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Proceedings of the Chemical Society. June/July 1959 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue June-July,
1959,
Page 169-200
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY JUNE/JULY 1959 CHEMICAL SOCIETY MEETING At a Scientific Meeting of the Chemical Society at Burlington House on Thursday May 7th 1959 with the President (Professor H. J. Emeldus) in the Chair the following papers were read and discussed. Recent Developments in the Chemistry of the In answer to Professor Lythgoe Dr. Battersby Ipecacuanha Alkaloids. By A. R. BATTERSBY stated that cis-3,4-diethylcyclopentanonehad been R. BINKS,G. C. DAVIDSON and B. J. T. HARPER S. GARRATT. The non-phenolic bases present in ipecacuanha have been re-examined and in addition to the known alkaloids emetine 0-methylpsychotrine and eme- tamine two new bases have been isolated. The structure of one of these named protoemetine has been elucidated and its biogenetic significance will be discussed.Suitable degradative experiments on 0-methylpsychotrine and protoemetine when coupled with stereospecific syntheses allow the stereochem- istry of emetine to be deduced. Sir Alexander Todd asked whether the Kuhn-Roth oxidation of protoemetine had yielded acetic acid or a mixture of acetic and propionic acid. Dr. Battersby replied that this had not been studied in the case of protoemetine but that oxidation of emetine which has a strictly analogous C-ethyl group yields about equal amounts of acetic and propionic acid. prepared by cyclising rneso-3,4-diethylpimelicacid with acetic anhydride according to Koelsch and Stratton’s method. Dr. Osbond mentioned finding that emetine is converted into rubremetine by mercuric acetate more slowly than is isoemetine.He asked whether this result could be used for stereochemical deductions. The answer was that this is not possible by inspection of ordinary blackboard drawings of the two mole- cules but that scale models of the intermediate mercurated complexes would probably be helpful. Aldol Pinacol and Benzoin-type Reactions of Al-Pyrroline 1-Oxides. By R. F. C. BROWN V. M. CLARK,M. LAMCHEN and B. SKLARZ Sir ALEXANDER TODD. Addition of the anion of the nitrone (I) to the nitrone (11) leads to the nitrone-hydroxylamine (111) in the di-2-pyrrolidinylmethaneseries. With 5 :5-di-methyl-dl-pyrroline 1-oxide (IV) as the sole reactant 169 an analogous aldol-type reaction leads to the bipyrrolyl derivative 0.Under certain conditions sodamide in liquid ammonia catalyses the benzoin- type dimerisation of the nitrone (IV) to the bi-2-pyrrolyl derivative (VI). The corresponding bishydroxylamine is obtained by pinacol-type reduction of the nitrone (IV) under aprotic conditions. Degradative proof of the struc- ture of the bi-derivative (VI) will be presented. . Dr. M. A. T. Rogers said that the dimerisations of nitrones described by Dr. Clark did not exhaust the record of nitrones in this respect for he (Dr. Rogers) had shown that the seven-membered ring nitrone (VII) gave during its spontaneous polymerisation 9-0-(IX) '0-(X> some of the dimer (IX) possibly by way of an inter- mediate (VIII).This intermediate would be closely analogous in spatial arrangement of atoms to the dimer (X)which as Dr. Clark had pointed out is the stable form of the six-membered ring nitrone and the startling differences in behaviour and stability of the five- six- and seven-membered ring nitrones appear to be a consequence of steric effects in (VII) and (X) and their homologues. Dr. Rogers asked whether the simple purely aliphatic non-cyclic nitrones could be induced to undergo dimerisations analogous to those which Dr. Clark had described. In reply Dr. Clark said that to his knowledge no such simple purely aliphatic non-cyclic nitrone had PROCEEDINGS yet been described. However if the mi-form of nitromethane (XI) were regarded as an example of this type of nitrone then its conversion under alkaline conditions into a salt of methazonic acid1 (XII) afforded another illustration of the benzoin- type dimerisation.Dr. Rogers added that he had shown that the nitrone (XIII) when quaternised with methyl iodide gave a dimeric substance isolated as picrate with the composition (XIV). Had Dr. Clark examined this compound to which Dr. Rogers and his colleagues had tentatively assigned structure (XV) ? 0-0 (x111) (X Iv) (xv) Dr. Clark replied that the Cambridge workers had not examined the products of methylation of their nitrones but that he expected the 0-methyl deriva- tive of (XIII) to lose a proton giving (XVI) which M",'2r OMe (XVI \ fimyl:2MemLJEz Me2 pJ Me2 '13 I OMe (XV II) OMe (XVIII) with (XIII) might yield the aldol-type product (XVII).Thermal elimination would then give (XVI 11) corresponding to Dr. Roger's product (XV). Professor Johnson asked Dr. Clark if he would indicate in general fashion the later stages in the synthesis of corrin as at present envisaged. All of the intermediates described in the paper contained gem-dimethyl groups which would not permit further condensation. In the Nottingham Laboratories a derivative (XIX) of corrin had been prepared recently by con- densation of the appropriate dipyrromethenes. The Dunstan and Goulding J. 1900,77 1264. JUNE/JULY 1959 nature of the bond between the hydroxyl group and the palladium atom was still to be determined.The ultraviolet and visible absorption spectrum of com-pound (XIX) resembled that of palladium Etiopor- phyrin I closely except that there was absorption further into the red region of the visible spectrum. i-Dr. Clark indicated the general features of the further work in progress at Cambridge and in par- ticular showed how N-hydroxypyrrolidines bearing an a-carboxyl group underwent oxidative decar- boxylation2 to ni trones having synthetic utility e.g. (XX) + (XXI). In reply to a question from Professor Lythgoe on the mechanism of the benzoin-type reaction Dr. Clark pointed out that the condensation might occur through the formation of the anion (=I) whose electron distribution might also be represented as (XXIII) where the carbon atom bears six electrons.This representation is then analogous to that of the cyanide ion viz. (XXIV). As the nitrone group also facilitates the removal of a proton from an adjacent carbon atom aldol- and benzoin-type products might be formed concurrently their ratio being dependent inter alia upon tempera- ture solvent and the nature of the base catalysing the reaction. When sodamide in triethylamine at room tempera- ture was used both types of product were obtained. Alderson Clark and Todd unpublished observations. 171 Perpendicular Conjugation in Some Octahedral Metallophthalocyanine derivative^.^ By J. A. ELVIDGE and A. B. P. LEVER. Manganous phthalocyanine and the newly authen- ticated hydroxychromic phthalocyanine have been converted by methanolic sodium hydroxide into the octahedral derivatives dihydroxymanganeseIv phthalocyanine [PcMn(OH),] and aquohydroxy-chromium1" phthalocyanine [PcCr(H,O)OH] res-pectively (where Pc = the phthalocyanine residue).These structures are substantiated by elementary analyses magnetic measurements infrared absorp- tion and conversions into other derivatives. Dihydroxymanganese'v phthalocyanine and aquo- hydroxychromic phthalocyanine are apparently unique in being dibasic acids. Thus preparation of the salts [P~Mn0,]~-2Naf [FCC~(OH)O]~-~N~+ and [PcCr(OH)0I2-2pyH+ has been substantiated. It seems that no examples are known in inorganic chemistry of the displacement of a proton from a hydroxy-group attached directly to a chelated metal atom.Presumably there must be means for stabilising the anions [PcMn0,I2- and [PcCr(OH)0I2- and this may be achieved through a sharing of the nega- tive charge with the aromatic r-electron system as is accepted for example in the phenoxide anion. For the sharing to be possible in the phthalocyanine anions there must be conjugation between the mutually perpendicular phthalocyanine and oxy-groups. Perpendicular conjugation is a new concept. It appears to be possible in the present cases to form wbonds by overlap of dZz-and/or &-orbitals of the metal atom with p-orbitals of the oxygen along the z-axis and with p-orbitals of the nitrogen along the x-and/or y-axis. Consequently there may be resonance sharing of the negative charge between the mutually perpendicular groupings of the molecule (cf.A). Whilst there are restrictions on the occurrence of perpendicular conjugation it seems that it would be possible in compounds of types other than those now described. Elvidge and Lever Proc. Chern. Soc. 1959 PROCEEDINGS LES DEBUTS DE LA CHIMIE DU FLUOR Par LOUIS DOMANGE (PROFESSEUR DE CHIMIE MI~RALE DE PHARMACIE DE PARIS) A LA FACULTB LES raisons pour lesquelles le fluor n’a CtC prkparC pour la premikre fois qu’h la fin du XIXihme sikcle on t CtC remarquablement Cnon- ctes en 1846 par le chimiste belgeL ouyet. Dans le compte rendu d’un memoire dCposk h 1’AcadC-mie des Sciences de Paris il a en effet Ccrit ce qui suit? “Relativement B la nature du fluor j’ai dQ faire remarquer que si des doutes subsistent encore dans l’esprit d’aprks les expkriences de MM.Knox et les miennes celh dCpend en grande partie de l’imperfection des appareils que nous sommes obligks d’employer. Que l’on con- sidkre en effet que nous sommes forcks de rejeter la plus grande partie des vases avec lesquels on expkrimente en chimie; que pour recueillir les gaz que nous pouvons dkgager dans nos ex-pkriences on ne put employer aucune des mkthodes suivies jusqu’g ce jour; que la plupart de ces essais doivent &re faits dans des vases opaques trks Cpais mauvais conducteurs de la chaleur trks fragiles peut-&re permkables ii l’air et l’on aomprendra quelles difficultks nous avons A vaincre pour donner une solution complkte B cet important problkme de chimie inorganique.” D’autre part on lit h la fin du meme compte rendu “En terminant mon Mkmoire j’ai fait remarquer qu’il est necessaire de prendre les plus grandes prkcautions pour se prkserver de l’atteinte des vapeurs fluorhydriques quand on voudra rCpCter ces experiences ;car elles agissent avec la plus grande knergie sur l’kconomie animale.Tous les chimistes qui se sont occupCs du fluor l’ont appris h leurs dkpens; MM. Gay-Lussac et Thenard ont fortement insist6 sur ses dangereux effets outre les douleurs aigues sous les ongles l’inflammation momentanke des yeux la fatigue de la vue on est atteint de maux de poitrine d’irritation prolongke du larynx de crachements kpais et parfois sanglants et il faut beaucoup de temps pour se rktablir.I1 est rare que ses effets soient instantanks et rapides. Le rkvkrend Th. Knox a failli en mourir ;le ma1 n’a disparu qu’en faisant usage de l’acide cyan- hydrique pendant six mois. M. George Knox en a ressenti les effets pendant trois annkes et a dii aller ii Naples pour se rktablir. Quant a moi ma santk en a CtC profondement altkrke et j’ai crachk le sang ii plusieurs reprises.” Louyet Compt. rend. 1846 23,960. a Fremy Ann. Chim. Phys. 1856,47 5. Peu de temps aprks Louyet payait de sa vie sa passion pour la science. Dans son mkmorable travail intitult “Re-cherchessur les fluorures,” Frkmy kcrit,2 en 1856 h propos des difficult& de cette chimie si particulikre “Dans un pareil travail dont les difficultks sont connues de tous les chimistes et arrivant aprks des savants tels que Davy Gay-Lussac Berzelius M.Thenard je ne devais pas compter sur une de ces bonnes fortunes scientifiques qui pouvait me conduire a la dkcouverte du fluor; mais je savais qu’une ktude gknkrale des fluorures prksenterait dans tous les cas un intkret vkritable pour la science. . . .” It est bien certain que l’isolement du fluor ne pouvait &re le rksultat d’une expkrience non raisonnke. Les propriCtCs du fluor inconnues ou seulement soupconnkes B cette Cpoque celles de l’acide fluorhydrique si dangereux et si difficile A manipuler 3i 1’Ctat anhydre empechaient absolu- ment toute possibilitk de preparation du fluor au moyen d’une expkrience faite au hasard.Ce hasard qui cependant avait souvent permis l’obtention d’klkments jusque-18 inconnus. Le premier obstacle ktait donc d’ordre materiel impossibilitC d’utiliser les instruments habituels des chimistes. Cet obstacle sCrieux a CtC l’une des causes de la lenteur avec laquelle la chimie du fluor a atteint le stade industriel. Entre les deux grandes guerres la “bakklite” a bien permis de travailler avec des solutions fluor- hydriques moyennemen t concentrkes et quelques progrks ont etk rkalisks mais son emploi ktait trks limitk. L’klan a pu etre donnk depuis la dernikre guerre griice A l’apparition des plastiques fluores ou fluochlores dont quelques-uns son t mhe transparents. L’emploi de ces plastiques a causk une veritable rkvolution dans les tech- niques des laboratoires et des industries spkcialises.Le deuxiime obstacle qui s’ktait montrk si meurtrier pour les pionniers de la chimie du flum n’en est plus gukre un maintenant. Le danger est kvidemment toujours prksent mais le connaissant mieux on a pu amener les moyens de protection A un tr&s haut degrk d’efficacitk. I1 est actuellement possible en travaillant bien en tendu avec de grandes precautions d’utiliser le fluor contenu sous pression dans des tubes d’acier de JUNE/JULY 1959 manipuler l’acide fluorhydrique anhydre les fluorures de chlore et de brome si redoutables sans accidents skrieux. En lisant les mkmoires relatifs A la chimie du fluor nous avons recherchk A partir de quel moment le nom de fluor a ktk employ6 pour designer cet klkment.Le “spath fluor”,* utilisk comme fondant est 21 l’origine de l’expression. On recontre dans les mkmoires les mots “acide fluorique” (pour dksigner l’acide fluorhydrique que l’on croyait oxygknk),? “fluates,” “principe fluorique.” H. Davy dans un mkmoire3 la Royal Society (de Londres) du 8 juillet 1813 fait allusion A l’existence de ce nouvel klkment de la facon suivante “De la skrie gknkrale des rksultats que je viens d’ktablir il parait raisonnable de conclure que dans les composks fluoriques il existe une substance particulihre douke d’une forte attrac- tion pour les corps mktalliques et pour l’hydro- ghne laquelle combinke avec certains corps inflammables forme des acides particuliers et qui en conskquence de ses fortes affinitks et de ses grandes energies dkcomposan tes sera trks difficile A examiner dans son ktat de puretk.Pour ne point employer de circonlocution on peut l’appeler ‘fluorine,’* nom qui m’a ktk suggkrk par M. Ampkre.” En franc;ais c’est le mot “fluor” qui a ktk adoptk. Pendant longtemps la vkritable nature de l’acide fluorhydrique fut inconnue. C’est a Ampkre et Davy que l’on doit d’avoir montrk que l’acide fluorhydrique ktait un acide non- oxygkne form6 d’hydrogkne et d’un principe inconnu. Les &changes de correspondance entre Ampere et Davy se sont montrks extremement fructueux. Davy s’exprime en ces termes :“Dam le temps oh je faisais ces recherches je requs de Paris de M.Ampkre deux lettres contenant des arguments ingknieux et neufs en faveur de l’analogie que prksentent les composks muria- tiques et fluoriques. M. Ampkre me fit part de ses idkes de la manikre la plus obligeante. Elles ktaient une conskquence des miennes sur le chlorine et appuykes de raisonnements tirks des expkriences de MM. Gay-Lussac et Thknard.” Si l’on se reporte aux kvknements qui se dkroulaient A cette kpoque il est impossible de rester insensible i l’klkgance du langage A tant de courtoisie. Avant eux Margraff,4 en 1768 avait ktudiC l’action de 1”‘huile de vitriol” sur la fluorine (spath-fluor) Scheele5 avait caractkrisk l’acide fluorhydrique en 1771 sans l’obtenir pur. Gay-Lussac et Thknard6 produisiren t en 1809 un acide concentrk pur mais non anhydre.La prksence de cette humiditk tr&s difficile A Cviter avait fait croire que l’acide fluorhydrique renfermait de l’oxygkne. Davy qui posskdait une grande expkrience en klectrolyse avait observk que l’oxygenes oit en nature soit combink ti d’autres klkments se dkgageait a l’klectrode nkgative. Afin de con- firmer la prksence ou l’absence d’oxygkne dans 1”‘acide fluorique” il entreprit l’klectrolyse de ce dernier. Ce faisant il ne semble pas qu’il ait cherchk a isoler de fluor mais A montrer la vkritable nature de l’acide fluorhydrique. I1 opera dans une capsule de platine. L’klectrods positive etait constituke par un fil de platine traversant un morceau de chlorure d’argent cornk.I1 observa la corrosion du fil de platine positif et il montra que le gaz dkgagk au p6le positif ktait de I’hydroghe. I1 fit kgalement passer des ktincelles klectriques dans l’acide fluorhydrique mais il ne put faire d’observations utiles tant l’atmosphkre etait devenue irrespirable par suite de la volatilisation de l’acide. Davy tira de ses expkriences les conclusions suivantes “. . . et la manihre la plus simple de les expliquer (les phknomknes observks) c’est de supposer l’acide fluorique ainsi que l’acide muriatique composk d’hydrogkne et d’une substance jusqu’ici inconnue sous une forme distincte posskdant comme l’oxygkne et le chlorine l’knergie klectrique nkgative par con- skquent port6e a la surface positive et fortement attirke par les substances mktalliques.” S’il n’obtenait pas de fluor par suite de l’humiditk renfermke dans ses matikres premieres Davy augmentait progressivement les connais- sances sur les proprikt6s de ce principe nouveau qui attaquait un grand nombre de substances.Entre autres observations il remarqua que l’acide fluorhydrique laissait passer le courant avec d’autant plus de difficult6 qu’il ktait plus anhydre. I1 nota d’autre part que si l’on partait de sels les * I1 est nkessaire de prkiser qu’en langue franpise le “fluor” dCsigne 1’CICment no 9. On I’appelle “fluorine” en anglais. Pour la langue franqaise fluorine est le nom du spath-fluor. t En franqais l’expression “acide fluorhydrique” dkigne aussi bien la solution que l’acide anhydre.Pour prkiser on ajoute parfois “anhydre,” ou “en solution.” En anglais l’acide anhydre est nommC “hydrogen fluoride.” C‘est mieux aim. Davy ibid. 1813 88 271. ‘Margraff Trans. de Berlin 1768. Scheele Mem. Acad. Sci. Stockholm 1771 2nd quarter; Mem. Chim.,1771 1 1. Gay-Lussac and Thenard Ann. Chim. Phys. 1809 19 204. “fluates,” il ktait nkcessaire de les obtenir aussi secs que possible. I1 essaya vainement l’action du chlore B chaud sur les fluorures de sodium de potassium de mercure d’argent. I1 en dkduisit que le fluor devait posskder une activitk chimique plus grande que celle des corps connus. Les expkriences de Davy furent de la plus grande importance car elles mirent en kvidence l’activitk du fluor sur le platine et l’or B chaud sur le verre etc.Elles fournirent B ses successeurs des renseignements prkcieux. Plus tard G. Knox et Th. Kn~x,~ membres de la Royal Irish Academy reprirent l’action du chlore sur le fluorure d’argent expkrimentke B nouveau sans succks par Aimkg dans un vase recouvert de caoutchouc. 11s opkraient dans des rkcipients de spath-fluor mais n’isolkrent pas le fluor. Aid6 par G. Knox qui lui prsta et lui fit construire des appareils en spath-fluor Louyetl (1846) fit A nouveau agir le chlore sur le fluorure d’argent. Aucune de ces expkrimentations ne put aboutir A un rksultat positif. A la suite des travaux de Louyet les idkes d’Ampkre et de Davy sur l’absence d’oxygkne dans l’acide fluorhydrique furent remises en question.Devant les difficultks rencontrkes pour dkshydrater l’acide fluorhydrique obtenu par action de l’acide sulfurique sur le spath-fluor Dumas suggtra a Louyetg (1847) de desskcher l’acide fluorhydrique par passage sur de l’an- hydride phosphorique. Cette idke malencon-treuse mais fort excusable puisqu’on ne connais- sait pas toutes les propriktks de cet acide embrouilla de nouveau le problkme. A la place de l’acide fluorhydrique Louyet manipulait en effet un oxyfluorure de phosphore composk oxygknk. I1 semble que personne avant Moissan ne se soit aperCu de la formation d’oxyfluorure au cours des expkriences de Louyet. I1 fallu attendre les admirables travaux de Frkmy,2 commencks vers 1850 et publiks en 1856 pour que la clartk revint dkfinitivement.11s confirmkrent la justesse des vues de Davy et Ampkre. Au dkbut de son mkmoire Frkmy s’exprime ainsi “Ayant eu l’occasion d’assister A quelques expkriences faites par M. Louyet et ne les ayant pas trouvkes satisfaisantes je me suis proposk de soumettre les faits qui avaient Ctk annoncks par le chimiste belge une vkrifica- tion strieuse . . . on voit que je me trouvais ainsi dans l’obligation d’examiner l’acide fluor-hydrique anhydre de faire une Ctude gknkrale des fluorures . . .” G.J. Knox and Th. Knox Proc. Roy. Irish Acad. 1841 9 107. a AimC Ann. Chim. Phys. 1833,55,443. Louyet Compt. rend. 1847,24 434. PROCEEDINGS Frkmy prkpara pour la premikre fois de l’acide fluorhydrique anhydre pur par une mkthode actuellement toujours valable dkcomposition par la chaleur du fluorhydrate KF,HF.I1 montra que les fluorures mktalliques anhydres ktaient bien des composts binaires et non des “fluates’’ dont le nom sous-entendait la presence d’oxy- gkne. Reprenant avec un soin extrEme le plus souvent dans le platine tous les essais par voie chimique de ses prkdkcesseurs en particulier les essais de dkplacement du fluor par le chlore ou l’oxygkne il n’obtint aucune trace de fluor. I1 dkcida alors de mettre en oeuvre l’klectrolyse. Les premikres expkriences lui montrkrent que lors de l’klectrolyse d’une solution d’acide fluor- hydrique on observe des dkgagements d’oxygkne et d’hydrogkne puis que une fois l’eau dkcom- poske le courant ne passe plus. I1 s’adressa ensuite aux fluorures mktalliques.Ayant observk qu’il ktait trks difficile d’obtenir des fluorures mktalliques rigoureusement anhydres il rksolut de faire passer le courant klectrique dans le spath- fluor fondu. I1 ktait stir ainsi de s’adresser A un sel anhydre. L’klectrolyse du fluorure de calcium fondu dans un creuset de platine pris comme cathodes avec une anode constituke par un fil de platine lui montra une vive effervescence au p81e positif avec dkgagement d’un gaz attaquant le verre. Malheureusement l’attaque du creuset de platine par le calcium mettait rapidement fin B l’opkration. I1 essaya ensuite plusieurs autres fluorures et s’adressa au fluorure de potassium fondu. I1 opkra alors dans une cornue de platine tubulke servant de cathode.Un gros fil de platine plongeant dans le fluorure fondu constituait l’anode. L’observation de Frkmy est saisissan te de prkcision et d’exactitude. “En mettant l’expkrience en activitk on voit le fluorure alcalin se dkcomposer rapidement; le fil de platine qui plonge dans le fluorure est attaquk par le fluor s’use et se transforme momentankment en fluorure de platine qui lui- meme ne tarde pas 2i se dkcomposer par l’action de la chaleur en produisant de la mousse de platine que l’on retrouve aprks l’expkrience . . . “I1 se dkgage par le col de la cornue de platine un gaz odorant qui dkcompose l’eau en produisant de l’acide fluorhydrique et qui dkplace l’iode des iodures ce gaz me parait &re le fluor.’’ Malheureusement l’usure du fil de ylatine et la projection de fluorure de potassium inter-rompaient l’expkrience assez rapidement.1,54; Lodon and Edinburgh Phil. Mag. and J. Sci. 1836 JUNE/JULY 1959 I1 apparait comme certain que Frkmy a isolk le fluor en tr&s petite quantitk. I1 est curieux mais il serait profondkment injuste de le lui reprocher qu’il n’ait pas song6 i klectrolyser le fluorhydrate KF,HF qu’il savait prkparer anhydre. Ce sel plus fusible que le fluorure KF lui aurait permis d’effectuer l’klectrolyse B une tempkrature plus basse qu’avec le fluorure KF. I1 aurait alors pu obtenir des quantitks apprkciables de fluor avant destruction totale de l’anode. Tout le travail de Frkmy a eu une importance considkrable pour la chimie du fluor.Moissan kcrit ii son sujet :“Le Mkmoire de ce savant com- portait un si grand nombre d’expkriences qu’il semble avoir dkcouragk les chimistes arr&tC I’essor de nouvelles recherches.” De fait jusqu’en 1869 on ne trouve plus de mkmoires sur ce sujet. A cette date un chimiste anglais Gore7lo reprit mkthodiquement l’ktude de l’acide fluorhydrique prkpark par la mkthode de Frkmy il effectua des recherches sur le fluorure d’argent et klectrolysa ce fluorure. L’on arrive maintenant aux recherches de Henri Moissan qui devaient aboutir i l’obtention de fluor en quantitk suffisante pour permettre I’ktude de ses propriktks physiques et chimiques. Etadiant avec soin les travaux de ses illustres predecesseurs Henri Moissan sut discerner les causes de leurs kchecs.I1 pensa tout d’abord qu’il serait plus facile d’isoler le fluor ii partir de ses composks mktalloidiques. Cette idke le con- duisit a prkparer et ktudier les proprietks des fluorures de phosphore d’arsenic de bore de silicium. I1 essaya l’action d’une ktincelle d’induction et du platine chauffk au rouge sur ces composks. I1 n’obtint que quelques manifesta- tions extkrieures de la prksence fugitive de fluor. Aucune de ces recherches pour intkressantes qu’elles fussent ne permit d’obtenir du fluor libre. Moissanll reporta alors ses efforts sur l’electrolyse du trifluorure d’arsenic liquide bien sec. Un creuset de platine servait de cathode l’anode ktait constituke par un fil de platine. I1 obtint autour de ce fil une petite gaine gazeuse qui posskdait la proprietk de dkcomposer l’iodure de potassium.Afin d’augmenter la conductibilitk du fluorure d’arsenic Moissan lui ajouta du fluorure de potassium. Mais observant les choses de plus prks il s’aperqut qu’il n’y avait pratique- ment aucun dkgagement gazeux extkrieur. Les bulles de gaz libkrkes a l’anode disparaissaient rapidement. Le trifluorure se transformait en pentafluorure sous l’action du fluor. Nullement dCcouragC Moissan entreprit l’klectrolyse de l’acide fluorhydrique anhydre. Bien antkrieurement Faraday Davy FrCmy et Gore avaient observe que l’acide anhydre ne conduisait pas le courant klectrique. Malgrk tout il dkcida de tenter l’expkrience A son tour. Un dktail expkrimental devait lui &re successivement favorable puis nkfaste.Dans un petit tube en U en platine refroid par du chlorure de mkthyle en kbullition Moissan condensa environ 30 ml d’acide an-hydre. Celui-ci provenait directement de la dkcomposition par la chaleur du fluorure KF,HF dans une cornue de platine suivant la mkthode de Frkmy. Chaque branche du tube ktait fermke par un bouchon de spath-fluor laissant passer une electrode de platine. Deux tubes ii dkgage-ment ktaient prkvus pour chacune d’elles l’un pour l’hydroghe l’autre pour le fluor tant at t endu. A la suite de ses ktudes sur le fluorure de silicium Moissan en avait dCduit que ce composk ktait trks stable et que le fluor devait trks probablement se combiner violemment avec le silicium.Ayant mis le courant klectrique Moissan eut la joie le 26 juin 1886 vers midi de constater avec Rigaud prkparateur de Troost et Friedel qui ktait par hasard en visite le dkgagement d’un gaz qui se combinait a froid avec le silicium en briilant avec un vif kclat. Pour la premikre fois le fluor ktait prkpark en quantitk notable et il ktait indubitablement caractkrisk par sa com-binaison avec I: silicium. Cette expkrience mkmorable eut lieu dans le laboratoire de prkparation de cours d’un amphi- thkiitre annexe de la Sorbonne sis rue Michelet ii Paris A c6tk de 1’Ecole de Pharmacie. Le lundi 28 juin 1886 le cklbbre chimiste Debray annonqait a1’Acadkmie des Sciences que Moissan ktait parvenu a isoler le fluor. Une Com- mission fut dksignke pour constater et vkrifier le fait.Avec beaucoup de soins Moissan prkpara pour la circonstance un acide fluorhydrique particulikrement pur. Le jour dit la Commission se rkunit mais le courant come l’avaient signal6 ses prkdkcesseurs refusa de traverser l’acide fluorhydrique et la Commission repartit sans avoir rien vu. Moissan trouva rapidement l’explication de ce qui s’ktait passk. Lors de sa premikre experience une petite quantitk de fluorure KF,HF avait 6tC entrainke avec l’acide fluorhydrique pendant la prkparation de ce dernier. Mais le jour 06 il prkpara l’acide pour loGore,Phil. Trans.,1870,160,227 ;1871,161,321 ;.Bull. SOC.chim. France 1871,14,38; Chem. News,1870,21,28. l1 Moissan “Le Fluor et ses ComposCs,” G.Steinhell Paris 1900. la Commission il conduisit la dkcomposition thermique du fluorure KF,HF avec un soin ex- treme et il obtint de l’acide pur anhydre mais complktement isolant! Se souvenant alors de ses experiences sur le trifluorure d’arsenic auquel il avait ajoutk du fluorure de potassium pour le rendre plus conducteur Moissan mis volontaire- ment une petite quantitk de ce sel dans l’acide fluorhydrique. Le courant klectrique traversait le mklange. La Commission fut k nouveau convoquke et elle put admirer la combustion vive du silicium du fer du mangankse de l’arsenic de l’antimoine pulvkrisks. Elle observa l’inflammation de l’alcool de l’kther du benzkne de l’essence de tkrkbenthine. Debray fut charge par l’Acadkmie des Sciences de rkdiger un rapport sur les travaux de Moissan.Voici ses conclusions “On trouvera dans le Mkmoire de M. Moissan le dktail de ces expkriences dklicates. Elles nous paraissent justifier sa conclusion finale Le gaz que l’klectrode dkgage de l’acide fluorhydrique anhydre est donc bien le fluor.’’ Ainsi se termine l’histoire de I’isolement du fluor. Cet isolement fut la conskquence des efforts dkployks durant un sikcle depuis les travaux de Margraff et de Scheele sur l’acide fluorhydrique par des savants ingknieux patients et courageux. Chacun apporta sa contribution a la connaissance de cette chimie spkciale permet- tant A son successeur de faire un nouveau pas en avant. Nombreux furent les incidents les uns tragiques comme les souffrances endurkes par les fri?res Knox et la mort de Louyet les autres quasi corniques comme l’kchec de l’expkrience de Moissan devant la solennelle Commission dksignke par 1’Acadkmie.L’ensemble forme une merveilleuse aventure. Et nous qui maintenant prktendons ne pas pouvoir travailler sans matkriel ultra-moderne et n’arriver A rien si nos laboratoires ne sont pas luxueux et confortables ne devons-nous pas &re remplis d’humilitk devant l’oeuvre accomplie par ces gkants de la Science? Comme l’a fait au cours d’une conference prononcke en 1952 notre vknkrk maitre Paul Lebeau je terminerai cet expose par une citation de Henri Moissan (1 887) PROCEEDINGS “L‘avancement de la science est lent; il ne se produit qu’k force de travail et de tknacitk.Et lorsqu’on est arrivk a un rbultat ne doit-on pas par reconnaissance se reporter aux efforts de ceux qui nous ont prkckdks de ceux qui ont luttk te peink avant nous. N’est-ce pas en effet un devoir de rappeler les difficultks qu’ils ont vaincues les vues qui les ont dirigks et comment des hommes diffkrents de pays et d’idkes de position et de caractkre mus seulement par l’amour de la Science se sont lkguks sans se connaitre la question inachevke afin qu’un dernier venu pu recueillir les recherches de ses devanciers y ajouter A son tour sa part d’intel- ligence et de travail ? Collaboration intellectuelle entikrement consacrke k la recherche de la vkritk et qui se poursuit de sikcle en sikcle. “Ce patrimoine scientifique que nous cherchons toujours a ktendre est une partie de la fortune de I’humanitk; nous devons garder un souvenir reconnaissant A tous ceux qui lui ont donne la chaleur de leur coeur et le meilleur de leur esprit.’’ Note sur Henri Moissan.1852-1907. Prix Nobel 1906. D’origine trks modeste Henri Moissan fit des etudes secondaires incomplktes faute de res-sources financikres au Collbge de Meaux. I1 fut apprenti horloger participa a la dkfense de Paris en 1870 puis entra comme stagiaire chez un pharmacien parisien. Conseille par Deherain il entra en 1872 au laboratoire de FrCmy puis chez Decaisne et Deherain. Ce dernier tout en l’aidant A vivre lui fit conqukrir les grades universitaires. I1 devint docteur 6s sciences et Debray l’accueillit dans son laboratoire.En 1879 il devint maitre de confkrences des travaux de chimie klkmentaire et de pharmacie A 1’Ecole de Pharmacie de Paris professeur agrkgk en 1882 titulaire de la Chaire de Toxi-cologie puis de la Chaire de Chimie minkrale. Enfin il passa A la Faculte des Sciences pour enseigner la Chimie gknkrale. Outre la chimie du fluor Henri Moissan laisse une oeuvre considerable dam la chimie des hau tes tempkratures. (D’aprks Paul Lebeau qui fut son klkve “Henri Moissan et son oeuvre,” Palais de I’Institut Paris 1953.) JUNE/JULY1959 TILDEN LECTURE* Nucleotides and Bacterial Cell Wall Components By J. BADDILEY (KING’SCOLLEGE OF DURHAM UPON TYNE) UNIVERSITY NEWCASTLE THISlecture is not intended as a review of progress or a comprehensive treatment of either nucleotides or the detailed chemistry of bacterial cell walls.I make no apology for my method of treatment but it should be emphasised that much distinguished work has been done by others on general nucleotide chem- istry and biochemistry and investigations of other aspects of cell-wall structure are now in progress in a number of laboratories. The intention here is to show how with the enthusiastic co-operation of worthy colleagues together with good equipment it is possible to follow up a chance observation and thereby make interesting and significant advances in new fields. This work arose from investigations1 on the un- related subject of the enzymic phosphorylation of pantothenic acid in Lactobacillus arabinosus and its significance in the biosynthesis of coenzyme A.Attempts to purify the pantothenic acid phosphate formed by this organism were complicated by the presence of nucleotides in our extracts. As relatively little was known at that time about the composition of nucleotide mixtures from bacteria a more careful investigation was undertaken. Paper chromato-graphy of hydrolysates of the nucleotide fraction obtained by vigorous acid treatment revealed the presence of the bases adenine guanine uracil and cytosine. In 1953 the only known natural compounds containing cytosine were the nucleic acids which were not present in the bacterial extracts. It is in- teresting to reflect that mono- di- and tri-phosphates of cytidine and a coenzyme cytidine diphosphate choline were discovered very shortly afterwards ; if our work had been carried out a little later we might have assumed that cytosine had arisen from the hydrolysis of these compounds and the work to be described in this Lecture would then not have been done.After careful analysis of the nucleotides from L. arabinosus by ion-exchange chromatography under gradient-elution conditions two cytidine derivatives were detected,2 and they were later i~olated.~ As the amounts of these nucleotides were very small nearly all our work on their structure was based on paper- chromatographic techniques. A method which has played a prominent part is that developed by Buchanan Dekker and Lone for the detection of nucleosides glycosides polyols and other glycols.This involves periodate oxidation on the paper followed by detection of the resulting aldehydes with Schiff’s reagent. When used under the conditions described more re~ently,~ this technique is highly sensitive and the colours formed are frequently diagnostic for glycol groupings of different types. Both nucleotides yielded cytidine-5’ phosphate (I) on acid hydrolysis. The other products were mixtures of phosphoric esters which were different in the two cases. From the general pattern of structure in the nucleotide coenzymes it was likely that these nucleotides from L. arabinosus would contain cytidine-5’ phosphate joined in pyrophosphate link- age to some hydroxy-compound.This was readily demonstrated by the action on them of rattlesnake venom. Crotalus atrox venom contains a pyrophos- phatase and a 5’-nucleotidase and so would give cytidine orthophosphate and a single organic phos- phate from each nucleotide. This was found to be the case and the identification of the resulting organic phosphates as L-a-glycerophosphate (11)6 and D-ribitol5-phosphate (HI)’** established the respective structures of the nucleotides as cytidine diphosphate glycerol (IV) (CDP-glycerol) and cytidine diphos- phate ribitol (V) (CDP-ribitol). Although the glycerophosphate and ribitol phos- phate were characterised by paper chromatography enzymic dephosphorylation and periodate oxida- tion and the structure of the nucleotides was con- firmed by hydrolysis with ammonia to cycIic phosphates anomalous behaviour was observed during acid-hydrolysis of CDP-ribitol.Even under mild conditions some inorganic phosphate was liberated. Complex chromatograms were obtained from the reaction mixture and it was possible to detect all the isomeric monophosphates of ribitol. * Delivered before the Society at Imperial College London on January 15th at the University College of North Wales Bangor on March 12th and at the Queen’s University Belfast on May 5th 1959. Pierpoint Hughes Baddiley and Mathias Biochem. J. 1955 61 390 368. Baddiley and Mathias J. 1954 2723. Baddiley Buchanan Carss Mathias and Sanderson Biochem. J. 1956 64 599. Buchanan Dekker and Long J.1950 3162. Baddiley Buchanan Handschumacher and Prescott J. 1956 281 8. Baddiley Buchanan Mathias and Sanderson J. 1956 4186. ’Baddiley Buchanan Carss and Mathias J. 1956 4583. * Baddiley Buchanan and Carss J. 1957 1869. These would have arisen by the usual acid-catalysed migration of the phosphate group.g Somewhat more prolonged hydrolysis liberated nearly all the phos- phorus originally associated with the ribitol phos- phate. The main product under these conditions was not ribitol and in fact not a trace of ribitol was de- tected in the reaction mixture. The identity of the product with 1,4-anhydroribitol (VI) was proved by periodate oxidation and by synthesis. Po? CH;O*PO,H 64 NH2 Under slightly more vigorous conditions ribitol itself was converted completely into anhydroribitol.Other pentitols gave anhydro-compounds much more slowly and most of the hexitols gave mixtures. HO OH (VI I) (VI) CHO I (V I CH,*O .POSH It was thus possible to identify any pentitoloi hexitol by examining the products of treatment with hot acid on paper chromatograms.’* The formation of anhydro-compounds under these conditions presum- able involves nucleophilic substitution e.g. (VII) at a terminal carbon atom by hydroxyl at position 4. Idem J. 1957,4058. lo Idem J. 1957 4138. PROCEEDINGS At pH 4 hydrolysis of all the polyol phosphates is normal the products being the free polyol and inorganic phosphate. The unexpectedly ready formation of anhydro- ribitol from ribitol and its phosphate was a most valuable means of identification during work on CDP-ribitol and its application to riboflavin 5’-phosphate has been offered as an explanation of the detection of so-called “lyxoflavin” in heart-muscle CH2*OH fi HOT2.OH CH2-0.POSH CH,*O-PO,H (1) (m> OH OH OH OH extract^.^ The value of this reaction is shown most clearly in the work described later on the biological function of CDP-glycerol and CDP-ribitol. The phosphate group in both the glycerophosphate and the ribitol phosphate residues of the nucleotides must occupy a terminal position since both yielded glycolaldehyde phosphate (VIII) on periodate oxida- tion. Both the polyol phosphates can exist in stereo- isomeric modifications but the extremely small amounts available and the low specific rotations of such compounds precluded determination of con-figuration by conventional methods.The glycero- phosphate must have the L-a-configuration since it was readily and completely oxidised to dihydroxy- acetone phosphate by the specific enzyme glycero- phosphate dehydrogenase. As ribitol phosphate had not been found hitherto in Nature no specific enzyme for its metabolism was known and its stereocheniistry had to be determined JUNE/JULY1959 by degradation to compounds which could be charac- terised enzymically. The cyclic phosphate obtained by the action of ammonia on CDP-ribitol was oxidised with periodate followed by bromine water. i"o'." otl COiH / CHiO.qH, + C0,ff t0.PO3H CH OH The resulting cyclic phosphate of glyceric acid was eluted from a paper chromatogram and treated with acid to give a mixture of the 2-and the 3-phosphate of glyceric acid.In the D-configuration these two compounds are well-known intermediates in the Embden-Meyerhof route for glucose metabolism in yeast and muscle whereas the L-compounds do not OCCUT naturally. The mixture obtained by us was readily utilised in an enzyme system from rabbit muscle and so the ribitol phosphate residue in CDP-ribitol must be D-ribitol 5-phosphate.* Chemical synthesis of the two nucleotides has been achieved by the carbodi-hide method. Unprotected polyol phosphates cannot be used in this route since cyclisation of the phosphates occurs with the com- plete exclusion of mixed pyrophosphate formation.CDP-glycerol was obtained from isopropy1idene-L- a-glycerophosphate (IX) and cytidine-5' phosphate in the presence of dicyclohexylcarbodi-imide fol-lowed by careful acid-hydrolysis of the isopropyl- idene group.ll CDP-ribitol of correct stereochemical composition was obtained by a similar reaction between cytidine-5' phosphate and ribose 5-phos- phate.12 The resulting CDP-ribose (X) was reduced with sodium borohydride to CDP-ribitol. It is not necessary to protect hydroxyl groups in this case since steric factors prevent ribose 5-phosphate from cyclising under normal conditions. The biological origin of the two nucleotides has been studied by Shaw.13 Both are formed from cytidine triphosphate (CTP) and the appropriate polyol phosphate in an enzymic reaction analogous to those whereby other nucleotide coenzymes are formed.CTP + Ribitol phosphate + CDP-ribitol + Pyrophosphate The biological function of these nucleotides was of particular interest. By analogy with other nucleotides it was likely that these cytidine derivatives would be ,O-CH (I X) C\ O-PO,H concerned in the metabolism of the polyol phosphate part of their molecules. It was thought possible that CDP-glycerol might participate in the biosynthesis of phospholipids6 and related compounds.14 However there was no experimental evidence for this and as ribitol phosphate had not been detected before in natural compounds a similar hypothetical role for CDP-ribitol seemed unlikely.An important function of nucleotides of this general type is in the biosynthesis of macromolecules. Examples of this have been demonstrated recently in the enzymic formation of cellulose15 and glycogen,16 where uridine diphosphate glucose participates in the transfer of glucose units and in chitin synthesis1' where uridine diphosphate acetylglucosamine serves a similar function. Consequently we looked foi large molecules containing ribitol- or glycerol-phosphate residues in extracts of L. arabinosus. Compounds which probably possess reasonably high molecular weight and containing these polyol phosphate residues were in fact found and isolated.ls Subse- quent work has shown that the ribitol phosphate polymer also contains alanine and glucose residues and is thus a member of a new group of natural polymers.In an effort to obtain information about the function of these compounds we examined hydro- lysates of isolated bacterial cell walls.lg These were prepared by Dr. M. R. J. Salton by standard methods described by him,20 and were free from other cell materials. Although the glycerophosphate polymer Baddiley Buchanan and Sanderson J. 1958 3107. la Baddiley Buchanan and Fawcett unpublished work la Shaw. Biochem. J.. 1957. 66. 52~. l4 Benson and Marus Bioihim. Biophys. Acta 1958 27 189. l8 Glaser ibid. 1957 25 436. l6 Leloir and Cardini J. Amer. Chem. Soc. 1957 79 6340. l7 Glaser and Brown Biochim. Biophys.Acta 1957 23 449; J. Biol. Chem. 1957 228 729. l8 Baddiley Buchanan and Greenberg Biochem. J. 1957 66 51~. loBaddiley Buchanan and Carss Biochim. Biophys. Acta 1958 27 220. ao Salton and Horne ibid. 1951 7 177. was absent from the walls examined at that time the ribitol-containing material was detected in the walls of several Gram-positive bacteria. We believe that the ribitol compounds are present in a number of bacterial cell walls where they may account for be- tween 40 % and 60% of the wall. Consequently the general name “teichoic acid” (TEE& = wall) has been given to the group. It is interesting that Mitchell and Moyle21 have detected a glycerophosphate poly- mer in preparations which probably consist of walls and intracellular membranes of a number of bacteria.Recent evidence suggests that these preparations sometimes contain ribitol derivatives.22 It was thought possible that the glycerophosphate polymer might be concerned with the protoplast membrane which is located just beneath the wall.23 Evidence for the presence of glycerophosphate derivatives in these membranes has been obtained by M~QuiIlen.~* Recent work (see below) indicates that some bacteria contain in their walls a teichoic acid bearing glycerol in the place of ribitol and it now seems likely that Mitchell and Moyle’s material contained teichoic acids together with other substances. Neither alanine nor sugars were recognised by these workers as components of their compounds. PROCEEDINGS and john son^ showed that three uridine derivatives accumulated in Staphylococcus aureus when grown in the presence of penicillin.One of these has been called uridine diphosphate acetylmuramic acid (XI ; R = OH) whereas the others are derivatives of this bearing either a D-alanine residue (XI; R = alanine) or a small peptide composed of lysine D-glutamic acid and Y Me-CHCOR Muramic acid has been found so far only in bacterial cell walls;28 lysine D-glutamic acid and D-alanine are also characteristic wall compon-ent~.~~~~~~~~ It seemed likely then that these nucleo- tides are connected in some way with wall synthesis. Moreover penicillin seriously affects bacterial walls during the very early stages of its action and this would be consistent with the accumulation of the uridine derivatives during these early ~tages.~~P~ One Products of acid hydrolysis of teichoic acid from diferent bacteria L.arabinosus B. subtiIis Staph. aureus + + + Alanine Glucose Glucosamine Inorganic phosphate Anhydroribitol Anhydroribitol phosphate Ribitol Ribitol glucosaminide Although the detailed mechanism of the enzymic synthesisof the teichoic acids has not been elucidated it is clear that the nucleotides are involved in the formation of polymers by transferring ribitol phos- phate or glycerophosphate residues. The relation be-tween CDP-ribitol CDP-glycerol and teichoic acids is strikingly similar to that of certain uridine deriva- tives detected earlier in Gram-positive bacteria.Park 21 Mitchell and Moyle J. Gen. Microbiol. 1951 5 981. 22 Idem personal communication. 2s Idem. J. Gen. Microbiol.. 1956. 15. 512. + + --+ + + + + + + + + + + + + -+ may visualise the nucleotides transferring acetyl- muramic acid and its peptides into the macro-molecular structure of the wall and penicillin through interference with wall formation causing the accumulation of the precursors. Park and Strominger (personal communication) have also observed the accumulation of a cytidine derivative in Staph. aureus which had been inhibited 24 McQuillen Biochim. Biophys. Act; 1955 17,382 and personal communication. 25 Park and Johnson J. Biol. Chem. 1949 179,585. 26 Park ibid. 1952 194,877 885. Park and Strominger Science 1957 125 99.28 Strange Biochem. J. 1956 64 23~; cf. Work Nature 1957 179,841. Salton Biochim. Biophys. Acta 1953 10 512. 30 Cummins and Harris J. Gem Microbiol. 1956 14 583. 31 Ikawa and Snell Biochim. Biophys. Acfa 1956 19 576. 52 Strominger,J Biol. Gem. 1957 224 509. JUNE/JULY 1959 by chloramphenicol or Crystal Violet. We have dentified this as CDP-ribitol,33 and it seems that these inhibitors which may affect the walls indirectly can cause the accumulation of wall precursors. The general structure of the teichoic acids follows from two types of experiment; acid-hydrolysis and alkali-hydrolysis followed by phosphatase treat-ment.33s34 In both procedures the products have been identified by paper chromatography.Teichoic acid from L. arabinosus 17-5 and Bacillus subtilis gave alanine and glucose in equimolar amounts on acid- hydrolysis. That from Staph. aureus H gave alanine and glucosamine. Other hydrolysis products in all cases included inorganic phosphate ribitol anhydro- ribitol and its 5-phosphate and the isomeric phosph- ates of ribitol. These are listed in the Table (p. 180). It was shown earlier that acid-hydrolysis of ribitol phosphates does not normally give free ribitol. How- ever the presence of the free polyol in hydrolysates of teichoic acids is readily explained on the basis of a polymeric structure e.g. (XII) or its isomers. OH (XI 1) Hydrolysis in a random manner at either side of the phosphate groups would yield ribitol together with other products.This and other physical properties strongly suggest the polymeric nature of the teichoic acids. The glucose residues are stable towards alkali and are readily hydrolysed in hot acids yielding glucose. These properties are consistent with those of glucoside. Alkali-hydrolysis confirmed this view. The acid from B. subtilis gave with hot alkali a mixture of phos- phates which on dephosphorylation with prostate phosphatase yielded a single ribitol monoglucoside. Similar treatment of the acid from Staph. aureus gave a ribitol glucosaminide whereas teichoic acid from L. arabinosus gave mono- and di-glucosides of ribitol together with some free ribitol. These findings would agree with a structure for teichoic acids of the type (XII) with glucosyl or glucosaminyl residues attached to hydroxyl groups on the ribitol units.The alanine residues are very labile towards alkali and amines. With dilute ammonia at room tempera- ture they are removed rapidly to give a mixture of alanine and its amide. Hydroxylamine similarly gives the amino-acid and its hydroxamic acid. This and 181 the demonstration (ninhydrin) that the amino-groups are free in teichoic acid indicate that the alanine residues are in ester linkage through their carboxyl groups with hydroxyl groups in the polymer. This is the first authenticated case of the natural Occurrence of an a-amino-ester. Snell Radin and Ika~a,3~ however noted that the D-alanine com- pounds in hot trichloroacetic acid-extracts of bacteria are very labile towards alkali.These workers also showed that the D-alanine is located in the cell walls. Dr. F. Neuhaus in these laboratories has now found that the alanine in teichoic acid has the D-configuration and it is highly probable that the labile D-alanine observed by Snell and his collabor- ators represented teichoic acid. The evidence available so far indicates that teichoic acid from B. subtih is best represented by the structure (XIII). It seems that in this material each ribitol residue bears one P-glucosyl substituent. As the ribitol residues in the polymer are destroyed by periodate they must have at least two adjacent OH unsubstituted hydroxyl groups. This being the case the alanine residue may be on one of the hydroxyl groups in the glucosyl substituent.0-AlanyI-D-gI ucosyIribito1 ,=b-OHj '1 I n (XIII) ro-Alanyl-N-acylglucosaminylriPitol I 1 L O=P-OH 1' In (XIV The teichoic acid from Staph. aureus may be represented by structure (XIV) in which the acyl substituent is probably acetyl. The behaviour of the glucosaminyl residue in this polymer towards acids and alkalis is very similar to that reported36 for N-acetylglucosaminides. The polymer from L. arabinosus probably resembles that from B. subtiZis (XIII) but contains unsubstituted ribitol residues as well as some with one and two glucose substituents. The teichoic acid from L. casei is a glycerophos- phate polymer containing alanine.37 Those from 33 Armstrong Baddiley Buchanan ,and Carss Nature 1958 181 1692.34 Armstrong Baddiley Buchanan Carss and Greenberg J. 1958 4344. 35 Snell Radin and Ikawa J. Biol. Chem. 1955 217 803. ''Foster Horton and Stacey J. 1957 81. 37 Unpublished observations by Miss Kelemen and Mr. Davison. Staph. albus and Staph. citreus are also glycerophos- phate derivatives and it is likely that other organisms may contain teichoic acids bearing other sugars and possibly other polyols. It is clear that there is still much work to be done on the teichoic acids from the structural as well as the enzymic viewpoint. Nevertheless I consider that PROCEEDINGS the work already accomplished has established their significance and much about their general structure.For this I wish to acknowledge the large part played by my colleagues Drs. J. G. Buchanan B. Carss G. R. Greenberg A. P. Mathias and A. R. Sander-son Mr. J. J. Armstrong Mr. C. P. Fawcett and others who have joined us more recently. SOME MODERN TEXTILE FINISHES By A. R. URQUHART (SHIRLEY MANCHESTER) INSTITUTE IN the years that have elapsed since the end of the second world war there has been a change little short of a revolution in the attitude of the consumer towards the textiles he uses for clothing and to some extent for other purposes also. This change of attitude derives from the new properties made available for the first time by the synthetic-polymer fibres. Nylon appeared in the shops shortly before the beginning of the war but because of its immediate and nearly com- plete mobilisation for war purposes it did not become generally available to the public until some time after the war had ended.One of its early applications was to underwear and it may be recalled that the advertisements of the time tended to emphasise the fxt that nylon garments dried quickly after washing and retained their shape without ironing. These are very desirable properties adding greatly to convenience par- ticularly for travellers but they are secondary properties not directly related to the primary purposes for which clothing is worn; otherwise we might all be wearing undervests of chain- mail. The quick drying after washing results from nylon’s being appreciably less hygroscopic than any of the fibres that had previously been used for such purposes and the emphasis that was placed on it was in a sense making a virtue out of a defect because in any underwear fabric a reasonable water absorption is desirable both for obvious hygienic reasons and because the heat that is released when water is absorbed can play an important part in preventing chill when one moves from warm to cold conditions.The reten- tion of shape without ironing is a consequence of the thermoplasticity of the polymer which permits the garments to be “set” in a given shape by the application of heat alone and to retain that shape so long as the temperature of the original setting is not exceeded. This was a new desirable feature without accompanying disad- vantages and the purveyors of the more tradi- tional garments naturally sought to impart to their products some of these secondary pro- perties without at the same time seriously affect- ing the primary properties that made their materials intrinsically suitable for use in clothing.Before we consider the means adopted to this end it is important to examine the rnagcitude of the problem and at the same time assist the development of a proper sense of proportion in the matter by providing a few production statistics. The most recent available data for the world production of the fibres mainly used in clothing refer to 1955; undoubtedly there will have been an increase in the production of synthetic-polymer fibres since then but it cannot have been sufficient to change appreciably the general picture.In that year of the total produc- tion of the fibres mentioned silk represented 0.2% wool 10-3% cotton 68.4% and man-made 21-1%. But of the man-made nearly 90 % comprised the cellulosic fibres viscose and acetate rayons so that the total production of the cel- lulosic fibres was over 87% and of nylon Terylene Orlon Acrilan and all the rest of them put together was 2.2%. These figures may possibly surprise those who have based their conceptions of the relative importance of the different fibres on the relative amounts of ad- vertising that they have attracted. One method by which the manufacturers of fabrics from natural fibres have sought to im-part the desirable easy-care properties depends on the use of blends of natural with synthetic- polymer fibres.But in order that such blended fabrics may be capable of being set and hence JUNE/JULY 1959 of acquiring the desired properties they generally require to contain about 50% of the synthetic component so that this cannot be a universal solution of the difficulty so long as the relative proportions of the two kinds of fibre are of the order of 87 to 2. Moreover the presence of the synthetic component can be responsible for de- fects that arise in wear the most obvious of which is that known as “pilling’’ though others will be mentioned later so that there is real demand for easy-care effects on fabrics made entirely from natural fibres or cellulosic rayons.The expression “easy-care” is applied to clothing that requires less than what over the years has come to be regarded as the normal attention on the part of the housewife during laundering and if one is prepared to admit degrees of “ease” in this respect one must recog- nise that the expression itself is newer than the feature it was coined to describe. During the past thirty years the “crease-resist” process has con- ferred some measure of easy-care on the materials in particular spun-rayon fabrics to which it has been applied. Because of its essential similarity to the modern easy-care finishes it is necessary to consider how in fact the crease-resist process achieves what it does. It will be generally agreed that the arrange- ment of the molecules in cellulose is such as to produce crystalline regions where the lateral bonding is strong and amorphous regions in which it is weak and that the transition from one kind of region to another is gradual rather than abrupt.Hence any stresses to which the cellulose fibre is subjected will not have any appreciable internal effect on the crystallites though it may change their dispositions because of the effect of the stresses in disrupting the amorphous parts. On the severity of this disruption will depend the tendency for the structure to resume its original disposition when the forces that caused the change have been removed; creases for example will be more or less permanent until something positive such as the application of counteracting stresses is done to remove them.The crease-resist finish involves impregnating the material with a low condensate of urea and formaldehyde together with an appropriate cata- lyst drying it and completing the condensation by baking at an elevated temperature. Although the mechanism is not known with certainty the resin probably forms additional and stronger cross-links between the molecules in the amor- phous regions minimising their disruption and assisting return to their original disposition spontaneously on removal of a stress without need for the application of a counteracting stress to effect recovery. Thus the function of the finish is to impart a kind of memory to the fabric and this explains why the same kind of process can be used to impart two apparently contrary effects-crease-resistance and permanence of pleating.It is true that minor modifications may be made in the formulation according to the purpose to be achieved yet the differences are in general small. What these processes do is to assist the fabric to retain the condition in which it was submitted to the process; if flat and un- creased it tends to remain flat and uncreased and if pleated or embossed to remain so. In other words such processes are essentially setting pro- cesses as that word is understood in its applica- tion to thermoplastics in general and thermo- plastic fibres in particular. But whereas the synthetic-polymer fibres being thermoplastic can be set by heat alone those concerned with cellulose fibres have had to call for assistance to the chemist and it is interesting to note that in making setting possible for cellulose he for the most part uses thermo-setting rather than thermoplastic additives so that the effect im- parted can be removed only by treatments that break down the resin.At the present time much attention is being devoted to finishes for cotton variously described as “easy-care” “drip-dry” and “wash-and-wear”. What is sought here is a finish that will enable a garment made from such treated fabric for example a shirt to be hand-washed at night hung up wet after slight hand-smoothing and found dry and ready to wear next morning with- out any need for ironing.In order that it may dry with the requisite speed the cotton should absorb less water; resin treatment of the kind referred to does in fact reduce the hygroscopicity of cellulose probably by combination of the resin to some of the hydroxyl groups in the amorphous regions. But in fact the reduction required is not large so that it can be achieved without serious impairment of the primary pro- perties that make cotton suitable for such usage. The other and more important characteristic is that the material should not crease readily so that the slight hand-smoothing given to it when wet and therefore swollen shall be adequate to remove any creases that have been formed during wear or washing. It is plain therefore why the crease-resist and wash-and-wear processes are so similar;a satis- factory wash-and-wear effect can be realised on cotton with the same resin formulation as for crease-resist on viscose rayon but diluted to half the concentration so that the amount of resin applied may correspond to the fact that in cotton there is only about half the proportion of amor- phous region that there is in the rayon.Some changes have of course been made particularly in the direction of increasing the proportion of formaldehyde in the liquor ;some melamine may also be used with the urea. One of the defects of these finishes is that the resins used can retain chlorine when the fabrics are treated with hypochlorite bleach liquors. The chloramines formed are not very stable and their decomposition yields hydrochloric acid which rots the fabric and amines which impart undesirable odour to the garment.This is a par- ticularly serious problem in America where the housewife (or laundry) appears to be consider- ably more indiscriminate in her use of relatively concentrated hypochlorite solutions than her counterpart in this country and one of the first requirements for a resin to be applied to a fabric there is that it shall not be capable of retaining any chlorine with which it may be brought into contact. For this reason much attention is being devoted to tertiary nitrogen-compounds and in particular to the so-called “cyclic ethylene ureas” of which the most used is 1:3-dibis- hydroxymethylimidazolid-2-one (I).Another compound (11) of this type has the trivial name co /\ HO-H,C-Y SJ*CHiOH HOaHC -CHeOH (ID) “triazone” while another that may be used is 4 :5-dihydroxy-1:3-bishydroxymethylimidazolid-2-one (111). The cyclic “ethylene ureas” have the PROCEEDINGS additional advantage of not being self-con-densing so that the catalysed bath remains stable for a longer time and this confers greater flexibility in processing. In considering the general applicability of this type of finish it is necessary to have some under- standing of the physical processes involved in crease-formation. A crease results from the application of a stress to a small area and the smaller that area for a given force the greater is the resultant strain and hence the more perman- ent the crease.It is for this reason that creases are more readily formed and when formed are more difficult to get rid of in close tightly woven fabrics than in more open structures; in close fabrics the stress is confined to a very small area whereas in more open fabrics the individual yarns are able to move and by distorting the structure distribute the stress over a greater area so decreasing the strain. The function of the crease-resist or drip-dry finish is to assist the fabric to return to its original conformation but the recovery from strains is not perfect and hence it is desirable to restrict as much as possible the strains imposed on the material. It is this that underlies the instructions to the housewife to avoid introducing creases during washing but it also emphasises that a drip-dry finish is not just a finish that can be applied to any fabric and ex- pected to give equally good results; the structure of the fabric to which it is applied is also important.In this country high-quality poplin has for long been the standard fabric for making first- quality shirts but it has a tightly woven structure that makes it in the present state of technological advancement intrinsically less suitable for the application of a drip-dry finish than a more open cloth that will permit relative movement of its component threads. Since the greater part of the cost of a finished fabric resides in the base cloth to which the finish is applied it is at present not unusual for the consumer to find that the degree of satisfaction he gains from an easy-care shirt is inversely related to what he pays for it.The high-quality base-fabric has another dis- advantage compared with a cheaper material of more open structure-a shirt made from it is liable to fray more rapidly at cuffs and collar. This is an intrinsic disability of the high-quality closely woven fabric for reasons already given JUNE~JULY 1959 but its effect is more pronounced in easy-care fabrics partly because the acid catalyst used in forming the resin can cause some degradation of the fibre and partly because the presence of the resin decreases its abrasion resistance. Hence where the stresses are highly concentrated the fabric may not have a very long life; some criticism of the process has arisen on this ac- count a life as short as 26 washes having been quoted for garments of this kind.A life as short as that however must have resulted from the application of the process to a fabric quite un- suited to it to bad processing that caused exces- sive degradation or to improper laundering; for shirts are in existence in excellent condition without any sign of fraying that have so far survived well over 100 washes. In shortening wear-life the housewife must bear some responsi- bility for her past experience of garments with- out such finishes leads her to doubt that garments will be satisfactorily laundered without at least some ironing and the high-temperature treat- ment involved has a deleterious effect on the resin particularly if bleach has been used during washing.There seems little doubt that the “easy- care” shirt laundered as it should be laundered will last at least as long as the ordinary shirt that is regularly submitted to the average laundry. So far finishes for cellulosic fibres only have been considered. Wool requires no crease-resistant treatment being in this respect the ideal towards which the other fibres aspire. It has of course the concomitant disadvantage that it does not retain creases where they are desired- in trousers pleated skirts etc. A good deal of investigation is going on in this field and there is little doubt that methods of permanently creasing all-wool materials will soon be in use if they are not already available.The methods used for the permanent waving of hair point the way here. So far in this article consideration has been given only to finishes intended to confer on the natural fibres some of the desirable properties of the synthetics; it would present a very one-sided picture if at least some mention were not made of the attempts being made to confer on the synthetics some of the desirable properties of the natural fibres. Man-made fibres in the early stages of their production have always been available first as continuous filaments and it has always been found necessary to produce them subsequently as short fibre in order that they might be spun on the machinery normally used for spinning natural fibres.At first sight it ap- pears anomalous that fibres should be produced in continuous lengths cut into short fibre and spun to form continuous yarns but of course the properties of yarns spun from short fibres are quite different from those of yarns composed of continuous filaments. The latter are very com- pact; the bulkiness of the former provides much greater covering power for a given weight and because of the amount of air held between the fibres much better heat insulation so that gar- ments made from spun yarns are more comfort- able in wear and pleasanter to the touch. Processes have recently been introduced by which continuous-filament yarns made from synthetic polymer fibres can acquire these desir- able bulking properties without putting them through the extra processes of cutting and spin- ning.These processes for the most part achieve their object by heat-setting the yarn when it is in a crimped condition produced for example by the introduction of false twist or by drawing the yarns over a knife edge so that one side of each filament becomes longer than the other pro- ducing a spiral or crimped form. This kind of treatment also imparts an apparent rubber-like elasticity so that garments made from these yarns can stretch to accommodate themselves to the varied contours to which they may be applied. But while such treatments can make the synthetic-polymer fibres equal to the natural fibres in insulating power they cannot of course provide that freedom from chill that results from the exothermacy of water absorption on a hygro- scopic fibre.To achieve this a modified polymer is required and direct production of such a modified polymer presents considerable diffi- culties. The groups in the polymer molecule that are capable of binding water molecules by hydrogen bonds are precisely those that are in- volved in polymerisation or condensation so that the introduction of even one such additional group would make the monomer trifunctional and hence result in the production of a three-dimensional polymer quite unsuitable for fibre production. The patent literature suggests that this difficulty can be overcome by blocking one of these groups in the monomer and after poly- merisation hydrolysing off the blocking radicals but this of course adds extra processes in the manufacture of a product that without such complications is not cheap; modification of the original polymer might perhaps be more practic- able but no fibres produced by either of these types of processes are currently available.Two other disadvantages of the synthetic-polymer fibres are possibly more amenable to alleviation by suitable finishes. These fibres ac- quire static charges readily and so act as electro- Static precipitators for the dust in their im-mediate neighbourhood. The speed with which garments made from them become soiled can PROCEEDINGS therefore be reduced by the application of suit- able anti-static finishes though it must be said that in the present state of our knowledge none of these finishes is satisfactorily fast to launder- ing.The fact that these fibres are hydrophobic and hence lipophilic makes the acquired dirt much more difficult to remove since it is usually associated with body fat and hence tightly bonded to the lipophilic substrate. Work is pro- ceeding with the object of finding a finish to make the surfaces of such fibres hydrophilic so that dirt may be removed as easily as from the other hydrophilic fibres but it is a very difficult problem to devise a finish of this kind that will itself be fast to laundering and one for whose solution we must look to the future.COMMUNICATIONS Pyridine and Methyl Acetylenedicarboxylate By R. M. ACHESON and G. A. TAYLOR (DEPARTMENT THE UNIVERSITY OF BIOCHEMISTRY OXFORD) PYRIDINE and methyl acetylenedicarboxylate yield labile (red) and stable (yellow) adducts for which structures (I) and (111) respectively were suggested,l and a third compound the structure of which is now established.2 Structures (I) and (111) were based on certain interconversions and on the oxidation of the stable adduct to picolinic acid N-oxide. The oxida- tion which has been confirmed shows the presence of ring A. The formation of the six-membered ring (B) was not conclusively demonstrated and proof of this has now been obtained. Hydrogenation of the stable adduct to a tetrahydro-derivative followed by oxidation with concentrated nitric acid gave an acid C,H,Q,N.Decarboxylation then gave pyridine and as the acid gave no colour with ferrous sulphate it must be pyridine-3,4,5-tricarboxylicacid (derived from ring B) a formulation agreeing with the ultra- violet absorption. We have not been able to isolate the labile (red) adduct from pyridine but labile and stable adducts have been obtained from 3-methyl- and 3,5-dimethyl- pyridine. Three isomeric adducts were obtained from 3-methylpyridine orange m.p. 121 "; yellow m.p. 205"; and yellow-brown m.p. 221". The orange adduct corresponding to the labile pyridine adduct was converted into its yellow isomer (m.p. 205") by prolonged boiling in benzene. From 3,5-dimethyl- pyridine only two adducts were formed; again the labile (red) adduct (m.p.141") was converted into the stable (yellow) adduct (m.p. 222") by heat. R = C0,Me and R' = R" = H,unless otherwise specified. The structure (I) originally proposed for the labile pyridine adduct suggests a type of quinquecovalent nitrogen and would now be interpreted as (11). As the labile adducts are stable to methanol the charged formulation (11) is improbable because addition of a proton at the carbanion to yield the corresponding pyridinium methoxide would be expected by ana10gy.~ The cyclic structure (111) is attractive for the labile adducts as isomerisation to a fully con- jugated structure such as (IVa or b) accounts for the formation of the stable adducts but a clear differenti- ation between these and the other two possible Diels et al.Annalen 1932 498 16; 1933 505 103; 1934 510 87. Professor R. B. Woodward personal communication; E. C. Kornfeld Ph.D. Thesis Harvard 1945. Acheson et al.,J. 1954 3240; 1956 246 2676. JUNE/JULY 1959 tautomers has not yet been made. The ultraviolet absorption spectra of the compounds are consistent with this isomerisation. Professor R. B. Woodward has independently2 suggested structures (111) and (IVa) for the pyridine adducts. Professor A. W. Johnson and Mr. J. C. Tebby since the submission of this note have informed us of experiments which suggest that the labile adducts can be better repre- sented as zwitterions involving a positive charge on the nitrogen atom than as (111).The ultraviolet absorption spectra of the labile pyridine adductl and our two labile adducts are very similar to each other and to that of the tetrahydro-derivative obtained from the labile 3-methylpyridine adduct. Nitric acid oxidation of this tetrahydro-derivative gave pyridine- 3,4,5-tricarboxylic acid which supports the bicyclic structures for all the labile adducts. Four adducts (111 and IV; R’ = H R” = Me and vice versa) were expected from 3-methylpyridine. For the two stable adducts steric interaction between the methyl and the ester groups is expected in (IV; R’ = Me) but not in (IV; R”= Me). This is shown in the absorption spectra which resemble those of the cor- responding 3,5-dimethylpyridine and pyridine ad- ducts respectively.On this basis structures can be allocated to the two stable adducts and one of these structures has been confirmed by the oxidation of the yellow-brown adduct (m.p. 221 ”) to 5-methyl- picolinic acid N-oxide. Since the labile pyridine adduct seems particularly unstable in comparison with the labile 3,5-dimethylpyridine adduct it ap- pears that steric hindrance stabilises the labile series of compounds. This supports the supposition that the mobile hydrogen atom is initially at the ring junction and is in conformity with the isolation of only the hindered labile adduct (111; R’ = Me) from 3-methylpyridine; the unhindered isomer (111 ; R”= Me) presumably rearranges rapidly as does the labile pyridine adduct.We thank Professor A. W. Johnson and Mr. J. C. Tebby for discussions and samples of materials for comparison. (Received April 2nd 1959.) An Exchange Reaction with 1,6-Anhydro-3,4-isopropylidene-2-0-methanesulphonyl-~-~-galactose By P. W. KENT,D. W. A. FARMER, and N. F. TAYLOR (DEPARTMENT UNIVERSITY OF BIOCHEMISTRY OF OXFORD) A NUMBER of primary-fluorinated monosaccharides (6-deoxy-6-fluoro-~-glucose,~~~ 6-deoxy-6-fluoro-~-galactose,25-deoxy-5-fluoro-~-ribose~~~) have already been synthesised by exchange of suitable substituted 6(or 5)-methanesulphonic esters with potassium fluoride. In the last two cases when methanol is used as a solvent methoxyl groups enter as well as fluorine. In attempts to obtain secondary-fluorinated sugars it has been found that in corresponding con- ditions exchange occurs without the introduction of fluorine and with one methoxyl group entering the molecule.1,6-Anhydro- 3,4-isopropylidene-2- U-methanesul- phonyl-p-~-galactose,~ heated with potassium fluor- ide dihydrate in methanol at 130” for 15 hours gave a quantitative yield of potassium methanesulphonate and a product P m.p. 72-73” [a] -75.1 (c 0.97 in chloroform). The latter was fluorine-free failed to restore the colour of Schiff’s reagent and had a methoxyl content of 12.9 % indicating one methoxyl group per molecule. It is clearly different from the Helferich and Gnuchtel Ber. 1941 74 1035. Taylor and Kent J. 1958 872. Kissman and Weiss J. Amer. Chem. Soc. 1958 50 5559. James Smith Stacey and Wiggins J.1946 625. Levene and Tipson J. Biol. Chem. 1931,93 623. li Newth and Wiggins J. 1950 1734. known 1,6-anhydro-3,4-isopropylidene-2-O-met11~ 1-p-~-galactose,~ m.p. 37”. Mild acid-hydrolysis of the product P gave a monomethyl-anhydro-sugar which reduced one mol. of sodium metaperiodate without liberation of formaldehyde or formic acid. With silver oxide and methyl iodide it gave a trimethyl derivative converted by concentrated nitric acid and after esterification ethanolic methylamine into riba-tri-O-methylglutaric bi~methylarnide.~ It is concluded that the initial exchange leads to 1,6-anhydro-3,4- isopropylidene-2-O-methyl-~-~-talose (product P). Under identical conditions it has been found that 1,6-anhydro -2- U-methanesulphonyl -,6 -D-altrose6 does not undergo exchange.Both the galactose and the altrose starting material can be considered to exist in “locked” chair con- formations differing only in the axial disposition of the acyl group in the former and its equatorial dis- position in the latter. It is of interest that the ex- change reaction leads to inversion at position 2 in other instances of exchange of secondary sulphonyl- oxy-derivatives’ in the carbohydrate series the con- figuration of the entering group has not been established and in the steroid series,* e.g. cholesteryl toluene-p-sulphonate exchange occurs without in- version. Recently a synthesis of 2’-deoxyuridine has been achievedg involving replacement of toluene-p-sul- phonyloxy in 5’-O-acetyl-2’-0-toluene-p-sulphonyl-uridine by iodine with apparent retention of con- figuration at position 2’.The reaction appears to PROCEEDINGS involve however the 02,2’-cyclouridine both its formation and its subsequent cleavage by iodide being accompanied by Walden inversion. The present work is thus in accord with these results in so far as six-membered and five-membered systems may be compared. Evidence has already been presentedlO which indicates that conformational features influence the ease of replacement of 6-methanesulphonyl groups of glucose and galactose. (Received,March 19th 1959.) Helferich and Gnuchtel Ber. 1938,71 712; Hess Littmann and Pfleger Annalen 1933 507 55; Hess and Kinzer Ber.1937 70 1139. a Stoll 2.physiol. Chem. 1932 207 147; Shoppee,J. 1946 1147; Winstein and Adams J. Arner. Chem. Sac. 1948 70 838. Brown Parihar Reese and Todd J. 1958 3055; Brown Parihar and Todd J. 1958 4242. lo Taylor Nature 1958 182 660. The Structure of the Lactone C,,,H,,O Obtained in The Baeyer-Villiger Oxidation of Camphor By J. D. CONNOLLY and K. H. OVERTON (DEPARTMENT UNIVERSITY OF CHEMISTRY OF GLASGOW) BAEYER on and VILLIGER,~ oxidation of camphor with Caro’s acid isolated in addition to a-campholide a crystalline lactone C,oH,,04 for which no struc- tural proposals are recorded in the literature. We have investigated the chemistry of this compound and base our conclusions [summarised in formula (I; R = R’ = OH)] on the following evidence.The lactone obtained in l0-15% yield under Baeyer and Villiger’s conditions,l consumed one equivalent of base on titration and was shown by Kuhn-Roth oxidation to contain two C-methyl groups. It had infrared bands (in Nujol) at 1393 1379 (CMe,) and (0-004~-in chloroform) at 3628 (free OH) 3524 (bonded OH) and 1773 (y-lactone) cm.-l. Acetylation gave either (pyridine acetic an- hydride) a monoacetate (I; R = OAc R’ = OH) or (refluxing acetyl chloride) a diacetate (I; R = R‘ = OAc). Oxidation by chromic acid in acetic acid afforded smoothly the cyclopentanone (11) [Vmax. 1787 (y-lactone) and 1747 (cyclopentanone) cm.-l (in carbon tetrachloride)] which forms a mono-benzylidene derivative. Treatment of compound (11) with refluxing 0.IN-ethanolic potassium hydroxide resulted in decarboxylation and formation of the cyclopentenone (III; R = OH) Amax.222 mp (E 12,000) Ymax. 3570 (free OH) 1710 (cyclopent- enone) and 1620 (conjugated ethylenic linkage) cm.-l (in carbon tetrachloride) which is reduced by zinc in refluxing acetic acid to the deoxy-ketone Baeyer and Villiger Ber. 1899 32 3625. Tiemann Ber. 1895,28 2166; 1897 30,405. Behal. Bull. SOC.chim. France. 1904 31 179. (111; R = H),nEo 1-4730 [2 4-dinitrophenylhydrazone m.p. 200-201 ’ Amax. 380 mp (E 27,800)]. Dehydra- tion of the original lactone with phosphorus oxy- chloride in pyridine afforded the diene lactone (IV) Amax. 262 mp (E 11,890),vmax. 1769 and 1749 (CO of lactone) and 1637 (conjugated ethylenic linkage) cm.-l (in carbon tetrachloride) which on hydrogena- tion over platinum gave dihydro-p-campholeno- lactone2 (V) (infrared spectrum identical with authentic material) reduced by lithium aluminium hydride to the known dioP (VI) (identical with authentic material by m.p.mixed m.p. and infrared spectrum). The tetramethylcyclopentenone which Locquin obtained4 by treating the lactone (I; R = R’ = OH) with hot phosphoric acid must on the basis of its stepwise oxidation to trimethylsuccinic acid (which we were able to confirm) have structure (LII;R = H) or (VII). While its properties [n”,” 1.4762 minor differences from the infrared spectrum of (111; R = H) in the fingerprint region; 2 4-dinitrophenyl- hydrazone m.p. 202-203” (mixed m.p.with the di- nitrophenylhydrazone of (III;R = H) 184-188”) Amax. 385 mp (E 24,800)] clearly distinguish it from the ketone (111; R = H) identity with the isomer (VII) was established by comparison of its semi- carbazone with that of an authentic specimen5 kindly provided by Dr. V. F. Kutcherov Moscow. We base our stereochemical assignments on (a)the Locquin Compt. rend. 1911 153 284. . Nazarov and Bakhmutskaya Zhur. obshchei Khim. 1950,20 1837. JUNE/JULY 1959 steric necessity of a cis-fused lactone ring and (b)evidence for intramolecular hydrogen-bonding in the infrared solution spectrum of (I; R = R' =OH),g Cole and Jefferies,J. 1956 4391. (INORGANIC MIXTURES of volatile silanes prepared by the action of 20% phosphoric acid on magnesium silicide (about 2 grams for each preparation) have been separated in a gas-liquid chromatographic column containing silicone 702 fluid supported on "Celite." Hydrogen was used as carrier gas with a katharo- meter detector.Twenty-one clearly defined peaks have been obtained and the substances which give rise to them are labelled A to U in the order of elution from the column. Their specific retention volumes (Vgvalues1) remain constant while the relative yields (as estimated from peak areas) vary from preparation to preparation with the larger peaks corresponding in general to the supposed straight-chain silanes. In a number of cases it has been found possible to isolate sufficient quantities of the pure silanes for identification.Thus the mass spectra of A B and C show that they are SiH, Si,H, and Si,H respective- ly D and E are tetrasilanes and H is a pentasilane. The molecular weights of C and E determined by use of a Martin density balance are 92-4 (Si,H required M 92.3) and 121.2 (Si4K, required M 122.4). The vapour pressures of A B and C agree with the values quoted by Stokland2 for SiH, Si2H, and Si,H,. Nuclear magnetic resonance spectra of B C,E G and Hare consistent with their being Si,H, Si,H, n-Si,H,, iso-Si,H,, and n-Si,H, respectively the spectra being characterised Littlewood Phillips and Price J. 1955 1480; Ambrose Keulemans and Purnell Analyt. Chem. 1958 30 1582. Stokland Kgl. norske Vidensk. Selskabs Skrifter 1950 No. 3 p. 1. Desty and Whyrnan Analyt.Chem. 1957 29 320. implying a cis-relation of the two hydroxyl groups. Formation of the lactone (I; R = R = OH) probably proceeds by breakdown of the inter-mediate hydroxy-perester (see VIII) of a type well- known in camphor chemistry and is not surprisingly attended by partial racemisation; its resolution is at present receiving our attention. The initial product of such breakdown or-campholenic acid (IX),was converted into the lactone (I; R = R' = OH) in 35 % yield under the same reaction conditions. Ultraviolet spectra refer to ethanol solutions. Grateful acknowledgement is made to Professor D. H. R. Barton F.R.S. for valuable discussion and the D.S.I.R. for a maintenance grant (to J.D.C.). (Received May 5th 1959.) The Separation of Volatile Silanes and Germanes by Gas-Liquid Chromatography By K.BORERand C. S. G. PHILLIPS CHEMISTRYLABORATORY, OXFORD) by a very small ratio of chemical shift to coupling constant for protons in -SiH,- and -SiH,. For the series of normal hydrocarbons it has been found that plots of log (retention volume) against the number of carbon atoms give good straight lines,3 12345678 No of Si atoms while for each carbon number the more branched isomers have lower values of retention volume. In the Figure log, Vgvalues for the silanes at 110" are plotted against the number of silicon atoms where these are known (i.e. up to H) and the remaining peaks (M to U)have been tentatively assigned to the hexa- hepta- and octa-silanes with M R,and U as the probable members of the normal series.I,J K L and M might correspond with the five saturated non-cyclic hexanes. From V values at different column temperatures heats of solution in the silicone fluid at 70" have been calculatedl as 4400 cal. mole-l for Si,H, 6000 for Si,H, 7100 for iso-Si,H,, and 7400 cal. for n-Si,H,,. Latent heats of evaporation extrapolated from Stokland's figures2 are 4400 (Si2H6) 6600 (si3H8) and 8300 cal. mole-' (Si4Hlo) at the same temperature. PROCEEDINGS Similar experiments with mixed germanes prepared from phosphoric acid and magnesium germanide have shown the existence of seven distinct peaks the first five of which can probably be assigned to GeH, Ge2H6 GeaH8 iso-Ge,H,, and n-Ge,H,,.We thankDr. C.J.Danby for mass spectra Dr.R. E. Richards and Mr. P. Higham for nuclear magnetic resonance spectra and Mr. P. L. Timms for the mole- cular-weight determinations. We are indebted to Imperial Chemical Industries Limited for the loan of apparatus and to D.S.I.R. for a maintenance grant (to K.B.). (Received April 29th 1959.) Peroxides formed during the Slow Combustion of Heptane By J. CARTLIDGE and C. F. H. TIPPER (DEPARTMENT AND PHYSICAL OF INORGANIC CHEMISTRY THEUNIVERSITY, LIVERPOOL) THE unequivocal identification of the peroxidic materials formed during uncatalysed slow combus- tion of hydrocarbons is of considerable importance for an understanding of the mechanism of these 0xidations.l There is some evidence1 that in the "low- temperature" range (Le.200-350") hydroperoxides are formed but there is a possibility that the main peroxides are derived from the aldehydes also present e.g. that they are peracids or aldehyde- hydrogen peroxide compounds.2 It has been found that in the presence of helium n-heptane is oxidised readily in a flow system at 250-275" (-10 g. per hour fuel passing through) and that the products condensable at -78" contain a relatively high yield of peroxides (-0.5 g. per hr.) the yield of free aldehyde being about the same. These products were separated into three fractions by vacuum-distillation. The first (from -45 ") contained unchanged heptane carbonyl com- pounds acids and higher olefins. The second (from room temperature) and the non-volatile residue were analysed by paper chromatography.By using refined methods developed in this lab~ratory,~ it has been possible to show that the second fraction contained only heptyl hydroperoxide (probably several iso-mers) and the residue (roughly half of the total peroxide) contained a mixture of aldehyde-peroxide compounds. No free hydrogen peroxide or peracid was detected and the amount (if any) present cannot exceed 1 % of the total peroxide. However hydrolysis of the residue gave a trace of hydrogen peroxide together with hydroperoxide and aldehydes. These aldehydes were shown to be formaldehyde acetalde- hyde and possibly propionaldehyde by paper chromatography of the dinitr~phenylhydrazones.~ The results also suggest strongly that the aldehyde compounds were derived at least partly from a di-hydroperoxide.Although this seems surprising Bawd has pointed out that certain reactions of RO radicals suggested to account for the production of some gas-phase oxidation products are of the type responsible for the formation of dihydroperoxide in the liquid-phase oxidation of 2,5-dimethyl-hexane and Ivanov5 claimed to have obtained C,H,(0.0H)2*O*0.CH2.0H on oxidation of cyclo- hexane at 316" in a flow system. The yield of peroxidic compounds decreased markedly relatively to that of free aldehyde when the temperature was raised or a reaction vessel of smaller diameter was used. This suggests that the hydroperoxides are the first molecular product of oxidation under these conditions and decompose at least partly on the walls giving aldehydes which may combine with unchanged hydroperoxide.The authors thank Shell Research Ltd. for a gift of pure heptane and the D.S.I.R. for a grant (to J.C.). (Received April 28th 1959.) Bawn Chem. SOC.Spec. Publ. No. 9 p. 65; Tipper Quart. Rev. 1957 11 313. Norrish Discuss. Furuduy Soc. 1951 10 269. Cartlidge and Tipper unpublished work. Rice Keller and Kirchner Anulyt. Chem. 1951 23 194. Ivanov Actu Physicochim. U.S.S.R.,1938 9 421. JUNE/ JULY1959 191 Structures of a-Elaterin and its Degradation Products By D. LAVIEand D. WILLNER INSTITUTE INSTITUTE (THE DANIEL SIEFF RESEARCH WEIZMANN OF SCIENCE REHOVOTH, ISRAEL) THEside chain of elaterin C32H4408 has recently been shown to be asin formula (I).' Dehydrogenation gave 1,2,8-trimethylphenanthrene,so elaterin is prob- ably a tetracyclic triterpenoid as is the whole group of the cucurbitacins.2 Of the eight oxygens of elaterin,3 four remain to be allocated.The presence of a 16-hydroxyl group has been determined as follows Treating elaterin with hot alkali cleaves the side chain at the double bond,' giving ecballic acid3 (11; R = H). Methyl ecballate (11; R = Me) with chromium trioxide in pyridine yielded a crystalline compound C27H& m.p. 185-187" [a] -110" (c 0.97 in chloroform) Amax. 287-295 mp (E 160) showing a new band in the infrared at 1743 cm.-l due to a ketone in a five-membered ring (cf.111). When this product was treated with alkali a new maximum developed at 245 mp (E 10,500) indicative of an ene-dione system4 (cf. IV). Further tetrahydroelaterin methyl ether m.p. 202-204" [a] + 53" (c 0.78 in chloroform) in which the enolic hydroxyl group of the diosphenol system is methylated3 [A,,,. 264 mp (E 5000)5] con- sumes only one mol. of periodic acid; the crystalline product C,&3,@5 m.p. 244-251 " (decomp.) Ymax. 1703 (COMe) 1696 (hindered ketone) 1648 (enol ether) cm.-l Amax. 265 mp (E 6000) has partial structure (V) and with alkali yielded a crystalline ketone (VI) (c2&340& m.p. 193-195" [a] + 14" (c 0.77 in chloroform) Ymax. 1698 16606 (ag- unsaturated ketone) 1645 and 1595 (double bond) cm.-l (no OH absorption) Amax.244 (E 12,000) and 266 mp (E 6500). The hindered ketone group7 can be placed in ring B or c possibly at position 11 by using the same arguments as for elatericin A.8 Tetrahydroelaterin is oxidised by alkaline hydrogen peroxide to an amorphous dicarboxylic acid which on pyrolysis formed a crystalline compound C23H3203 m.p. 195-197" [a] + 48" (c 0.6 in chloroform) showing the strong absorption at 1740 cm.-l of a ketone in a five-membered ring which according to Blanc's rule locates the original diketone system in ring A.~The spectroscopic evidence Vmax. 1740 1695 1668 (c$-unsaturated ketone) and 1598 crn.-l Amax. 240 mp (E 9000) pointed toward structure (VII) for this compound. Inasmuch as tetrahydroelaterin still contained the diosphenol chromophore it can be assumed that elaterin contains in addition to the double bond in the side chain one isolated double bond which can be in ring B or c possibly at position 6,7.These deductions lead to a probable structure (I) for a-elaterin and (11) for ecballic acid. We thank the National Cancer Institute of the National Institutes of Health Public Health Service for a research grant and Dr. P. R. Enslin National Chemical Research Laboratory Pretoria South Africa for exchange of information before its pubii- cation. (Received March 12th 1959.) Lavie Shvo and Willner Chem. and Ind. 1958 1361 ;Lavie Shvo and Willner J. Amer. Chem. SOC.,in the press ; Enslin and Norton Chem. and Ind. 1959 162. a Rivett and Enslin Proc.Chem. Soc. 1958 301. Lavie and Szinai J. Amer. Chem. SOC.,1958 80 707. Dorfman Chem. Rev. 1953 53 67; Sandoval Romo Rosenkranz Kaufman and Djerassi J. Amer. Chem. Suc., 1951 73,3820. Hanson Jaquiss Lamberton Robertson and Savige J. 1954 4238. Cole "Fortschritte der Chemie Organische Naturstoffe," Springer Verlag Vienna 1956 Vol. XIII p. 37. Cf. Lavie and Willner J. Amer. Chem. Soc. 1958 80 710 for a hindered ketone group in elatericin B; and Gilbert and Mathieson Tetrahedron 1958,4 302 for an isolated ketone group in elaterin. Lavie and Shvo Chem. and Id. 1959,429. Gascoigne and Simes Quart. Rev. 1955 9 328. PROCEEDINGS Isolycoctonine and the Structure of Hydroxylycoctonine Salts By 0. E. EDWARDS, M. Los and L. MARION (DIVISION NATIONAL COUNCXL OTTAWA) OF PURECHEMISTRY RESEARCH OF CANADA LYCOCTONINE is readily oxidised1+2 to the carbinol- amine hydroxylycoctonine (I).This compound is anomalous in forming anhydronium salts although the obvious structure for these salts is extremely ~trained,~ and these salts have hitherto inexplicable infrared ab~orption.~.~ In addition hydroxylycoc- tonine can be reduced catalytically1 to an isomer of lycoctonine (isolycoctonine) an observation not readily reconciled3 with structure (I). We now present proof that isolycoctonine has structure (II) and suggest that the above an-hydronium salts are derived from structure (111). Isolycoctonine is a tertiary base (inert to nitrous acid etc.) containing a ketone carbonyl (maX. 1712 cm.-l).The lactam derived from isolycoctonine (isolycoctonam) m.p. 184" [011 45.2" vmax. 1703 1640 1618 cm.-l was oxidised with lead tetra- acetate to a keto-acid which readily formed a 6-or larger-ring lactone vmax. 1737 1704 1637 cm.-l. This lactone lost the elements of methanol when heated with dilute acid giving an ap-unsaturated keto-lactone m.p. 258" [a] -104" Amax. 305 mp (E 57) shoulder at 225 mp (E 8230) vmax. 1738,1671 and 1635 cm.-l. Treatment of isolycoctonam with zinc in refluxing acetic acid-acetic anhydride removed the hydroxyl adjacent to the carbonyl group. The product was stable to alkali but when treated with sodium amalgam gave a "diol" m.p. 199" [a] -29" in which one methoxyl group had been replaced by hydrogen.This methoxyl must have been 01 to the ketone-carbonyl group,4 hence the above reactions establish the presence in isolycoctonine of the sequence (IV). Structure (11) contains this sequence and has the 1,5-relation between the primary hydroxyl and the ketone-carbonyl group which is required for spon- taneous lactone formation. This structure in which only one bond has been ruptured and no skeletal rearrangement has taken place is also consonant with the mild conditions'under which it is formed. The $-unsaturated keto-lactone must then have structure (V) and the product of reduction by sodium amalgam must have structure (VI). -q-$,C,-CH2-C-Me0 0 C OH bMe (IV) OH (V) (VI) The rapidity with which hydroxylycoctonine is reduced catalytically to the compound (11) in acetic acid and the fact that its salts are reduced by lithium aluminium hydride* to the dihyrdo-derivative of (11) suggest that these salts in the solid state and in solution have the open structure 011).This would also provide the first explanation of the infrared absorption of these salts [wax.1710 cm.-l (C=O) and 1670 cm.-l(> C=+N <)I and is consistent with the presence of carbonyl absorption in the ultra- violet region (Amax. 330 mp; E 70). In order to account for the ready reversion of the anhydro-salts (111) to hydroxylycoctonine (I) on basification the 15-hydrogen atom would have to be acidic a phenomenon which has ample pre~edent.~ This question and the mechanism of the ring-opening will be discussed later.Attempts to synthesise a salt (111) from isolycoctonine are under way. One of us (M.L.) is indebted to the National Research Council of Canada for a Post-doctorate Fellow ship. (Received April 20th 1959.) * Unoublished exoeriments bv Dr. D. K. R. Stewart. Edwards and Marion Canah. J. Chem. 1952 30 627. Cookson and Trevett Chem. and Ind. 1956 276. Edwards Marion and Stewart Canad. J. Chem. 1956,34 1315. Edwards Marion and Palmer ibid. 1958 36 1097. Breslow J. Amer. Chem. SOC.,1958 80 3719. JUNE/JULY 1959 OxoNum Cation Intermediates in the Nucleophilic Degradation of Diethylsulphonylpyranosylmethane Derivatives By L. HOUGHand A. C. RICHARDSON (THEUNIVERSITY, BRISTOL) THEoxidations of D-galactose and D-glucose diethyl dithioacetals with aqueous peroxypropionic acid afforded diethylsulphonyl -01 -D -lyxopyranosyl-methane (I) and the D-arabo-isomer 1espectively.l These cyclic derivatives (e.g.I) underwent a nucleo- philic replacement reaction in aqueous ammonia forming the aldopentose (e.g. 111) and diethylsul- phonylmethane (IV). A polarimetric study of the kinetics of this reaction has suggested that the re- action proceeds by the SJ mechanism the rate- determining step being the dissociation of the C(a)-C(l)bond.* The participation of the lone pair of electrons on the ring-oxygen atom was essential for this reaction to proceed and undoubtedly re- sulted in the formation of an oxonium cation (11). Thus in agreement with this mechanism the di-sulphones which did not contain an ethereal oxygen atom adjacent to the diethylsulphonylmethyl group failed to undergo cleavage in aqueous ammonia.The hydrogen substituent at C,, of the cyclic disulphones is activated by participation with the ring-oxygen atom and by the presence of the electro- philic sulphone groups so that these derivatives be- haved as very weak acids and could be titrated potentiometrically with sodium hydroxide solution. Further as a result of this activation methylation of the tri-0-acetyl derivative of (I) with methyl iodide and silver oxide followed by deacetylation resulted in the formation of the ethyl derivative (V). This neutral product and similar derivatives were stable HO :q”&2 H H HH R =S02Et towards aqueous ammonia and sodium hydroxide at room temperature.The sulphone groups would exert an electron-attracting inductive effect (-I) on C, of the cyclic disulphones thus making C(a) cationoid and facilitating the cleavage of the C(a>-C(l) bond. A methyl group at C,,, however would exert an opposite inductive effect (+I) which would tend to neutralise the inductive effect of the sulphone groups and hence inhibit the cleavage as in the case of (V). Steric reasons for the stability of the ethyl derivatives were ruled out by the stability of 2,2-di- ethylsulphonyl-1 -methoxypropane in aqueous am- monia. Theoretical considerations have led us to conclude that the fusion of a five-membered cyclic acetal ring to a pyranoside ring holds the latter in a half-chair conformation.Since the intermediate oxonium cation (11) also possesses a half-chair conformation W) in which C (5) ring 0,C(l),and C(z)are coplanar H HO-4 HO-H ti’ 2-1 \ /-/+\ 0-5 ?-OH 0 I3 (Vl) (VI II) it seemed likely that the superimposition of a planar five-membered isopropylidene ring (e.g. as in VII) on the original cyclic disulphone (I) would impede the formation of the intermediate state thus de- creasing the rate of reaction. Consequently the 2,3-0-isopropylidene derivative (VII) was prepared and it was found to be stable in aqueous ammonia. This evidence is therefore consistent with the existence of the isopropylidene derivative in a half-chair con- formation (VIU) from which oxonium cation forma- tion was impossible unless the pyranoside ring Hough and Taylor J.1956 970. * The compounds of type (I) being regarded as C-substituted 1-deoxypentopyranoses it becomes possible to assign the aconfiguration to the CHR group. The term C(aj-C(,) bond means the (+)bond from C(J to the carbon of the CHR group. If the orientation of this group had been /3 the bond would have been called C(,q-C(,). adopted the sterically unfavoured planar form. On the other hand the 3,4-0-isopropylidene-derivative (IX) of the D-arabo cyclic disulphone was slowly de- graded in ammonia to 3,4-O-isopropylidene-~-arabinose and diethylsulphonylmethane.If this iso- propylidene derivative is assumed to exist in the half- chair conformation (X) in which C(2) C,) C,,) and C(5) are coplanar the degradation can proceed PROCEEDINGS through an intermediary oxonium cation in which all the steric requirements are satisfied if the half- boat conformation (XI) is adopted.The above data are in full accord with the S,l mechanism for the degradation of the cyclic disul- phones and provide good evidence of an intermediary oxonium cation. (Received April 13th 1959.) The Crystal Structure of Mono(thiourea)lead(Ir) Acetate By M. NARDELLI and G. FAVA CHEMISTRY INSTITUTE (STRUCTURAL LABORATORY OF CHEMISTRY UNIVERSITY ITALY) OF PARMA MONO(THIOUREA)LEAD(II) ACETATE Pb [SC(NH2)2](CH3-C02)2 crystallizes in very slend- er colourless monoclinic needles elongated along [loo].The unit cell dimensions are a = 4.55 f 0-01A b = 15.81 f0.03 A c = 14.28 & 0.07 A, fi = 106.4 %-0.1 O 2 = 4 D = 2.66 (by flotation) D = 2.70. Space group P 2,/c (C52h,No. 14). Cu-Kcc radiation (A = 1.5418 A) single-crystal rota- tion photographs around [lo01 and [OlO] Weissen- berg photographs of the Okl lkl 2k1 h0Z reflexions. The solution of the structure was obtained by the heavy-atom method starting from the lead co-ordinates determined from P( V,W) and P(U,W) Patterson projections. The positions of the other atoms were found by ineaiis of po(Y,Z),po(X,Z),and Ipl( Y,Z)I Fourier projections. At the present stage of this work the reliability indices (unobserved re- flexions not included) are R(0kl) = 0.13 R(1kZ) = 0.14. The structure is now being refined to improve the co-ordinates of light-atoms.The positions of lead and sulphur atoms are nevertheless sufficiently definite to show that in this compound the sulphur atom of every thiourea molecule is co-ordinated by three lead atoms (see Figure). The co-ordination polyhedron around each lead atom is completed by the oxygen atoms of acetic acid groups but at the present stage of this research its form cannot yet be surely defined. Nevertheless it can be seen that the co-ordination polyhedra form a double chain ninning along [loo]. The three bond-lengths Pb-S are somewhat different from one another the shortest (3.08 A) is nearly equal to the mean value we have found1 for the same distances in Pb[SC(NH,),],CI,; the other two are considerably longer (3.17and 3.36 A).It is interesting that among thiourea-metal \ @ Pb Bond-distances and angles between Pb and S in Pb [SC(NH2) 2](CH3C02) (clinographic projection). complexes of known structure the compound Pb[SC(NH2),](CH3CO2)) is the only compound in which the sulphur atom of the organic molecule forms three co-ordinative bonds. The sulphur atom is monoco-ordinated in Ni [SC(NH2)2],C1,,2 Cd [SC(NH2)2]2C12,3 Zn[SC(NH2)2]2C12,4 and bicoordinated in Ni [SC(NH.J2l2(NCS); and Pb[SC(NH,) ]2C12.1 (Received May lst 1959.) Nardelli and Fava Acta Cryst. in print. Cavalca Nardelli and Braibanti Gazzetta 1956 86 942. Nardelli Cavalca and Braibanti ibid. 1957 87,137. Kunchur and Truter J. 1958,701. Nardelli Braibanti and Fava Gazzetta 1957 87 1209.JUNE/ JULY 1959 195 Manganese Bhthalocyanine as an Oxygen Carrier By J. A. ELVIDGE and A. B. P. LEVER CHEMISTRY LABORATORIES COLLEGE, (ORGANIC RESEARCH IMPERIAL LONDON,S.W.7) MANGANESE phthalocyanine can combine reversibly with oxygen it appears to be the first example of a manganese compound that behaves as an oxygen carrier. This is of interest in view of the recent im- plication of manganese possibly as a porphyrin complex in the metabolism of human red blood- ce1ls.l The mode of combination with oxygen is different from that for haemoglobin. A solution of manganese(I1) phthalocyanine2 in pyridine (necessarily <5 x lo4 molar) absorbs oxygen in the cold the olive-green solution (A,,,.7125 A) becoming dark blue (A,,, 6200 A). Boiling this gives back the green solution of manganese phthalocyanine which when cooled re-absorbs oxygen. (It is of course stable under nitrogen.) The cycle can be repeated many times with little destruc- tion of the pigment. Several species are involved and the accompanying scheme is suggested. lattice structure 0,as indicated by the infrared absorption. This is closely similar to that of man- ganese phthalocyanine (I) but with additional ab- sorption at 820cm.-l characteristic of the Mn-0-Mn linkage.3 The compound (V) with pyridine under nitrogen gives the blue solution of (IV) boiling pyridine gives a green solution of manganese phthalocyanine (I). Interaction of oxygen with manganese phthalo- cyanine in pyridine would not be expected to give the product (IV) directly.The possible first intermediate (11) must be very labile whilst the peroxy-compound (III) which would correspond with the oxygen up- take would not account for the visible-light absorp- tion of the solution. These Likely intermediates then may be present in only very small concentration and the oxygenated species in solution is best regarded as compound (IV). Q __t 92 t H= where PcMn= C,&,N8Mn and Py= pyridine The evidence is as follows. Pyridinet plays an essential part because it cannot be replaced by non- donor solvents such as o-dichlorobenzene. The oxygen uptake measured with a Barcroft respiro- meter is 1 molecule per 2 molecules of manganese phthalocyanine (I).The isolated product has the formula PcMnO-py the quadrivalent structure (IV) is supported by the infrared absorption (bands characteristic of pyridine and a strong band at 1096 cm.-l for the Mn=O linkage3) and by polaro- graphy in pyridine containing O.O5~-lithium bromide which shows two reduction steps with half-wave potentials at -0-76 and -0.94 v corresponding to the processes (IV) + PcMnnIOH -+(I) + H,O. Heating compound (IV) at 180°/15 mm gives a thermally stable product PcMnwO (peff.3.77 B.M.) which evidently has an extended six-co-ordinate Manganese phthalocyanine readily decomposes hydrogen peroxide but is itself fairly rapidly destroyed. It catalyses efficiently the aerial oxidation of e.g.benzaldehyde and aniline but is in general too rapidly destroyed to be of value in syntheses. Catalase and oxidase properties are shown strongly by iron phthalocyanine and weakly by the chromium and cobalt comple~es,~ but manganese phthalo- cyanine was apparently not examined. We thank Dr. J. Lewis for helpful discussion of infrared and magnetic data and Mr. W. P. Griffith for the polarography. Grateful acknowledgement is made to the Department of Scientific and Industrial Research for a maintenance grant (to A.B.P.L.). (Received April 15th 1959.) * It is uncertain whether oxygen or pyridine N-oxide is formed. t Acid-free freshly distilled from barium oxide. Borg and Cotzias Nature 1958 182,1677. Barrett Dent and Linstead J.1936 1719; Linstead and Robertson ibid. p. 1736. Dr. J. Lewis unpublished work. A. H. Cook,J. 1938 1761 1768 1774. PROCEEDINGS NEWS AND ANNOUNCEMENTS The Research Fund.-The Research Fund of the Chemical Society provides grants for the assistance of research in all branches of Chemistry. About seven hundred pounds per annum is available for this purpose. Applications for grants will be con-sidered in November next and should be submitted on the appropriate form not later than Saturday November 14th 1959. Applications from Fellows will receive prior consideration. Reports on grants outstanding from previous years should be made by November 1 st. Forms of application together with the regulations governing the award of grants may be obtained from the General Secretary.Election of New Fellows.-1 57 Candidates whose names were published in Proceedings for March and April have been elected to the Fellowship. Library of the Chemical Society.-From July 16th until September 30th 1959 the Library will close at 5 p.m. instead of at 7.30 p.m. It will not be open on August 3rd and 4th. International Tables for X-Ray Crystallography.- Volume I1 (Mathematical Tables) of the Tables for X-Ray Crystallography published for the Inter- national Union of Crystallography is now ready. The price is E5 15s. inclusive of postage and packing but Fellows of the Chemical Society may obtain one copy for their personal use only at the subscription price of &3 10s. post free by using a special order form available with the prospectus from the Kynoch Press Witton Birmingham 6 England.Conference.-The Third Australasian Conference on Radiation Biology will be held at the University of Sydney from August 15th to 18th 1960. It is expected that two or more guest speakers will deliver addresses to the Conference on the primary biochemical and biological protection and the delayed somatic effects of radiation. Papers in general of 2,500 words (250 word sum- mary) are invited in radiation biology radiation chemistry and radiation physics. Further particulars will be available from the convener Dr. Peter Ilbery Department of Preventive Medicine University of Sydney N.S.W. Deaths.-We regret to announce the deaths of the following Fellows :Professor Hilmar Johannes Backer (29.4.59) Emeritus Professor of Organic Chemistry of the University of Groningen; Mr.Harry Lucas (29.1.59) formerly of the South of England College of Pharmacy and Dr. Andrew Turnbull (25.4.59) formerly with the Coastal Forestal Land Timber and Railways Co. Ltd. Harpenden. Personal.-Professor E. L. Hirst and Professor R. G. W. Norrish have been elected Honorary Members of the Polish Chemical Society. Dr. Albert Parker C.B.E. was elected to Honorary Membership of the Institutiozi of Gas Engineers at their Annual Meeting on May 26th. Dr. F. M. Brewer has recently taken office as Mayor of Oxford. Dr. C. H. Giles has received the D.Sc. degree of the University of Glasgow for his work on surface- activity and adsorption.Dr. E. W. Abel has been appointed Lecturer in Inorganic Chemistry at the University of Bristol as from August lst 1959. Professor Holger Erdtman Professor of Organic Chemistry at the Royal Institute of Technology Stockholm will visit South Africa in July as the guest of the South African Chemical Institute and the South African Council for Scientific and In- dustrial Research. He will be accompanied by his wife Dr. Gunhild Aulin-Erdtman. Professor and Mrs. Erdtman will take part in the proceedings of the 13th Annual Convention of the South African Chemical Institute to be held in Pretoria from July 20-24th. Dr. T. B. H. McMurry has been elected to a Fellowship of Trinity College Dublin.Dr. J. 0.V. Oubridge of Liverpool College of Technology has accepted a Research Fellowship offered by the Canadian Defence Research Board for the session 1959-60 and tenable at Hamilton College McMaster University Hamilton Ontario. Professor R. A. Robinson bas been appointed Professor of Chemistry in the newly established Kuala Lumpur division of the University of Malaya. Dr. C. J. M. Stirling has been appointed Lecturer in Organic Chemistry and Dr. W. R. Jackson Assistant Lecturer in Organic Chemistry at the Queen’s University Belfast. Mu. A. Norton has been appointed a Director of Rowntree & Co. Ltd. JUNEIJULY 1959 OBITUARY NOTICE GEORGE MACDONALD BENNETT 1892-1959 G. M. BENNETT was born on October 25th 1892 in the City of Lincoln where his father was a Baptist Minister afterwards moving to the Mare Street Baptist Church in Hackney.For health reasons Mr. Bennett senior had to give up his work as an active Minister and he opened a private boarding school at Clacton-on-Sea. Here he was soon joined and later succeeded by Harold Picton one of Ramsay’s students who is well-known to chemists for his col- laboration with S. E. Linder on “Solution and Pseudo-Solution,” describing colloidal arsenious sulphide solutions. G. M. Bennett became a pupil at Picton’s school called Clacton College. There were never more than twenty boys and the school was very advanced in many ways. Languages were taught by the direct method and chemistry by the heuristic method.Games were played but not made as important as in most schools. G. M. Bennett had a fine quick brain and a retentive memory. In 1909 he passed the External London Intermediate in Arts and obtained a Univer- sity Exhibition in Arts. With this he entered East London College (now Queen Mary College) to study chemistry. In 191 1 he took an External London B.A. in French Latin Physics and Chemistry and in 1912 obtained a very good First Class in the Internal Honours B.Sc. degree in Chemistry. J. T. Hewitt F.R.S. was the Professor assisted by Clarence Smith and F. G. Pope. Bennett was highly appreciative of their teaching with its emphasis on research and on the importance of reading the original chemical literature. He took little part in the social or athletic side of undergraduate life but attended various evening courses including one on colloids started at Sir John Cass Technical Institute by Emil Hatshek.For most men this would have been enough in the way of undergraduate study but Bennett took an Open Exhibition in Mathematics and Natural Sciences at St. John’s College Cambridge in 1913 became a Foundation Scholar in 1914 and took a First Class in Part I and Part I1 of the Natural Sciences Tripos in the minimum time. At Part I he included mineralogy as a subject and this gave him an interest and skill in what was then called crystal- lography. In later years he frequently measured the crystals of compounds he had made. Bennett as an undergraduate at Cambridge came under the in- fluence of W.J. Pope (later Sir William) W. H. Mill? S. Ruhemann R. H. Adie and H. J. H. Fenton in Chemistry J. J. Thomson (later Sir Joseph) and A. F. C. Searle in Physics and A. Hutchinson in Mineralogy. Bennett’s first publication was a paper from East London College with A. D. Mitchell at present an Assistant Editor of the Journal in the Zeitschriff fur physikalische Chemie (1913) on total molecular sur- face energy and chemical constitution. It was shown that for non-associated liquids this energy (y -tdy/di)(M~)~’~ is virtually independent of temp- erature. Atom and group constants and the degree of association of numerous liquids were evaluated. One may contrast the labour then involved with modern calculations using machines.Two years later Bennett determined the surface tension of acetic acid under its own vapour from 15” to 150° and from the observations that the total molecular surface energy was almost constant over this temperature range concluded that acetic acid is a normal liquid consist- ing exclusively of the complex molecules (C2H,02),. As a piece of vacation work in 1913-1914 Bennett and the present writer studied the action of an-hydrous chromic chloride on Grignard reagents. This they showed to take place quantitatively according to the equation 2RMgHal + 2CrCI = R*R + ZCrCI L 2MgClHal (or an equivalent mixture) At that period this provided an excellent method for preparing diary1 hydrocarbons. I remember we were delighted to see the magnificent peach-blossom coloured water-repellant chromic chloride dissolve violently in the ether to give a green solution.From 1915 to 1918 Bennett acted as one of W. J. Pope’s research assistants for work on explosives and other problems and towards the end of this period he carried out the first experiment for making mustard gas from disulphur dichloride and ethylene. In spare time in 1917 he proved by crystallographic measurements that some supposedly isomeric ferro- cyanides were identical save for a colour difference caused by traces of impurity. The years 1919 to 1921 were spent by Bennett as research chemist in charge of the laboratories of Messrs. Strange & Graham Ltd. Here he was con- cerned with fine chemicals and with fermentation processes one of these providing citric acid from cane sugar.Whilst in this post he prepared and examined authentic 2,2’-dichlorodiethyl disulphide in connection with the formation of mustard gas from disulphur dichloride and ethylene. In 1921 Bennett was appointed Senior Demon- strator in Chemistry in Guy’s Hospital Medical School where he carried out an investigation of monothioethylene glycol. He also published an in- teresting paper on “autoreduction of sulphurous PROCEEDINGS acid,” showing that this acid liberated in aqueous solution from its salts at temperature of 100-120” may undergo instantaneous autoreduction with pro- duction of hydrogen sulphide. With C. s. Gibson Bennett examined the meso-and racemic forms of tetrahydro-2,3-diphenylquinoxaline effecting the optical resolution of the latter.From 1924 to 1931 Bennett was Lecturer in Organic Chemistry in the University of Sheffield then becoming Firth Professor until 1938. His mental and experimental activities were very great at this period and his enthusiasm was infectious. He now was able to develop his ideas and with colleagues and postgraduate students carried out researches on a variety of problems many of them dealing with the chemistry of compounds containing sulphur. One series of investigations concerned the effect on the reactivity of OH or C1 in the homologous series [HO(or Cl).(CH,),],S of varying the value of n. Thus for example it was found that although the replacement of OH by Cl is brought about in a few minutes by the action of hot concentrated hydro- chloric acid in the case of 2,2’-dihydroxydiethyl sulphide 110 such replacement occurred with 3,3’- dihydroxydi-n-propyl sulphide.The 3,3’-dichloro- compound was readily obtained from the latter by the action of thionyl chloride in presence of di- methylaniline and was sharply distinguished from most sulphides by its apparent inability to form a sulphoxide the sulphone being the lowest isolable oxidation product. In extension of this problem it was found that whereas 3,3’-dibenzyloxydipropyl sulphide readily gave the 3,3’-dihydroxy-~ompound with hydrobromic acid 4,4’-dibenzyloxydibutyl sul- phide was converted by the latter into tetrahydro- 1-4-hydroxybutylthiophenbromide.4-Chlorobutyl phenyl sulphide and 5-chloropentyl phenyl sulphide both underwent cyclisation to sulphonium salts when heated. From kinetic experiments done in 50% acetone-water at 80” it was found that the king was formed 76 times as fast as the 6-ring. This result appeared to be satisfactorily explained on the prob- ability of 1 :5 as against 1 :6 collisions. The sulphur atom activated the chlorine atom as the Zatter approached. Related work was done on the replacement of C1 by OH or by I in a series of chloroalkyl nitrophenyl- alkyl sulphides. The reactions were studied quantita- tively the rates varied in opposite senses as between the hydrolysis and the replacement of OH by I as expected. An examination was made of conditions under which cyclisation occurred with w-chloroalkyl sul-phides containing 7-1 1,14,16 and 18 carbon atoms between Cl and S.Using very dilute solutions in boil- ing acetophenone in presence of sodium iodide only three chlorosulphides gave a simple ring the rest giving polymers. Two new compounds hexadeca- methylene and octadecamethylene sulphide were crystalline the first of these smelling of musk. In an elaborate piece of work the relative re- activities of alcohols and glycols with hydrobromic acid were determined. It had previously been shown that the reactivity of a hydroxyl group with hydro- bromic acid was greatly enhanced by the presence of a sulphur atom in the 18 6 or E position to it (separated by 2,4 or 5 carbon atoms) but depressed if the sulphur atom is in the y-position and as al- ready indicated an explanation based on the steric accessibility of the separated groups was advanced.In 1935 it was shown that these phenomena are repeated when oxygen replaces sulphur. Thus of the straight chain glycols HOfCH,];OH by far the most reactive is tetramethylene glycol the next most reactive being pentamethylene glycol. This brief sketch gives only a slight indication of the valuable contributions made by Bennett and his colleagues to reactivity problems. Another important series of publications concerned the stereochemistry of sulphur in heterocyclic compounds. Thus follow- ing the sulphoxide work of Kenyon and Phillips Bennett looked for and found two disulphoxides of dithian.He also settled an important point in con- nection with trimethylene sulphide the dimethiodide of which Langmuir had mentioned in 1920 as being the only substance known of the type [SRJI,. This Bennett proved to be 3-iodopropyldimethylsulphon-ium iodide. Earlier Bennett had effected for the first time the closure of a simple heterocyclic ring by means of the Dieckmann reaction ethyl 4-hydroxy-d3-penthien-3-carboxylate being produced from ethyl ,8-thiodipro- pionate and slowly changing into the keto-ester ethyl 4-oxopenthian-3-carboxylate. In 1929 stereoisomeric pairs of sulphoxides of penthianols were isolated 0 ,C%-CH2\ ,OH CH;C%\ ,OH S’ /c\ s\ CH?CH2,=\ R 0’ \CH;CH2 R A study of the regulated oxidation of trithian led to the isolation and proof of the configuration of all the theoretically possible mono- di- and tri-sulphoxides.In an interesting collaboration with E. V. Bell and F. G. Mann it was confirmed that the supposed third isomeride of trithioacetaldehyde was a mixture of the a-and /iI-compounds. In 1928 Bennett and Willis suggested that although for molecular compounds to be formed by nitro- compounds it had been thought that at least a second nitro-group was usually necessary methoxycarbonyl or chlorosulphonyl groups could act in a similar way. JUNE/JULY1959 Later (1936) Bennett and R. L. Wain (now University Professor of Agricultural Chemistry at Wye College) broadened the scope of this enquiry and made some remarkable observations.Thus the nitrile ester amide and acid chloride of 3,5-dinitro- benzoic acid all readily yield a number of molecular compounds usually of the molecular ratio 1 :1. The dinitronitrile forms a 2 1 compound with benzidine and also with diphenyl fluorene and anthracene- substances having in the molecule two separate ben- zene nuclei not directly fused together and each separate nucleus acting as a donating centre. No fewer than 47 molecular compounds were isolated. The same authors noting that cineole formed stable molecular compounds with phenols prepared a number of related cyclic ethers and examined their power of addition. It was found as had been thought probable that tetramethylphthalan C,H <(CMe&,> 0 formed 1:1 compounds with a-and p-naphthol p-bromophenol p-iodophenol catechol and p-xylenol.On the other hand with resorcinol a 2 ether 1 phenol compound was formed and no addition occurred with sym-trichloro- or sym-tribromo-phenol. These results clearly showed that addition was between the oxygen of the ether and the hydroxyl group of the phenols co-ordination through hydrogen being the key factor. A related problem was on the influence of structure on the solubilities of ethers. Thus at 10.0” the figures in parentheses were the solubilities found in water ethyl n-propyl ether (2-74) pentamethylene oxide (10.70) P-methyltetramethylene oxide (1 1-25) a-rnethyltetramethylene oxide (1 8.20) Pp’-dimethyl-trimethylene oxide (19.3 1).The most interesting effect is that substitution of a secondary for a primary radical attached to the oxygen atom increased the solubility as shown in previous work at Sheffield. The extreme development of chemical reactivity due to a tertiary radical is seen in &a’-dimethyltri-methylene oxide and 01 a‘-methylethylethylene oxide by the immediate rupture of the ring on dissolution in water. Another fact discovered was the large increase of solubility caused by ring-closure. Of the greatest interest was Bennett’s work on thianthren. With S. Glasstone it was shown that this substance had a dipole moment of 1.5 D approxi-mately the value recorded by E. Bergmann and M. Tschudnowsky and therefore as these authors sug- gested had molecules folded about the S-S axis.Bennett and Dearns looked for but could not find a third possible disulphoxide. This would have been what might be called the all-cis isomeride and would nowadays be regarded as being impossible as there are several parallel cases. Bennett and Glasstone again joined forces on “an analysis of the dipole moments of some aromatic compounds.” They analysed the data for the dipole moments of para-substituted anisoles phenols di- phenyl ethers and anilines by a direct method and concluded that in all these substances there was a deviation from strict additivity of the bond moments. The deviation was attributed to the mesomeric effect. They also showed that the use which had been made of the dipole moment of aromatic compounds for the computation of the valency angle of oxygen (and thus probably of sulphur) was unsound.Bennett had a deep interest in liquid crystals and his practical demonstration with a lantern of the beauty of mesomorphic state changes as seen through Nicols was a great pleasure to witness and remember. Of more than ordinary importance was his work with Brynmor Jones (later Professor of Chemistry and now Vice-Chancellor at Hull) on the mesomorphism and polymorphism of p-alkoxybenzoic and p-alkoxy- cinnamic acid. In this research it was observed that p-n-propoxybenzoic acid was then the simplest compound known to form liquid crystals. In 1938 Bennett was appointed as a University Professor of Chemistry at King’s College London and as a result spent the war period at Bristol.Here he worked on explosives problems. In 1946 he arranged a Discussion on “Nitration” in the rooms of the Society. To this he contributed two papers. In the first (describing work done in col- laboration with Gwyn Williams later University Professor of Chemistry at Royal Holloway College) it was recorded that direct evidence had been ob- tained that nitric acid exists as a positive ion in sulphuric acid. This had been proved by electrolysing solutions of nitric acid or barium nitrate in oleum the nitric acid migrating to the cathode 2-4 tiines as fast as the barium ion. Migration in 98.7% sul- phuric acid was also observed and similar results were found with N,O in oleum. It was further shown that the formation of water according to the equation HNO + 2H,S04 = NO,+ + H,O+ + 2HS04-follows from the fact that addition of nitric acid to oleum weakens the Raman lines of pyrosulphuric acid and strengthens those of sulphuric acid.The second paper dealt with the kinetics of nitration of 2,4-dinitrotoluene in sulphuric acid solu- tion. The sulphuric acid used varied from 87.4% aqueous acid to oleum of 29.1 % SO3 and tempera- tures varied from 60” to 120”.It was concluded that the nitration involved attack by the NO,+ ion and a proton-acceptor simultaneously the actual proton- accepting species being HS0,- H,SO, and HS207- thus Ar-H + NO,+ + HS0,-+ Ar-NO + H,SO A further indication of Bennett’s great versatility is that his last publication was on synthetic anti- malarials an account of the synthesis of numerous dialkylaminoarylaminoquinolines.This was con-joint partly with Professor D. H. Hey his successor at King’s In 1945 Bennett was offered the post of Govern- ment Chemist. After much careful thought he accepted this appointment as a duty although it meant giving up his academic research. As the head of the important Government Laboratory he was very successful as a chemist and as a personality. He was elected to the Fellowship of the Royal Society in 1947 and was created C.B. in 1948. He held the degrees of M.A. and Sc.D. (Cambridge) and B.A. and Ph.D. (London). Since 1946 he had been a member of the Royal Commission on Awards to Inventors.Bennett was a Fellow of St. John’s College Cambridge from 1917 to 1923 and a Fellow of Queen Mary College from 1939 to the time of his death. He had served on the Council of the Chemical Society and was an Honorary Secretary from 1939 to 1946. He had a period on the Council of the Faraday Society and one as a director of the Bureau of Chemical Abstracts. He had been Honorary Secretary of the Chemical Council and a Vice-President of the Royal Institute of Chemistry. In 1918 Bennett married Doris Laycock who had recently taken Part I1 of the Classical Tripos. Her death at Christmas in 1957 was a great blow to him. They had no children. Some time before his peaceful death on February 9th 1959 he had had an attack of coronary thrombosis.Bennett with his shortish sturdy figure changed very little in appearance over the fifty years in which I knew him. He had little colour and his facial expression was normally serious. Yet in a debate I have seen it dissolve in delight at a point well made. He had the rare quality of natural dignity buoyed up by youthfulness. E. E. TURNER. 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 Proceeding.s. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Bottom Alan Edward. 20 Lilian Avenue Wallsend Northumberland.Bretzel Luciana Naldini D.Chem. Via Saldini 50 Milano Italy. Browning David Robert. 35 Cheshire Avenue Areley Kings Stourport-on-Severn Worcestershire. Clement Peter William. 40 Mill Hill Deal Kent. Crout David Herbert George B.A. Valmer Higher Lane Langland Swansea Glam. Cureton Pamela Helen. 25 View Street Chatswood N.S.W. Australia. Dickens Peter George M.A. D.Phi1. 120 Woodstock Road Oxford. Doering Charles Henry B.Sc. 1574-39th Avenue San Francisco 22 California U.S.A. Eastwood Frank Warburton M.Sc. D.Phi1. 32 City Road Cambridge. Felix Arthur. 1551 University Avenue Bronx 53 New York U.S.A. Fraser Robert Rowntree M.Sc. Ph.D. Department of Chemistry University of Ottawa Ottawa Canada. Giza Chester Anthony M.S.Sterling Chemistry Labora- tory Yale University New Haven Conn. U.S.A. Grant Frederick Warren jun. B.S. Ph.D. Department of Chemistry The Johns Hopkins University Baltimore 18 Maryland U.S.A. Grindley Robert M.Sc. Ph.D. Dagmar House Great North Road Hatfield Herts. Hawkins Stanley Wallace B.A. 15A Heathdene Road Wallington Surrey. Huggins David Anthony. 15 Alexandra Road Leeds 6 Yorks. Jambrich Martin. 283 Svit pod Tatrami Czechoslovakia. Kaegi Hans Heinrich. Laboratorium fur Organische Chemie Eidgenossische Technische Hochschule Uni- versitatsstrasse Zurich Switzerland. Khan Ahsan Ullah. 2 Blagrove Road London W.10. Khan Mirza Mohammad Taqui M.Sc. 15-4-479 Yakutpura Hyderabad (A.P.) India. Krasinski Andrzej Hubert Antoni. 47 Foxhall Road Sherwood Rise Nottingham.Kwon Joon Taek B.S. Box 65 Baker Laboratory, Cornell University Ithaca N.Y. U.S.A. Livingston David Campbell. 41 Robertson Street, Greenock Scotland. Lunn Geoffrey David. 26 The Drive Harrow Middx. McDonald Alison Jean B.Sc. 33 Scotts Lane Shortlands Bromley Kent. Moreau David Merlin M.A. The Yews Berrick Benson Oxon. Moye Anthony Joseph M.S. Department of Chemistry, Iowa State College Ames Iowa U.S.A. Muxart Roland. 4 Avenue de la Convention Arcueil Seine France. Russell Richard Uniacke B.Sc. 25 Bellewe Road Southbourne Bournemouth Hants. Samuels Edwin B.Sc. Chemistry Department The University Sheffield. Sarett Lewis Hastings E.S. Ph.D. Merck & Co. Inc. Rahway N.J. U.S.A. Sartain David.23 Hollingbourne Gardens Ealing W. 13. Saxelby Derek. 52 Outwoods Drive Loughborough Leicestershire. Silcox Norman Wesley M.S. Ph.D. 25 Middle Street South Dartmouth Mass. U.S.A. Slack Sharon K. B.S. 344 Grove Street East Lansing Michigan U.S.A. Sy Michel D.es.Sc. Laboratoire de Synthkse Organique Ecole Veterinaire Maisons-Alfort Seine France. Szymanski Jan Tomasz. 21 Comeragh Road London W.14. Thomas Eric Lionel BSc. Glendale Yniscedwyn Road Ystradgynlais Swansea Glam. Turner Raymond BSc. 21 Skipton Road Billingham Co. Durham. Walls Graham Henry Francis. 16 Randall Close Langley Slough Bucks. Ward Ronald Sydney B.Sc. F.R.I.C. 27 Franklyn Road Walton-on-Thames Surrey. Wishlade John Lewis. The Manor House Northfield Birmingham 3 1.
ISSN:0369-8718
DOI:10.1039/PS9590000169
出版商:RSC
年代:1959
数据来源: RSC
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