethers Arensl reported that diphenylketen and ethoxyacetylene reacted in nitromethane at low temperature to furnish an adduct formulated on sound analogy as 3-ethoxy-4,4-diphenylcyclobuten-one.Recently2 this proposal has been withdrawn but without an alternative formulation. We now show that the adduct has structure (IV) being pro- duced by an unusual rearrangement represented schematically in the formulae (I)and (11). The adduct (IV) has Amax. 248 (E 17,000) and 342 mp (E 4500;all ultraviolet data in EtOH) vmax. (in CHCI,) 1689 cm.-l (cyclopentenone) and shows (quantitative nuclear magnetic resonance spectrum) four vinyl hydrogen atoms (at positions 6 7 8 and 9)at T 3-68,one vinyl hydrogen (position 5) at T 3-21 five aromatic hydrogens (phenyl residue) at 72-83 one vinyl hydrogen (position 2) a to the ketone at 7 4-80,and bands for an ethoxyl group.Selective hydrogenation over 5 % palladised calcium or strontium carbonate in benzene gave a quantitative yield of the tetrahydro-derivative (In) m.p. 165-165.5",Amax. 279 mp (E 16,600) Vmax. (in CCl,) 1686 cm.-l (cyclopentenone) which showed one vinyl hydrogen (5) at r 3.40 3.32 3-26 and 3.165 one vinyl hydrogen (2)as above as well as the usual signals for one phenyl residue and one ethoxyl group. The tetrahydro-derivative was smoothly converted by osmium tetroxide into the a-glycol (V) m.p. 216-219" Amax. 248 mp (E 13,500) Vmax. (in CHCI,) 1700 cm.-l (cyclopentenone). The change in ultraviolet spectrum from (111) to (V) established the presence in (111) of a linearly conjugated dienone. Reduction of the ketone (HI) with lithium aluminium hydride and treatment of the product with dilute sulphuric acid3 gave the dienone (VI) m.p.122-122.5" Amax. 256 mp (E 10,OOO broad band) Vmax. (in CClJ 1708 (cyclopentenone) and 1659 crn.-l (cisoid C=C; abnormally strong4). This experiment confirms the presence of an enol ether of a B-diketone in (IV). Alternative evidence for this conclusion had been provided earlier.' Selective hydrogenation of the dienone (VI) over 5 % palladised strontium carbonate in ethanol gave the dihydro-derivative (VU) [2,4-dinitrophenyl-hydrazone m.p. 196-197" Amax. 385 mp (E 23,900)] reduction of which with sodium boro-hydride gave an allylic alcohol (X) showing only benzene absorption in the ultraviolet region and oxidised by manganese dioxide back to the ketone (VII).Clearly the ethylenic linkage of the latter is not in conjugation with the phenyl residue. The enone (VU) with osmium tetroxide gave smoothly a diol (IX; R = H) m.p. 93-96' vmttx. (in CHCl,) 1725 cm.-' (hydrogen-bonded cyclo- pentanone) which showed only benzene absorption in the ultraviolet spectrum. It gave a crystalline 3,5-dinitrobenzoate which in contrast to its pre- cursor (IX;R = H) was stable to chromic acid. The presence of a secondary-tertiary a-glycol is thus established and hence the degree of substitution in the enone (VU). Oxidation of the dienone (VI) with permanganate-periodate gave 6-benzoylvaleric acid (VHI). The relationship between the butadiene system (positions 6-9) of compound (IV) and the phenyl residue is thus demonstrated.The adduct (IV) gave a black crystalline chromium carbonyl complex of the composition [IV + Cr(CO),] m.p. 207-210" (decomp.) Amax. 340 l Nieuwenhuis and Arens Rec. Trav. chim. 1958 77 1153. J. F. Arens in "Advances in Organic Chemistry. Methods and Results," Vol. 11 eds. R. A. Raphael E. C. Taylor, and H. Wynberg Interscience Publ. tnc. 1960 pp. 117-212. Procedure of Woodward Sondheimer Taub Heusler and McLamore J. Amer. Chem. Suc. 1952,74,4223. Erskine and Waight J. 1960 3425; Barton and Narayanan J. 1958 963. (E 9400) 420 (E 5400) and 540mp (E 2901 Vmax. (in CS,) 1698 (cyclopentenone) 19 15. 1930 and 1992 (Cr-CO) cm.-l. Its formulation as (XI) based on the presence of a cycloheptatriene system is unexcep- tionaL5 It regenerated the adduct (IV) on treatment with pyridine.This compound is under X-ray examination in Glasgow by Professor J. M.Robert-son Dr. G. A. Sim and their collaborators. We thank Professor G. Wilkinson and Miss Abel Bennett Burton and Wilkinson J. 1958 4559. PROCEEDINGS Christina Mannerskantz for helpful advice on the preparation of compound (XI). This work was made possible by Postdoctoral Fellowships from the following agencies N.A.T.O. (J.N.G.) U.S. Public Health Service (R.C.P.) and the Stiftung fur Stipendien auf dem Gebiete der Chemie (Switzerland) (O.A.S.). We thank Drs. L. M. Jackman and J. W. Lown for the determination and interpretation of the nuclear magnetic resonance spectra.(Received November 21st 1961 .) Radiation-induced Formation of Hydroperoxides from Olefinic Compounds By P. G. CLAY,M. MCCARGO J. J. WEISS,and J. WHISTON G. SCHOLES UNIVERS~TY NEWCASTLE (KING'S COLLEGE OF DURHAM UPON TYNE,1) IT has been shown that a-hydroxy-hydroperoxides can be formed in the radiolysis of aqueous oxygen- ated solutions of various unsaturated organic probably by successive addition of the radiation-produced hydroxyl radicals and molecular oxygen at the double bond with subsequent reduc- tion of the peroxy-radicals formed. In recent studies of the action of 6oCo y-rays on oxygenated solutions it was found that under certain estimated by methods previously reported1 [see Table (a)]. The effects of pH and oxygen concentration (see Table) indicate that hydroperoxide A is formed by primary attack at the double bond by the negative polaron4 (H,O)- (reactions 1 2).Reaction (2) is followed by addition of oxygen and reduction of the peroxy-radical (RO,) to give hydroperoxide A which is presumably HO,.H,CCHMeCO,H. The de-Initial yields (G-values i.e. molecules/100 ev) of organic hydroperoxides on 6oCoy-irradiation of aqueous solutions of methacrylic acid and of allyl alcohol at diflerent oxygen concentrations. (a) Methacrylic acid (lOe3~) Oxygen (lo3 mole/l.) 1-26 pH 1.2 G(hydro-G(hydro-peroxide A) peroxide B) 0.25 0 1 -26 4.7 1-20 1 -30 5-47 4.7 0 1-40 conditions a double bond can also be attacked primarily by the reducing species formed from the water giving a radical which on reaction with oxygen affords hydroperoxides whose structures correspond to addition of the elements of hydrogen peroxide across the double bond.We here report experiments with methacrylic acid and allyl alcohol. Solutions of methacrylic acid were irradiated at different pH's and at varying oxygen pressures. Two organic hydroperoxides (A and B)were detected and I (b) Ally1 alcohol Alcohol Oxygen (mole/l.) (1O3mole/l.) 10-3 1.26 10-3 1.26 10-2 1.26 lo-' 1-26 10-3 5.47 lo" 20.65 pH G(hydro-G(hydro-peroxide C) peroxide D) 1.2 1.20 0.40 5.0 0.13 1-27 1.2 1.21 0.49 1.2 1.30 0.80 1-2 0.47 0.23 1.2 0-15 0.15 creased yield of hydroperoxide A in acid solution could then be ascribed to the process (H20)-+ H,O+ + H + 2H20 competing with reaction (l) and the inhibiting effect of higher oxygen concentra- tions to the competing reaction (H,O)- + 0,-+ 0,-+ H,O.CH,:CMe-CO,H + (H,O)-+ [CH,:CMeCO,H]- + H,O . . . (1) J. -CH,.CHMe.CO,H . . . (2) Scholes and Weiss. Radiation Res. 1959 Supp. 1 177. a Clay Weiss and Whiston Proc. Chem. Soc. 1959 125. * Scholes and Weiss Nature 1960 185 305. Weiss Nature 1960 186 751. JANUARY 1962 The second hydroperoxide (B) which is only detectable at higher pH’s is a hydroxy-hydroper- oxide. This follows from the fact that a hydroperoxide which reacts at the same rate with iodide ions was obtained in the photolysis of solutions of hydrogen peroxide containing methacrylic acid and oxygen; in the latter case hydroxyl radicals which are produced by the photolysis of hydrogen peroxide attack primarily the double bond.When solutions of allyl alcohol were irradiated with y-rays two organic hydroperoxides were observed. Table (b) shows the yields of these (C and D) as a function of the concentrations of the solute and oxygen and at different pH’s. Since at pH 1.2 the yields of both peroxides decreased with increasing oxygen concentration but increased with increasing allyl alcohol concentration we assume that both these hydroperoxides result from initial attack at the double bond by the reducing species formed from the water. The yield of hydroperoxide C decreased with increasing pH but that of D increased; thus the former peroxide is the result of the primary reaction of a hydrogen atom with allyl alcohol and the latter results from the primary attack by the negative polaron.Hydroperoxide D reacts with iodide at the same rate as does CH3CH(02H)CH2.0H and is thus formed by reactions (3 4). We assume therefore that the isomeric hydroperoxide C has the structure H02CH2CH2.CH2.OH. H+ CH,:CH*CH,*OH + (H20)-+ CH,-CH*CH,OH + H,O . (3) CH,.CH.CH,+OH + 0,-+ CH,-CH.CH,.OH A,. 4 Redn. CH,.CH.CH,*OH I O,H . . . (4) In the allyl alcohol system no stable hydroxy- hydroperoxide was observed a fact substantiated by the observation that no organic hydroperoxide could be detected in the photolysis of hydrogen peroxide solutions containing allyl alcohol and oxygen.Reaction of hydroxyl radicals with allyl alcohol in the presence of oxygen leads to acraldehyde glycol- laldehyde and formaldehyde.2 We thank the D.S.I.R. for the award of a Fellow- ship (to J.W.) and of a Studentship (to M.M.) and the British Oxgen Company for a Fellowship (to P.G.C.). (Received November 14th 1961.) Unusual Valency States of Chromium and Manganese in Oleum By H. C. MISHRAand M. C.R. SYMONS (DEPARTMENT THE UNIVERSITY, OF CHEMISTRY LEICESTER) CHROMATES and permanganates dissolve readily in 100% sulphuric acid probably as the corresponding su1phates.l Such solutions slowly decompose at room temperature with evolution of oxygen and the formation of tervalent chromium or of manganese dioxide.In 65 % oleum however oxygen evolution is rapid and the resulting solutions which are blue and green respectively are stable. In contrast vanadates dissolve probably as sulphates without undergoing a change in valency in either solvent. Spectr op ho t ome tric magnetic conduct ome tric and analytical studies show that the blue manganese compound is quadrivalent and that the green solu- tions contain chromium entirely in the quinquevalent state. Both compounds are monomeric and are probably uncharged sulphates. The evidence for quadrivalent manganese is as follows (i) oxygen corresponding to a valency change of three was evolved; (ii) the manganese had a magnetic susceptibility close to that expected for Mishra and Symons unpublished results.three unpaired electrons on the “spin-only” approxi- mation; (iii) manganese dioxide dissolved without formation of oxygen or sulphur dioxide to give identical solutions ;(iv) a well-resolved electron-spin resonance spectrum was obtained at room tempera- ture consisting of six lines having a hyperline splitting of 100 gauss and a g-value of 2.000 in accord with expectation for quadrivalent manganese; and (v) similarly the visible spectrum consisting of a weak band at 570 mp is reasonable for a sulphate complex with relatively weak bonding. Evidence for quinquevalent chromium is similar (i) oxygen evolution was quantitatively in accord with a valency change of unity; (ii) the magnetic susceptibility corresponded to one unpaired electron; (iii)a well-resolved electron-spin resonance spectrum showing hyperfine structure from 53Cr nuclei in natural abundance was in accord with expectation for a sulphate complex.Also no detectable resonance at room temperature would be expected for quadri- valent chromium because of broadening from zero- field interactions of a triplet molecule and we found that tervalent chromium although soluble in the medium gave no detectable resonance absorption at room temperature. a Lott and Symons J. 1959 829. Bailey and Symons J. 1957 203. PROCEEDINGS For comparison we recall that manganese dioxide is also soluble in concentrated aqueous alkali but then disproportionates to MnV and Mn*11,2 whereas the chromate ion reacts with molten alkali to give oxygen and hypochromate? (Received November 29th 1961.) Dual Mechanism in the Pyrolysis of Di-isopropylmercury By B.H. M. BILLINGE and B. G. GOWENLOCK (DEPARTMENT 15) OF CHEMISTRY THE UNIVERSITY BIRMINGHAM WEhave reexamined the flow pyrolysis of di-isopropylmercury and confirmed the kinetic para- meters [log A (sec.-l) 16.7 E 40.4 kcal. mole-l] reported by Chilton and Gowen1ock.l The extent of the decomposition was measured as in the former investigation by weighing the mercury produced. 0 -7-I Li e!!/ -41 I I I 1 1‘1 1-87 1-96 205 2-14 2-23 10’1T A Best straight-line Arrhenius plot for 240-300” ; velocity constants based on mercury produced. B Best straight-line Arrhenius plot for 170-230” ; velocity constants based on gas-liquid chromato-graphy of hydrocarbon products.Velocity constants based on chromatography 0 unpacked vessel 8 mm. ; unpacked vessel 15 mm.; 0 packed vessel 8 mm.; packed vessel 12 mm. Packing increases the surface; volume ratio by a factor of 14. produced can be accurately weighed and at lower temperatures where the quantities produced are too small for this. Above 240” the agreement between the first-order rate constants calculated by either method is good and the Arrhenius parameters are the typical “class II” examples as stated previously.1 However as the temperature falls a curvature in the Arrhenius plot ensues and the parameters approach those typical of “class I” decompositions [log A (sec.-l) 11.0 E 27.0 kcal.mole-l]. The Figure shows these results. This is the first example known to us of a homogeneous gas-phase decomposition where the same molecule exhibits two sets of Arrhenius parameters. There is some evidence that dimethyl- mercury shows class I [log A (sec.-l) 13-14 E 51-52 kcal. rn~le-~]~ and also class 11parameters [log A (sec.-l) 15.7 E 57-9 kcal. However as that study was made with different apparatus and conditions and as some of the work may be in the region of fall-off from unim~lecularity,~ there is some uncertainty about it. Pritchard5 pointed out that an Arrhenius plot would be curved if the measured rate constant k is the sum of the rate constants for the two decom- position mechanisms e.g. k = k + k, where k is the rate constant for the reaction HgR -+ R.+ ‘HgR and k is the rate constant for the reaction HgRz -+ 2R-+ Hg.We therefore suggest that this dual mechanism operates in the pyrolysis of di- isopropylmercury class I1 and class I mechanisms predominating at higher and lower temperatures respectively. We thank British Nylon Spinners Ltd. for a research grant (to B.H.M.B.) and Dr. L. H. Long (Received November loth 1961). Chilton and Gowenlock Truns. Furaduy SOC.,1953,49 1451. Carter Chappell and Warhurst J. 1956 106. Gowenlock Polanyi and Warhurst Proc. Roy. Sac. 1953 A 218 269; Laurie and Long Truns. Furaduy SOC. 1955,51 665; Price and Trotman-Dickenson ibid. 1957,53 939. Russell and Ekrnstein J. Chem. Phys. 1959 30 607; Long personal communication.Pritchard J. Chem. Phys. 1956 25 267. JANUARY 1962 A Stereochemical Factor in Cyclopropyl Conjugation By EDWARD M. KOSOWER OF CHEMISTRY UNIVERSITY LONGISLAND CENTRE, (DEPARTMENT STATE OF NEWYORK OYSTER BAY,N.Y. U.S.A.) and M. ITO OF CHEMISTRY UNIVERSITY (DEPARTMENT OF WISCONSIN,MADISON6 WISCONSIN,U.S.A.) THE suggestion has been made that interaction [3,1 ,O]hexan-Zone (11). Qualitatively the n+n* between a cyclopropyl ring and a carbonyl group is transitions may be described as shown in (1) and (2). most effective when the plane of the ring and the It would have been expected that the n+n* p-orbitals of the carbonyl group are para1lel.l We transition energy for ketone (II) would be several now report results which support this proposal and kcal./mole less than that for its analogue (I) because indicate that the geometric factor is of appreciable (a) the ground state of the former is more strained importance.and therefore higher in energy and (b) the positive 0.7. charge in the excited state of the former should be accommodated more effectively by a secondary--“.-+{p(-J (1) primary carbon combination than by a primary- primary one. In fact & (11) is 5.1 kcal./mole greater than ET (I)in 2,2,4-trimethylpentane (“iso-octane”). The parallel relationship between the cyclopropane (2) *&+\& ring and the carbonyl group thus leads to an inter- action in the excited state which may be as much as The Table and the Figure give the ultraviolet 7-8 kcal./mole greater than in non-parallel cases absorption of spiro [4,2]heptan-1-one2 (II) which is (ex.m. to be compared (see Table) with that3 of bicyclo- The geometric factor is apparently still important Ketone (I) Ketone (11) Solvent (Z)f n+m* n+* Solvent(2)t v+n* n+rr CH2Pr1ButS(60.1) 1945 (3020) 2925 (21) CH,Pr’But$ (60.1) 1880 (5700) 2884 (18) MeCN (71-3) 1980 (3100) 2869 (26) H20(94-6) 1967 (5120) 2721 (57) MeOH (83.6) 2006 (3490) 2806 (30) CHF2CF2CH2.0H (96.3) 2050 (4300) 2746 (39) when the cyclopropyl ring is a p-substituent on an afl-unsaturated ketone. By assuming that each p-alkyl substituent lowers the n+n* transition energy by 1.95 kcal./mole,* and making appropriate 8 5 (cni’) Spectrum of spiro [2,4Jheptan-1-one (I) (0.0267~)in corrections for solvent effects transition energies for 2,2,4-trimethylpentane.Left-hand curve 1= 001 cm. the system RCH = CHCO-(where R = cyclo-Right-hand curve 1 = 1-00cm. propyl) are estimated for spiro [2,5]octa-174-dien-3- Cromwell and Hudson J. Amer. Chem. SOC.,1953 75 872; cf. also Music and Matsen ibid. 1950,72 5256. * Mayer and Schubert Chem. Ber. 1958,91,768. Kosower J. Amer. Chem. SOC.,1958,80 3261. .I Estimated by comparison of ultraviolet maxima for bicyclo [3,1 ,O]hexan-Zone and dihydrolumisantonin in ethanol (cf. Barton and Gilham J. 1960 4596 footnote). one5 (IJI) 1 -dehydrocycloartanone6 (IV) and the 5,9-cy~lo-steroid~(V) as follows (III)105.1 kcal./ mole; (IV)110.1 kcal./mole; and (V) 113-6kcal./mole. The differences presumably correspond in whole or in part to the overlap possible between the cyclo- propyl ring and the ap-unsaturated ketone system in the excited state? The solvent effect upon the T+T* transition of ketone (I) (ca.8.5 kcal./mole difference between the most and least polar solvents) is comparable to those observed for such cyclic @-unsaturated ketones as cyclohex-2-enone and isoph~rone.~ It would be of some interest to examine the PROCEEDINGS solvolytic reactivities of derivatives of the alcohol derivable from ketone (I) by reduction. However great caution should be exercised in extrapolating spectroscopic results (where the Franck-Condon rule applies) to solvolytic reactions in which re- arrangement of the cybotactic regionlo to accom- modate the charges present in the transition state Occurs.The authors are grateful to Mr. D. E. Cardy for the preparation of ketone (I) and to the Air Force Office of Scientific Research for financial support. (Received November 21.~4 1961 .) Baird and Winstein J. Amer. Chem. SOC. 1957 79 4238. Irvine Henry and Spring J. 1955 1316. Gnoj Oliveto Robinson and Barton Proc. Chem. SOC.. 1961 207. * These cases are of course different from the symmetry-forbidden transitions discussed by Wilcox jun. and Craig (J. Amer. Chem. SOC. 1961 83 4258). @ Kosower Wu and Sorensen J. Amer. Chem. SOC.,1961,83 3147. lo Kosower J. Amer. Chem. SOC. 1958 80 3253. Stimulated Light Emission in Organic Molecules By D. J. MORANTZ,B. G. WHITE and A.J. C. WRIGHT (CHEMISTRY WOOLWICH L~DON, DEPARTMENT POLYTECHNIC S.E. 18) RADIATION of the frequency which is emitted by an excited species can itself stimulate emission from the excited species. A pair of reflecting plates amplifies such an emission to an intense burst of light thus “quenching” the excited state. This is in part the principle of the light maser.l Whilst current interest in the light maser is centred on communication problems its potential as an in- tense and highly monochromatic light source for photochemical investigations has been pointed out.2 The only solid-state optical masers constructed to date depend on the electronic transitions of inorganic ions especially Cr3+ in ruby. The close analogy between the multiplicity-forbidden doublet +quartet transition in the C?+ ion in an octahedral field and the triplet +singlet transition in organic molecules in a rigid glass matrix was considered by one of us (D.J.M.) in a phosphorescence study? We have now demonstrated possibility of stimulated emission in an aromatic system.We used an intense flash of white light to populate the triplet state. The stimulated emission was generated by two parallel reflecting plates. The medium was a rigid organic glass at 77”~. The pro- cedures and results were similar to those described by Maiman et aL4 for a ruby maser. Our observa- tions are summarised as follows. Sharp “bursts” of light were observed superimposed on the phos- phorescent decay. After the burst the level of the phosphorescence was reduced below the value ob- tained without reflecting plates and the amount of reduction is a function of the flash intensity.The greater the flash intensity the less is the residual phosphorescence. At a critical light intensity we observed a series of several consecutive major bursts ; when the flash intensity was increased above this critical value only one major burst was observed. Figs. 1 and 2 are representative of some of the oscil- lograph traces showing the consecutive bursts. In addition to examining single species we have observed these phenomena in an energy-transfer system exemplified by benzophenone as donor and naphthalene as acceptor i.e. the Ermolaev-Terenin donor-acceptor system;5 the stimulated emission was observed in the acceptor.These observations support our view of the generality of these phenomena. It appears that optical masers may be constructed by using systems such as aromatic molecules in glass matrices. These should make available an extensive and variable choice of Schawlow and Tomes Phys. Rev. 1958,112 1940. Schawlow “Quantum Electronics,” Columbia University Press New York 1960 p. 552. a British Rayon Research Association Report R4004 (1958). Maiman Hoskins D’Haenens Asawa and Evtuhov Phys. Rev. 1961 123 1151. Ermolaev and Terenin Pamiati S. I. Vavilova Akad. Nauk S.S.S.R.,1952 137. JANUARY 1962 27 operating frequencies in the visible and ultraviolet as well as in the infrared region. Only one reference is known to the authors con- cerning the possibility of an organic maser namely 1 a speculative paper6 which appeared whilst our work I was in progress.The suggestion was that organic I (21 molecules e.g. naphthalene in a crystal matrix should give maser action. We agree with that sug- gestion but feel it is worth recommending the use of organic glass matrices as a simpler technique for exploratory work. Consecutive bursts observed with (FIG. 1) aceto-I phenone and (FIG.2) benzaldehyde each -lo-% in a rigidglass at 77"~. Time base -5 millisec. We thank Dr. A. I. Vogel for facilities for this work. Twoof us (A.J.C.W. and B.G.W.) acknowledge the tenure of L.C.C. Research Assistantships. (Received November 14th 1961.) Brock Csavinsky Hormats Nedderman Stirpe and Unterleitner J.Chem. Phys. 1961.35 759. A 2,3-Seco-triterpenein Nature By K. J. CROWLEY (LNSTITUTO VENEZOLANO CIENTIFICAS(I.V.I.C.), DE INVESTIGACIONES APARTADO VENEZUELA) 1827 CARACAS 2,3-sECO-OLEANA-12-ENE-2,3,28-TRIOIC acid (I; R = H) has been prepared from oleanolic acid.lS2 It Bas now been isolated in 0.15% yield from the oily heart- wood of Bursera graveozens (H.B.K.) Tr. et P1. var. villosula Cuatr. It provides a unique example of 2,3-biogenetic cleavage of the triterpenoid skeleton. The acid Cz,H,,(C0,H),,0~5C2H,~OH, obtained by washing the ethanolic extract of the wood with cold aqueous sodium hydroxide had m.p. 296" (decornp.) [a]","+ 65" (c 1.0 in pyridine) gave the reported2 dour reaction with sulphuric acid and yielded the known1 trimethyl ester (I; R = Me) the ketoester (II;R = Me) and oxime the keto-acid (IJ; R = H), and bromo-lactone.K I thank Dr. J. M. Cruxent for obtaining the wood and Dr. G. Taylor and his staff Royal Botanic Gardens Kew for its botanical classifkation. (Received November 20th 1961.) Ruzicka and van der Sluys-Veer,Helv. Chim. Am 1938 21 1371. Kitasato Acta Phyrochim. Tokyo 1938 10,239. PROCEEDINGS NEWS AND ANNOUNCEMENTS Research Fund.-Grants for research have been awarded by Council to the following ;E s. d. Balasubramanian S. K. (London) . . 30 0 0 Brown M. G. (Nottingham) .. . . 20 0 0 Elmore D. T. (Belfast) .. .. . . 28 0 0 Finch A. (London) .. .. .. 60 0 0 Hallam H.E. (Swansea) .. .. 44 0 0 Hills G. J. (London) .. .. .. 17 10 0 Irving R. J. (London) .. .. . . 35 0 0 Jones N. (Coventry) .. .. .. 35 0 0 Lee W. H. (London) .. .. * 25 -0 Lock C. J. L. (London) .. 38 * McKean D. C. (Aberdeen) . . -90 Morantz D. J. (London) .. -* 50 O’Colla P. S. (Galway) .. .. -40 Orville-Thomas W. J. (AbeWwYth) . . 100 0 0 Peacocke T. *. (Leatherhead) * -l8 lo .I Perkins P. G. (Sheffield) * * 30 Powell D. B. (London) . . .. -* 30 Praill P. F. G. (London) .. -lo lo Priyadarshini Miss U. (India) .. *. 56 Reid D. H. (St. Andrews) .. -58 Robbins R. F. (Hatfield) .. ** l2 Smeeth A. G. (London) .. * -45 Summer G. H. R. (Swansea) .. * 25 Sutherland J. K. (London) .. -55 l3 Thomas J. M. (Bangor) ..70 Thynne J. (Leeds) .. .. -* 35 White R. F. M. (London) . . 25 Election of New Fellows.-111 Candidates whose names were published in Proceedings for November have been elected to the Fellowship. Deaths.-We regret to announce the deaths of the following Dr. B. A. Ferrone (15.7.61) of the University of Texas U.S.A.; Mr. A. F. Mason (29.11.61) of Southport; and Mr. J. Rennie (9.1.611 of W. B. Cartwright Ltd. International Atomic Weights 1961.-A list of the International Atomic Weights for 1961 including the latest conventions agreed by the International Unions of Pure and Applied physics and of pure and Applied Chemistry printed on card are available from the General Secretary price 2s. per copy. Dexter Award in the astory of Che&try.-Nominations are invited for the 1962 Dexter Award in the history of chemistv by the Divi- sion of History of Chemistry of the herican Chemical Society.The Award consists of a suitable plaque and $l,OOO. The of the 1961 Award was Dr. J. R. Partington Professor Emeritus of Queen Mary College London England. “The Award shall be made on the basis of services which have advanced the history of chemistry in any of the following ways by publication of an important book or article; by significant contributions to the bibliography of the history of chemistry; or by meritorious services over a long period of time which have resulted in the advancement of the history of chemistry.” All information in duplicate should be sent to the Secretary of the Division of History of Chemistry by March loth 1962.Information should be as detailed as possible and should include outstanding as well as minor contributions of the nominee. Symposium on Nitrogen Heterocyclic Chemistry.- This Symposium arranged by Hatfield College of Technology with the support of The Chemical Society will be held at Hatfield on May 10-1 lth 1962. The following papers wilt be presented “Ex-periments on a Synthesis of Vitamin Biz," by Dr. J. W. Cornforth; “The Electrophilic Substitution of Nitrogen Heterocyclic Compounds,” by Professor P. B. D. de la Mare; “Meso-ionic Compounds,” by Professor W. Baker; “The Synthesis of Heterocyclic Compounds by the Extrusion of Sulphur,” by Dr. J. D. Loudon; “N-Oxides,” by Dr.A. Katritzky; “New Cyclisation Reactions in the Heterocyclic Series,” by Professor D. H. Hey; “Porphyrin P.M.R. Spectra,” by Dr. A. H. Jackson; “The Stereochem- istry of Simple Quinolizidines,” by Dr. K. Schofield; and “The Electronic Spectra of Nitrogen Hetero- cyclic Compounds,’’ by Dr. S. F. Mason. Any en- quiries concerning the Symposium should be addressed to Dr. R. F. Robbins Head of the Department of Science Hatfield College of Tech- nology Hatfield Herts. from whom forms of application to register can be obtained. International Symposium on Carbohydrate Chem-istry.-An International Symposium on Carbo-hydrate Chemistry sponsored by the Chemical Society in association with the University of Birmingham will be held in Birmingham on July 16-20th 1962.The full programme will include Some fifty invited lectures and papers and will be distributed in due course to all Fellows of the Chem- ical Society and to those who have already expressed an interest in the meeting. Additional copies will be available not later than March 30th 1962 from the General Secretary The Chemical society Burlington House London W. 1. Meanwhile further details of the meeting are available from Dr. A. B. Foster, Chemistry Department University of Birmingham Edgbaston Birmingham 15. Papers read at the meeting will not be published in fidl in collective Other Symposia.-The 25th Winter Congress of the International Institute of Sugar Beet Researches will be held in Brussels on February 20th-22st JANUARY 1962 1962.Details may be obtained from the Secretary of the Institute Mr. 0. J. Kint 152 rue Beauduin Tirlemont Belgium. A Symposium on Cellular Basis and Aetiology of the Late Somatic Effects of Ionizing Radiations will be held in London on March 27-30th 1962. En- quiries should be addressed to Dr. P. Alexander Chester Beatty Institute Institute of Cancer Re- search Royal Cancer Hospital Fulham Road London S.W.3. A International Symposium on Nutritional Absorption in Vegetables will be held in Pisa and Florence on April 9-14th 1962. Enquiries should be addressed to the Organising Committee c/o Instituto di Chimica Agraria Universita degli Studi di Pisa Via S. Michele degli Scalzi 2 Pisa Italy. An International Congress on Hormonal Steroids will be held in Milan on May 14-18thy 1962.Enquiries should be addressed to Professor L. Martini and Professor A. Pecile Instituto de Farma- cologia e Terapia 21 Via A. del Sarto Milan Italy. The 1st European Plastic and Rubber Conference organised by the Socidt6 de Chimie Industrielle will be held in Paris on May 18-29th 1962. Enquiries should be addressed to Soci6t6 de Chimie Industrielle 28 rue Saint-Dominique Paris 7e France. A European Symposium on Fresh Water from the Sea will be held in Athens on May 3lst-June 3rd 1962 in conjunction with the 39th Event of European Federation of Chemical Engineering. Enquiries should be addressed to P.O.B. 1199 Omonoia Athens Greece. An lnternational Symposium on the Organic Chemistry of Natural Products under the auspices of the lnternational Union of Pure and Applied Chemistry and in connection with the 75th anni- versary of the foundation of the “Soci6t6 Chimique de Belgique” is to be held in Brussels on June 12-15th 1962.Copies of the second circular can be obtained from the Secretariat of the International Symposium of Organic Chemistry c/o Fkdkration des Industries Chimiques de Belgique 32 rue Joseph 11 Brussels 4. The 3rd Congress of the European Federation of Chemical Engineering will be held in London on June 20-29th 1962. Copies of the Preliminary Pro- gramme may be had from Mr. J. B. Brennan Secre- tary Co-ordinating Committee The Institution of Chemical Engineers 16 Belgrave Square London S.W.1. The 3rd International Symposium on Rarefied Gas Dynamics will be held in Paris on June 26-29thY 1962. Enquiries should be addressed to the General Secretary M. Pierre Bartoli Universitk de Paris A la Sorbonne 47 rue des Ecoles Paris 5e France. The 2nd Congress of the International Federation of Societies of Cosmetic Chemists will be held in London on July 2nd-5thY 1962. Enquiries should be addressed to the Organiser of the Congress MI. A. Herzka c/o Pressurized Packaging Consultants Ltd. Ashbourne House Alberon Gardens London N.W.ll England. An International Conference on the Physics of Semiconductors sponsored by the International Union of Pure and Applied Physics and the British National Committee for Pure and Applied Physics of the Royal Society will be held in Exeter England on July 16-20th 1962.Enquiries should be ad-dressed to the Administration Assistant Institute of Physics and the Physical Society 47 Belgrave Square London S.W. 1,England. An International Symposium on Far Infrared Spectroscopy will be held in Cincinnati Ohio on August 21st-24th 1962. Enquiries should be addressed to the Office of Information Wright Air Development Division Wright-Patterson Air Force Base Cincinnati Ohio U.S.A. An International Conference on Water Pollution Research will be held in London on September 3rd-7th 1962. Enquiries should be addressed to the Secretary-General Mr. J. E. Holmstrom Scientific Conference Centre Headington Hill Hall Oxford England.An International Symposium on Molecular Struc- ture and Spectroscopy sponsored by the Inter- national Union of Pure and Applied Chemistry in co-operation with Japanese learned societies will be held in Tokyo on September lO-lSth 1962. En- quiries should be addressed to the Secretary Organising Committee Science Council of Japan Ueno Park Tokyo Japan. The 8th International Conference on Low Temperature Physics sponsored by the Inter-national Union of Pure and Applied Physics will be held in London on September 16th-22nd 1962. Enquiries should be addressed to LT 8 Queen Mary College University of London Mile End Road London E. 1 England. The 14th Meeting of the International Committee of Electrochemical Thermodynamics and Kinetics will be held in Rome on September 24-29th 1962.Enquiries should be addressed to the Secretary- General Dr. N. Ibl c/o Laboratory of Physical Chemistry Federal Polytechnicum 6 Universitats- strasse Zurich Switzerland. The German Society of Physiological Chemistry and the Austrian Biochemical Society will hold a joint meeting at the University of Vienna from September 26-29thY 1962. At the same time the German Pharmacological Society will convene in Vienna for its 27th annual meeting. Enquiries should be addressed to Dr. K. H. Spitzky Officer for the Secretariat Weher Medizinische Akademie fur Arztliche Fortbildung Wein IX Alserstrasse 4 Austria. The 2nd International Symposium on Phos-phorylated Glucides will be held in Milan on October 12-14th 1962.Enquiries should be ad- dressed to Dr. Italo Sagone Secretary Via Modica 6 Milan Italy. An International Congress on “Problems of Choice in the Field of Plastics” will be held in Amsterdam on October 15-17th 1962 and will precede the 3rd International Plastics Exhibition “macroPlastic” to be held in Utrecht October 18-25th 1962. Enquiries should be addressed to the Secretariat of the Congress Tesselschadestraat 5 Amsterdam (W) Holland. The 3rd International Reinforced Plastics Con- ference will be held in London on November 28--30th 1962. Enquiries should be addressed to British Plastics Federation 4748 Piccadilly London W. 1 England. The 6th General Assembly and International Congress of the International Union of Crystallo- graphy will be held in Rome from September 9-14th 1963.One or more Symposia associated with the Congress will follow during the period September 1618th. Detailed information will be published in September 1962 and copies of the First Notification may be obtained from the Assistant Secretary The Royal Society Burlington House London W.l. PROCEEDINGS Personal.-Mr. K. W. Allen is Visiting Research Associate and Instructor at the Crystallography Laboratory University of Pittsburgh and not at the University of Pennsylvania as reported in the Proceedings for October 1961. Mr. T. A. Cooper of Balliol College Oxford has been awarded the Gibbs Scholarship in Chemistry for 1961. Professor F. G. Hollimun of the University of Cape Town has been appointed Director of Combined Studies at the University of Leeds as from July 1st next.Dr. D. I. McGilvray has been appointed Chief Chemist of McCorquodale Colour Display Limited Newton-le-Willows Lancashire. Mr. V. W. Slater a Director of Laporte In- dustries Ltd. has retired after 41 years’ service. Dr. W. A. Waterswill be away from Oxford during January-April 1962. After visiting Malaya to act as external examiner of the University of Malaya in both Singapore and Kuala Lumpur he will spend February and March on a lecture tour of Australia at the invitation of the Royal Australian Chemical Institute. He will also lecture in New Zealand at the invitation of the New Zealand Institute of Chemistry and on his return at the University of Delhi India.Professor F. H. Westheimer of Harvard Univer- sity has been appointed Morrell Lecturer at the University of Cambridge for the academic year 1962-63. FORTHCOMING SCIENTIFIC MEETINGS London Thursday February lst 1962 at 7.30 p.m. Tilden Lecture “Hydrido- and Related Organo- complexes of Transition Metals,” by Dr. J. Chatt M.A. F.R.S.To be held in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington S.W.7. Thursday February 15th at 7.30 p.m. Centenary Lecture “Calabash-curare Alkaloids,” by Professor H. Schmid Dr.Phi1. To be held in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington. Aberdeen Monday February 19th 1962 at 8 p.m.Centenary Lecture “Calabash-curare Alkaloids,” by Professor H. Schmid Dr.Phil. to be given in the Chemistry Department The University. Aberystwyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratory University College of Wales.) Thursday February Sth 1962 at 5 p.m. Lecture “Aspects of Molecular Behaviour,” by Dr. Manse1 Davies M.Sc. Thursday February 22nd at 5 p.m. Lecture “Getting Married,” by Professor D. V. Lindley. Birmingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University.) Monday February 12th 1962 at 4.30 p.m. Centenary Lecture “Calabash-curare Alkaloids,” by Professor H.Schmid Dr.Phil. Friday March 2nd at 4.30 p.m. Lecture “Phytol-the Cinderella of Natural Pro- ducts,” by Professor B. C. L. Weedon D.Sc. F.R.I.C. JANUARYI962 Bristol (Joint Meetings with the Society of Chemical In-dustry and the Royal Institute of Chemistry to be held in the Department of Chemistry The Univer- sity unless otherwise stated.) Thursday February lst 1962 at 6.30 p.m. Jubilee Memorial Lecture of the Society of Chemical Industry “The Organisation of Research and Development,” by Dr. F. Roffey F.R.I.C. Thursday February 8th at 6.30 p.m. Lecture “Some Aspects of Structure and Reactivity in Ionic Solutions,” by Professor K. W. Sykes M.A. D.Phi1. Tuesday February 13th at 5.15 p.m. Tilden Lecture “Stereoselectivity in the Reactions of Cyclic Compounds,” by Professor H.B. Henbest D.Sc. Ph.D. F.R.I.C. Thursday February 22nd at 7.30 p.m. Lecture “Rocket Fuels,” by Dr. W. G. S. Parker F.R.I.C. To be given at Gloucester Technical College. Thursday March lst at 6.30 p.m. Lecture “Fuel Technology in the U.S.S.R.,” by Dr. Idris Jones C.B.E. Joint Meeting with the Institute of Fuel. Cambridge (Meetings will be held in the University Chemical Laboratory Lensfield Road.) Friday February 2nd 1962 at 8.30 p.m. Official Meeting and Lecture “A Few Chemical Problems Connected with Cancer Chemotherapy,” by Professor F. Bergel D.Sc. F.R.S. Joint Meeting with the University Chemical Society. Monday February 5th at 5 p.m.Lecture “Experiments on a Synthesis of Vitamin BI2,” by Dr. J. W. Cornforth. Friday February 9th at 8.30 p.m. Lecture “Non-stoicheiometric Compounds,” by Dr. J. S. Anderson F.R.S. Joint Meeting with the University Chemical Society. Friday February 16th at 8.30 p.m. Lecture “New Fluorine Compounds in Nature; their Biochemical and Pathological Effects,” by Sir Rudolph Peters M.D. F.R.S. Joint Meeting with the University Chemical Society. Monday February 19th at 5 p.m. Lecture “Some Nuclear Magnetic Resonance Studies of Amino-acids and their Complex Ions,” by Dr. L. Pratt M.A. Friday March 2nd at 8.30 p.m. Lecture “Molecular Shapes and Sizes,”by Dr. L. E. Sutton M.A. F.R.S. Joint Meeting with the University Chemical Society. Monday March 5th at 5 p.m.Lecture “Chains and Rings in Solution,” by Dr. F. J. C. Rossotti M.A. Tuesday March 6th at 4.30 p.m. Lecture “The Mass Spectrometer in Chemical Physics,” by Dr. J. Cuthbert. Cardiff Friday February 2nd 1962 at 5 p.m. Lecture “Chemistry of Proteins,” by Dr. F. Sanger F.R.S. to be given in the Department of Chemistry The University Cathays Park. Dublin Friday February 23rd 1962 at 7.45 p.m. Lecture “Chemical Effects of Ionising Radiations,” by Professor J. Weiss Ph.D. Dr.Ing. Joint Meeting with the Werner Society to be held in the Depart- ment of Chemistry Trinity College. Durham (Joint Meetings with the Durham Colleges Chemical Society to be held in the Science Laboratories The University.) Monday February 12th 1962 at 5 p.m.Lecture “Polymer Formation and Stability,” by Professor F. S. Dainton Sc.D. F.R.S. Monday February 26th at 5 p.m. Lecture “Some Organo-Transition Metal Cam- plexes,’’ by Dr. M. L. H. Green. Edinburgh Tuesday February 6th 1962 at 4.30 p.m. Lecture “Nuclear Magnetic Resonance and the Stereochemistry of Organic Compounds,” by Dr. L. M. Jackman. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Thursday February 8th at 7.30 p.m. Lecture “Isotactic Polymerisations,” by Professor G. M. Burnett Ph.D. D.Sc. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Exeter (Meetings to be held in the Washington Singer Laboratories Prince of Wales Road.) Friday February 2nd 1962 at 5.15 p.m.Lecture “Some Recent Advances in the Chemistry of Aromatic Fluorine Compounds,” by Professor M. Stacey D.Sc. F.R.S. Friday March 2nd at 5.15 p.m. Liversidge Lecture “Stereospecific Polymerisation,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Glasgow Friday February 16th 1962 at 4 p.m. Lecture “Atomic Orbitals in Molecules,” by Profes- sor D. P. Craig D.Sc. F.R.S. Joint Meeting with the Alchemists’ Club to be held in the Chemistry De partment The University. Wednesday February 21st at 4 p.m. Official Meeting and Centenary Lecture “Calabash- curare Alkaloids,” by Professor H. Schmid Dr.Phi1. To be given in the Chemistry Department The University.Hull (Meetings will be held in the Chemistry Department The University.) Thursday February lst 1962 at 7.30 p.m. Lecture “Recent Advances in the Mass-spectro- metry of Organic Compounds,” by Dr. J. H. Beynon A.R.I.C. Joint Meeting with the Royal Institute of Chemistry. Tuesday February 13th at 5 p.m. Lecture “Some Problems in Phosphorus Chem- istry,” by Dr. F. H. Pollard. Joint Meeting with the University Students Chemical Society. LeedS Thursday March lst 1962 at 6.30 p.m. Liversidge Lecture “Stereospecific Polymerisation,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. to be given in the Chemistry Lecture Theatre The University. Leicester Monday February 19th 1962 at 4.30 p.m.Lecture “The Kinetics of Halogenation of Acetone,” by Mr. R. P. Bell M.A. F.R.S. Joint Meeting with the University Chemical Society to be held in the University. Liverpool Thursday February 22nd 1962 at 5 p.m. Lecture “Some Recent Work of the National Chemical Laboratory,” by Dr. J. S.Anderson F.R.S. Joint Meeting with the Student Chemical Society to be held in the Department of Inorganic and Physical Chemistry The University. Manchester Thursday February 8th 1962 at 4 p.m. Lecture “Some Aspects of Stereospecific Polymers,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Joint Meeting with the University Chemical Society to be held in the Large Chemistry Lecture Theatre The University. Thursday February 22nd at 6.30 p.m. Lecture “Energy Transfer between Molecules,” by Professor G.Porter M.A. Ph.D. F.R.S. To be PROCEEDINGS given in Room F1 The Manchester College of Science and Technology. Tuesday February 27th at 4.30 p.m. Lecture “The Use of Radioisotopes in the Study of Surface Films,” by Professor N. K. Adam M.A. Sc.D. F.R.S. Joint Meeting with the University Faculty of Technology Union Chemical Society to be held in Room Fl The Manchester College of Science and Technology. Newcastle upon Tyne (Meetings to be held in the Chemistry Department King’s College.) Friday February 2nd 1962 at 5.30 p.m. Bedson Club Lecture “The Catalytic Oxidation of Naphthalene,” by Dr. H. L. Riley F.R.I.C. Tuesday February 13th at 5.30 p.m. Lecture “Alkaloid Biosynthesis,” by Dr.A. R. Battersby. Friday February 23rd at 5.30 p.m. Bedson Club Lecture “The Production of Some Antibiotics on an Industrial Scale,” by Dr. I. L. S. Mitchell. North Wales Thursday February lst 1962 at 5.45 p.m. Lecture “The Chemistry of Proteins,” by Dr. F. Sanger F.R.S. Joint Meeting with the University College of North Wales Chemical Society to be held in the Chemistry Department University College Bangor. Nottingham (Meetings will be held in the Chemistry Department The University.) Tuesday February 13th 1962 at 5 p.m. Centenary Lecture “Calabash-curare Alkaloids,” by Professor H. Schmid Dr.Phi1. Tuesday February 20th at 8 p.m. Lecture “Stereochemical Correlations,” by Profes- sor W. Klyne M.A. D.Sc.F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Uni- versity Chemical Society. Tuesday March 6th at 5 p.m. Lecture “Chemical Reprocessing of Plutonium-containing Fuels,” by Dr. D. M. Donaldson A.R.I.C. Joint Meeting with the University Chemical Society. Oxford (Joint Meetings with the Alembic Club to be held in the Inorganic Chemistry Laboratory.) Monday February 12th 1962 at 8.30 p.m. Tilden Lecture “Stereoselectivity in Reactions of Cyclic Compounds,” by Professor H. B. Henbest D.Sc.,Ph.D. F.R.I.C. JANUARY 1962 Monday February 19th at 8.30 p.m. Lecture “Chemical Transmission of Nerve Effects,” by Sir Lindor Brown C.B.E. F.R.S. Monday March 5th at 8.30 p.m. Lecture “Surfaces of Metals,” by Professor A.W. Adamson. Joint Meeting with the Royal Institute of Chemistry. Reading Wednesday February 14th 1962 at 6 p.m. Lecture “Free-radical Polymerisation in the Solid State,” by Dr. C. H. Bamford M.A. F.R.I.C. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry to be held in the Large Chemistry Lecture Theatre The University. St. Andrews and Dundee Tuesday February 6th 1962 at 5 p.m. Lecture “A Few Chemical Problems Connected with Cancer Chemotherapy,” by Professor F. Bergel D.Sc. F.R.S. To be given in the Chemistry Depart- ment Queen’s College Dundee. Friday February 9th at 5.15 p.m. Lecture “The Relationship between Physical Chem- istry and Physics,” by Professor T. L. Cottrell D.Sc. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry to be held in the Chemistry Department St.Salvators College St. Andrews. Friday February 23rd at 5.15 p.m. Lecture “The Synthesis of Pure Triglycerides and their Analysis by means of Enzymes,” by Dr. A. Crossley A.R.I.C. Joint Meeting with the University Chemical Society to be held in the Chemistry Department St. Salvators College St. Andrews. Sheffield Friday February 23rd 1962 at 4.30 p.m. Centenary Lecture “Calabash-curare Alkaloids,” by Professor H. Schmid Dr.Phi1. Joint Meeting with the Royal Institute of Chemistry to be held in the Chemistry Department The University. Southampton Friday February 2nd 1962 at 5 p.m. Lecture “Carbonyls Computers and Crystallo-graphy,” by Dr.0. S. Milk. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University Wednesday February 14th at 7 p.m. Lecture “Lignefied Gases,” by Dr. S. A. Miller M,A. Joint Meeting with the Portsmouth and District Chemical Society to be held in the College of Technology Portsmouth. Thursday February 15th at 5 p.m. Lecture “Resonance-Alive or Dead?” by Profes- sor C. A. Coulson D.Sc. F.R.S. Joint Meeting with the University Chemical Society and the Royal Insti- tute of Chemistry to be held in the Institute of Education The University. Swansea Monday March 5th 1962 at 4.30 p.m. Lecture “The Active Centres of Enzymes,” by Professor H. N. Rydon D.Sc. D.Phil. F.R.I.C.Joint Meeting with the University College Chemical Society to be held in the Department of Chemistry University College. 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.) Abell Paul Irving Ph.D. Department of Chemistry University of Rhode Island Kingston Rhode Island U.S.A. Abraham Raymond John Ph.D. Department of Organic Chemistry The University Liverpool. Adler Melvin B.S. 3133 Rochambeau Avenue Bronx 67, New York U.S.A. Ahmad Nisar Ahmad M.Sc.Department of Organic Chemistry The University Manchester 13. Alston Terence George B.Sc. 26 Woodside Close, Alperton Wembley Middlesex. Arient Joseph D.Chem. Byzkumny ustav organickych syntez Pardubice-Rybitvi Czechoslovakia. Armour Margaret Ann B.Sc. 20 Bingham Terrace Edinburgh 15. Austin John Dudley B.Sc. Department of Chemistry, The University Leicester. Bailey Joan Elizabeth B.Sc. 7 Lithos Road London N.W.3. Banks Reginald George Sinclair. Neighbridge House Ludford Ludlow Salop. Barnes Andrew Nicholas Morrison. 16 Holmwood Gardens Wallington Surrey. Barker William Wilson B.Sc. Chemistry Department University of Western Australia Nedlands Western Australia. Bastin Martin William. 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Chambers Richard Frank. St. Catharine’s College, Cambridge. Chester Arthur W. B.S. 11 11 F University Village East Lansing Michigan U.S.A. Clarke John Alfred B.Sc. 3 Whitcombe Place Ripley Derbyshire. Clifton Brian George B.Sc. Edward Davies Chemical Laboratories University College of Wales Aberyst- wyth. Cook Christopher David B.Sc. M.A. Department of Chemistry University of Toronto Toronto 5 Canada. Craig Christopher Bradberry. 6 Rivey Close West Byfleet Surrey. Csizmadia Imre G. M.Sc. 4639 W. 10th Avenue Vancouver 8 B.C.Canada. Csizmadia Valeria M. M.Sc. 4639 W. 10th Avenue Vancouver 8 B.C. Canada. Das Manik Lal D.Phi1. Department of Biological Science Purdue University Lafayette Indiana U.S.A. Davies Malcolm. The Lindens Heytesbury Warminster Wilts. Dearden Michael Bailey. Earles Cottage Hollinwood Road Disley Stockport Cheshire. Di Tullio Vincent Anthony B.Sc. Room 504A McGill University Montreal Canada. 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New York. 1961. Rules for I.U.P.A.C. notation for organic compounds. Issued by the Commission on codification ciphering and punched card techniques. Pp. 107. Longmans. London.1961. (Presented by the publishers.) Experimental nuclear chemistry. G. R. Choppin. Pp. 226. Prentice-Hall. New Jersey. 1961. Separation of isotopes. Edited by H. London. Pp.488. Newnes. London. 1961. Valency and molecular structure. E. Cartmell and G. W. A. Fowles. 2nd edn. Pp. 294. Butterworths. London. 1961. Spectroscopy.S. Walker and N. Straw. Vol. 1. Pp.267. Chapman & Hall. London. 1961. Molecular spectroscopy. G. H. Beaven E. A. Johnson M. A. Willis and R. G. J. Miller. Pp. 336. Heywood. London. 1961. Direct methods in crystallography. M. M. Woolfson. Pp. 144. Clarendon Press. Oxford. 1961. Kinetics and mechanism a study of homogeneous chemical reactions. A. A. Frost and R. C. Pearson. 2nd edn. Pp. 405. John Wiley & Sons.New York. 1961. Critical solution temperatures. A. W. Francis. (Ad- vances in Chemistry Series No. 31). Pp. 246. A.C.S. Washington. 1961. Chimie physique des semiconducteurs. J. P. Suchet. Pp. 221. Dunod. Paris. 1961. (Presented by the publisher.) Photometric titrations. J. B. Headridge. Pp. 131. Pergamon Press. Oxford. 1961. Principles and applications of paper electrophoresis. C. Wunderly. Pp. 242. Elsevier. Amsterdam. 1961. Gas chromatography abstracts. Edited by C. E. H. Knapman; Sponsored by the Gas Chromatography Dis- cussion Group. 1958-1960 (3 Vols.). Butterworths. London. 1958-1 960. Absorption distillation and cooling towers. W. S. Norman. Pp.477. Longmans. London. 1961. Structural principles in inorganic compounds.W. E. Addison. Pp. 183. Longmans. London. 1961. Nouveau traite de chimie minerale. Edited by P. Pascal. Vol. 15 (2). Pp.639. Masson. Paris. 1961. Phosphorus and its compounds. J. R. Van Wazer. Vol. 2. Pp. 2046. Interscience. New York. 1961. A guidebook to mechanism in organic chemistry. P. Sykes. Pp. 247. Longmans. London. 1961. Techniques of organic chemistry. Edited by A. Weiss- berger. Vol. 8. Part 1. Investigation of rates and mechan- isms of reactions. Edited by S. L. Friess E. S. Lewis and A. Weissberger. 2nd edn. Pp. 702. Interscience. New York. 1 961. Isopropyl alcohol. L. F. Hatch. Pp. 184. McGraw-Hill. New York. 1961. Chromatography of steroids. I. E. Bush. Pp. 437. Pergamon Press. Oxford. 1961. Quantitative organic microanalysis.A. Steyermark. 2nd edn. Pp. 665. Academic Press. New York. 1961. Protein structure. H. A. Scheraga. Pp. 305. Academic Press. New York. 1961. Metabolic pathways. Edited by D. M. Greenberg. Academic Press. New York. 1961. Textbook of pharmaceutical chemistry. A. 0. Bentley and J. E. Driver. 7th edn. Revised by J. E. Driver. Pp. 728. O.U.P. London. 1960. Introduction to physiological and pathological chem- istry. L. E. Arnow and M.C. D’Andrea Logan. Pp. 490. Mosby. St. Louis. 1961. (Presented by the publisher.) Medicinal chemistry; a series of reviews prepared under the auspices of the Division of Medicinal Chemistry of the American Chemical Society. Edited by W. E. Hartung. VoI. 5. Pp.432. John Wiley & Sons. New York. 1961. Chemical control of insects.T. F. West and J. E. Hardy. 2nd edn. Pp. 206. Chapman & Hall. London. 1961. Nitric acid manufacture and uses. F. D. Miles. Pp.75. O.U.P. London. 1961. Minerals for the chemical and allied industries. S. J. Johnstone and M. G. Johnstone. 2nd edn. Pp. 788. Chapman & Hall. London. 1961. Asphalt; its composition properties and uses. R. N. Traxler. Pp. 294. Reinhold. New York. 1961. Toxicity of industrial metals. E. Browning. Pp. 325. Butterworths. London. 1961. Paint technology manuals. Part 2. Soivents oils, resins and driers. Edited by I. C. R. Bews. Pp. 239. Chapman & Hall. London. 1961. An introduction to sewage treatment. Issued by the Institute of Sewage Purification. Pp. 45. Inst. Sewage Purification.London. 1960. Proceedings of the fourth International Congress of Biochemistry Vienna 1958. Edited by 0. Hoffmann-Ostenhof. Issued by the Jnternational Union of Biochem- istry. Vol. 8. Proteins. Edited by H. Neurath and H. Tuppy. Pp. 258. Pergamon Press. London. 1960. (Pre-sented by Prof. G. W. Kenner.) Borax to boranes a symposium presented before the Division of inorganic chemistry at the 133rd National Meeting of the A.C.S. California 1958 and the 135th Meeting Boston 1959. (Advances in Chemistry Series No. 32.) Pp. 244. A.C.S. Washington. 1961. Transactions of the symposium on electrode processes. Edited by E. Yeager. Papers presented at a symposium of the Theoretical Electrochemistry Division of the Electrochemical Society Philadelphia 1959.Sponsored by the Electrochemical Society Inc. Pp. 374. John Wiley & Sons. New York. 1961. Proceedings of the Fourth International Symposium on the Reactivity of Solids Amsterdam 1960. Edited by J. H. de Boer. Pp. 762. Elsevier. Amsterdam. 1961. Proceedings of the Fifth International Instruments and Measurements Conference Stockholm 1960. Edited by Helge von Koch and Gregory Ljungberg. Vol. 1. Pp. 506. Academic Press. New York. 1961. Recent developments in the chemistry of natural phenolic compounds. Proceedings of the Plant Phenolics Group Symposium. Edited by W. D. Ollis. Pp. 237. Pergamon Press. Oxford. 1961. NEW JOURNALS Chromatographic Reviews from 1961,3. Phytochemistry from 1961,l. Radiochemistry from 1960,l.
ISSN:0369-8718
DOI:10.1039/PS9620000001
出版商:RSC
年代:1962
数据来源: RSC
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