Barbier-Grignard: Explosive Reaction

Barbier-Grignard: explosive reaction

Tadeusz Urbański

The early paper by P. Barbier (1898) and the thesis of V. Grignard 1. The statement of Barbier on (1901) led to the foundation of the 'Grignard reaction'. It follows, his prior use of magnesium for syn­ however, from existing documents, the discussion between Barbier thesis is well documented by his paper—Comptes Rendus, 1 899,128, and Grignard (1910) and a letter of Grignard (1912) that the reaction 110. Here hedescribed a modification should more correctly be called 'Barbier-Grignard reaction' but that of reaction of Saytzeff (as he pointed the reagent should be named the familiar 'Grignard reagent.' out) by replacing zinc with mag­ nesium. Starting from methyl- heptenone he obtained dimethyl- There is no doubt that Grignard is Grignard studied chemistry under heptenol: one of the best known names of Barbier and received in 1901 his great chemist-founders of present degree of Docteur ès sciences on the CH day chemistry. It obviously is due basis of his thesis where he investi­ 3 to the fact that every organic chemist gated the use of magnesium for \ has carried out the Grignard-reaction organic synthesis on the suggestion С = СН CH2CH2CO CH3 + at least once in their lifetime. For a of Barbier. A few days later Barbier long time the use of the reaction was sent a letter to the editor of Salut / limited to laboratory /'e small scale Public. The letter contains some CH3 work. However, in the late 30s and statements important to the history An ether CH I + Mg > after World War 2 it penetrated into of the reaction. Here are main 3 chemical factories thanks to С H 3 С H 3 parts of the text: \ I (/) improvement in the design of С = СН CH2 CH2-C-0-Mg I air-tight reactors and (//*) introduc­ / I Monsieur le rédacteur en chef du tion of less volatile and relatively CH3 CH3 high boiling point solvents with an Salut Public H20 + H2S04 ether function such as tetrahydro- J'ai lu un peu tardivement dans le Salut Public du lundi 9 décembre l'article furane and dioxane. intitulé: 'L'oevre d'un savant.' Cet article The Grignard reaction is now used relatif aux travaux de M, Grignard, exact CH3 CH3 dans son ensemble, renferme néanmoins in chemical industry in the pro­ \ I une affirmation erronée évidemment in• duction of some fine chemicals, С = СН CH CH -C-0H + volontaire qu'il m'est impossible de ne pas 2 2 drugs, scents etc. / I vous signaler. Je fais allusion à la phrase: The increasing importance of the 'La méthode nouvelle découverte par le СН 3 С H з reaction compels us to look into the jeune docteur . . .' qui attribue à M, history of this remarkable achieve­ Grignard un travail qui ne lui appartient Mg (ОН) I ment which in 1912 brought the aucunement. In his paper he gives a detailed Nobel Prize to Victor Grignard, C'est moi qui, dans le courant de l'année description of the procedure which professor at the University of Nancy. 1899. ai institué cette nouvelle méthode is the same as the classical procedure He shared it with another French de synthèse des matières organiques basée of the Grignard reaction. chemist—Paul Sabatier, professor at sur l'emploi du magnesium ainsi que le Barbier ends his paper with a the University of Toulouse who prouve mon mémoire aux Comptes rendus remark that he was able to carry out received the Nobel Prize for his de l'Académie des Sciences, tome CXXXVIII, a number of synthesis by this method page 110 année 1899. catalytic hydrogénation of organic and he intends to report them in the L'oeuvre de Grignard a consisté à compounds which he developed future. with Senderens. développer les conséquences normales de cette découverte qui m'appartient intégrale• Two more papers of a polemic On 9 December 1912 the French ment. Ce travail exécuté très brillamment character are pertinent to the history journal Salut Public published a note a value à son auteur les récompenses et les of the reaction. L'oevre d'un savant giving informa­ faveurs que vous savez, ce dont j'ai été 2. Barbier published a note tion on Victor Grignard's Nobel très heureux. 'Sur l'origine de l'introduction du Prize. Il n'entre pas dans mes vues de diminuer magnesium dans la synthèse organi• The note invoked a strong re­ la valeur des recherches d'un de mes que' i n Bulletin de la Société chimique meilleurs élèves, mais la justice et la vérité action from P. Barbier, professor at de France. 1910, 7, 206. exigent qu'il soit rendu à chacun ce que lui the University of Lyon, where appartient. . . . The author draws attention to the . . . Je tiens à vôtre disposition les pièces wrong tendency, which could be Tadeusz Urbański is emeritus professor qui en justifient la légitimité. seen in the current chemical litera­ in the Chemical Faculty. Technical Veuillez agréer. . . . ture and encyolopaedic publications, University, Warsaw. Poland. A member 1—1 Professeur P. Barbier in which the discovery of using of the Polish Academy of Sciences, he Faculté des Sciences de L yon magnesium in organic synthesis is has written over 500 papers, and one assigned exclusively to Grignard. of his books Chemistry and technology Here are a few facts which should of explosives has been translated into This is not justified as the author several languages. make the Barbier-Grignard problem had introduced magnesium into unambiguously clear. chemical technique for the first time 191 for the synthesis of dimethyl- part which he played in developing l'honneur que m'ont fait les chemists heptenol. After this introduction the new reaction. en attachant mon nom). Barbier repeated nearly a complete Although Barbier himself does Grignard also pointed out that the text of his paper published 1899 in not blame Grignard, it seems worth development of mixed magnesium Comptes Rendus. He adds that by recalling all the documents which organic compounds produced a great this method he also obtained the referred to the problem. impact upon the development of secondary methylated alcohol Grignard pointed out many times mixed zinc organic compounds deriving from citronellal. He explains {eg Thesis, Ann. /'Univ. Lyon, Ann according to Bewad and particularly that he has not published the Chem. Phys. 1901 ; Revue general to Blaise and his school. description of it. as at the time he Science, 1903) the importance, both 4. The last important document is handed the whole problem to Grig- theoretical and practical, of the syn• a hand-written letter of V. Grignard nard of replacing zinc by magnesium thesis by Barbier of dimethylheptenol to his friend Meunier (13 November in order to find whether the reaction (incidentally Sand and Singer as well 1912). with magnesium has a general as Harries and Weil, Chemische character and whether it is advan• Berichte, 1 902 and 1 904 respectively, ... /1 vrai dire et entre nous, j'aurais tageous to replace zinc by mag• described once more this alcohol. préféré, quitte à attendre encore un peu, nesium. A detailed description of Evidently they had no knowledge of voir partager le prix entre Sabatier et Senderens et le partager ensuite—moi the reaction can be found (according the synthesis of Barbier). тете avec Barbier, Mais que puit—je to Barbier) in the excellent thesis of A number of authors describing contre un tel verdict sinon m'en féliciter! Grignard presented to the faculty of the use of magnesium in organic Tu sera bien aimable de me donner science in Lyon. Thanks to his chemistry also gave the true picture, ausitôtque tu le pourras quelques renseigne­ success Grignard became, and is eg: Valeur, Bulletin des Sciences ments sur l'état de la santé et sur l'état still, a co-worker of Barbier. Grig• Pharmaceutiques, 1902; Kiages. d'esprit de M, Barbier, nard fully used the opportunity Chemiker Zeitung. 1905; Waters, Je me demande comment il va prendre offered to him by the problem. American Chemical Journal, 1905;la chose. Mais s'il se considère comme Schmidt, Ahrens' Sammlung, 1905; frustré, je ne pense pas qu'il puisse m'en His aim was first to isolate mag• rendre responsable. . . .' nesium-organic derivatives and then Die organischer Magnesium verbin- let them react further. Thanks to dungen und ihre Anwendung zu Thus speak the documents. his experimental skill he was able Synthesen. vol 2, Stuttgart. 1 905 and It should be pointed out that the to do so. Thus his skill was in 1908; Moissan, Comptes Rendus. case Sabatier—Senderens is not iden• isolating the 'reagents' which can 1906; MacKenzie. Chemical News. tical to this of Grignard-Barbier. bear his name. However, Barbier 1907; Meyer-Jackobson, Lehrbuch Sabatier carried out his work with has the right to consider himself as der organische Chemische, 1907, Senderens and the whole idea and being the author of the principle of and certainly other authors of which trend of the research derived from the reaction. Grignard was not aware. Sabatier. In short—Senderens was Barbier points out that Grignard It would be difficult now to ask experimenting under the guidance of always recalls the part played by chemists to change the name of the Sabatier. In contrast, in the case Barbier in the discovery of the new reaction which has been accepted of Grignard-Barbier, the original reaction. Also a number of authors— for nearly 10 years. idea and first experiments belonged he says—mention Barbier next to Furthermore Grignard draws atten• to Barbier. Subsequently Barbier Grignard and some of them even tion to the fact that a few methods could claim much more rights mention Barbier only (Am. Chem. exist for using magnesium in organic for participating in the prize than J.. 1904. 31. 642). synthesis. He mentioned two of Senderens. (Senderens. a humble The author finishes his paper with them. catholic priest, never claimed such the words: The first is similar to Saytzeff a right, although his friend used reaction but of a much wider scope, to raise it and Sabatier always l'introduction du magnésium dans la it combines two different compounds loyally stressed the great contribu• synthèse organique est assez féconde pour in the presence of magnesium. This tion of Senderens to the work.) que chacun de nous ait le droit de revendi­ is the method of Barbier. It was Looking back at the problem quer la part qui lui revient et il me semble applied and perfected by a number of Grignard-Barbier one could say that qu'en toute équité, il conviendrait désormais authors such as Houben, Lespieu. d'associer nos deux noms pour désigner the reaction should from the begin• cette réaction.' Jaworsky, Pariselle, numerous chem• ning be called Barbier-Grignard Re• ists of the school of Reformatsky. action, but the magnesium organic 3. V. Grignard reacted to the Here allyl halogenides were used. reagent can be called Grignard re• above paper of Barbier in his note Zelinsky and Gutt, Schroeter, Dar- agent because it was isolated and Sur l'emploi du magnesium on zens. Rassow and Bauer, Ferrazio analysed by Grignard. chimie organique published in used esters of halogenated acids and So much can be said on the basis of Bulletin de la Société chimique de Sommelet used chloromethylic official documents. There are, how• France. 1910. 7, 453. ethers, etc. ever, some undocumented stories by Grignard says that in November The second method derived from co-workers and students of Grignard 1909 he left Lyon to Nancy which the work of Frankland, Wanklyn and and Barbier. It seems that Barbier delayed his reading the paper by Wagner. It is based on discovery of underestimated his discovery and Barbier published in the same journal, combination of mixed magnesium- importance of the reaction he des• p 206 on the use of magnesium in organic compounds {combinaisons cribed 1899. organic synthesis. organomegnésiennes mixtes) and An insufficiently informed reader application. Acknowledgements may think that Barbier's paper Grignard said that he could accept The author is much indebted to attacked Grignard, and may create the honour given to him by chemists Professor Jacques Dreux, Université a belief that he (Grignard) silently of calling only the second reaction Claude Bernard, Lyon, for supplying agreed with omitting the name of with his name (c'est pour celle-ci him with documents quoted in this his highly esteemed master, in the seulement que je puis acceptor present article. 192