Barbier-Grignard: explosive reaction - Warsaw University of ...

Barbier-Grignard: explosive reaction Tadeusz

Urbański

The early paper by P. Barbier (1898) and the thesis of V. Grignard (1901) led to the foundation of the 'Grignard reaction'. It follows, however, from existing documents, the discussion between Barbier and Grignard (1910) and a letter of Grignard (1912) that the reaction should more correctly be called 'Barbier-Grignard reaction' but that the reagent should be named the familiar 'Grignard reagent.' T h e r e is no d o u b t that G r i g n a r d is o n e of the best k n o w n n a m e s of great c h e m i s t - f o u n d e r s of present day chemistry. It o b v i o u s l y is d u e to the fact that every o r g a n i c c h e m i s t has carried out the G r i g n a r d - r e a c t i o n at least o n c e in their lifetime. For a l o n g t i m e the use o f the r e a c t i o n w a s l i m i t e d to l a b o r a t o r y /'e s m a l l s c a l e w o r k . H o w e v e r , in the late 30s a n d after W o r l d W a r 2 it penetrated into c h e m i c a l factories t h a n k s to (/) i m p r o v e m e n t in the d e s i g n of a i r - t i g h t reactors a n d (//*) i n t r o d u c ­ t i o n of less v o l a t i l e a n d relatively h i g h b o i l i n g p o i n t s o l v e n t s w i t h an ether f u n c t i o n s u c h as t e t r a h y d r o furane a n d d i o x a n e . T h e G r i g n a r d r e a c t i o n is n o w u s e d in c h e m i c a l i n d u s t r y in the p r o ­ d u c t i o n of s o m e fine c h e m i c a l s , d r u g s , s c e n t s etc. T h e i n c r e a s i n g i m p o r t a n c e of the r e a c t i o n c o m p e l s us to l o o k into the h i s t o r y of this remarkable a c h i e v e ­ m e n t w h i c h in 1 9 1 2 b r o u g h t the Nobel Prize to V i c t o r G r i g n a r d , professor at the U n i v e r s i t y of N a n c y . H e s h a r e d it w i t h a n o t h e r F r e n c h c h e m i s t — P a u l Sabatier, professor at the U n i v e r s i t y of T o u l o u s e who r e c e i v e d the N o b e l Prize for his c a t a l y t i c h y d r o g é n a t i o n of o r g a n i c compounds w h i c h he developed with Senderens. O n 9 D e c e m b e r 1 9 1 2 the F r e n c h j o u r n a l Salut Public p u b l i s h e d a note L'oevre d'un savant g i v i n g i n f o r m a ­ tion on Victor Grignard's Nobel Prize. T h e note i n v o k e d a s t r o n g re­ a c t i o n from P. Barbier, professor at the U n i v e r s i t y of Lyon, where Tadeusz Urbański is emeritus professor in the Chemical Faculty. Technical University, Warsaw. Poland. A member of the Polish Academy of Sciences, he has written over 500 papers, and one of his books Chemistry

and

technology

of explosives has been translated into several languages.

Grignard studied chemistry under Barbier a n d r e c e i v e d in 1901 his d e g r e e of Docteur ès sciences o n the basis of his thesis w h e r e he i n v e s t i ­ gated the use of m a g n e s i u m for o r g a n i c s y n t h e s i s o n the s u g g e s t i o n of Barbier. A f e w days later Barbier sent a letter to the e d i t o r of Salut Public. T h e letter c o n t a i n s s o m e s t a t e m e n t s important to the history of the r e a c t i o n . Here are m a i n parts o f the text:

1. T h e statement of B a r b i e r o n his prior use of m a g n e s i u m for s y n ­ thesis is w e l l d o c u m e n t e d b y his

paper—Comptes Rendus, 1 8 9 9 , 1 2 8 , 1 1 0 . Here h e d e s c r i b e d a m o d i f i c a t i o n of r e a c t i o n of Saytzeff (as he p o i n t e d out) b y r e p l a c i n g z i n c w i t h m a g ­ nesium. Starting from methylh e p t e n o n e he o b t a i n e d d i m e t h y l heptenol: CH

3

\ С = СН C H C H C O CH3 2

2

CH

3

An ether

CH

> СH3 I С = СН C H C H - C - 0 - M g I / I 3

I + Mg

СH3 \

2

Monsieur

le rédacteur en chef du Salut Public J'ai lu un peu tardivement dans le Salut Public du lundi 9 décembre l'article intitulé: 'L'oevre d'un savant.' Cet article relatif aux travaux de M, Grignard, exact dans son ensemble, renferme néanmoins une affirmation erronée évidemment involontaire qu'il m'est impossible de ne pas vous signaler. Je fais allusion à la phrase: 'La méthode nouvelle découverte par le jeune docteur . . .' qui attribue à M, Grignard un travail qui ne lui appartient aucunement. C'est moi qui, dans le courant de l'année 1899. ai institué cette nouvelle méthode de synthèse des matières organiques basée sur l'emploi du magnesium ainsi que le prouve mon mémoire aux Comptes rendus de l'Académie des Sciences, tome CXXXVIII, page 110 année 1899. L'oeuvre de Grignard a consisté à développer les conséquences normales de cette découverte qui m'appartient intégralement. Ce travail exécuté très brillamment a value à son auteur les récompenses et les faveurs que vous savez, ce dont j'ai été très heureux. Il n'entre pas dans mes vues de diminuer la valeur des recherches d'un de mes meilleurs élèves, mais la justice et la vérité exigent qu'il soit rendu à chacun ce que lui appartient. . . . . . . Je tiens à vôtre disposition les pièces qui en justifient la légitimité. Veuillez agréer. . . . 1—1 Professeur P. Barbier Faculté des Sciences de L yon

Here are a f e w facts w h i c h s h o u l d m a k e the B a r b i e r - G r i g n a r d p r o b l e m u n a m b i g u o u s l y clear.

+

/

CH

2

3

CH3

H 0 + H S0 2

2

CH3

4

CH3

\

I С = СН C H C H - C - 0 H + / I 2

СН 3

2

СHз

Mg (ОН) I In his paper he g i v e s a d e t a i l e d d e s c r i p t i o n of the p r o c e d u r e w h i c h is the s a m e as the c l a s s i c a l p r o c e d u r e of the G r i g n a r d r e a c t i o n . Barbier e n d s his paper w i t h a remark that he w a s able to carry out a n u m b e r of s y n t h e s i s by this m e t h o d a n d he intends to report t h e m in the future. T w o more papers of a p o l e m i c character are pertinent to the history of the r e a c t i o n . 2. Barbier published a note

'Sur l'origine de l'introduction du magnesium dans la synthèse organique' i n Bulletin de la Société chimique de France. 1 9 1 0 , 7, 2 0 6 . T h e a u t h o r d r a w s attention to the w r o n g t e n d e n c y , w h i c h c o u l d be s e e n in the current c h e m i c a l litera­ ture a n d e n c y o l o p a e d i c p u b l i c a t i o n s , in w h i c h the d i s c o v e r y of u s i n g m a g n e s i u m in o r g a n i c s y n t h e s i s is a s s i g n e d e x c l u s i v e l y to G r i g n a r d . T h i s is not justified as the a u t h o r had introduced magnesium into c h e m i c a l t e c h n i q u e for the first t i m e 191

for the synthesis of dimethylheptenol. After this i n t r o d u c t i o n Barbier repeated nearly a c o m p l e t e text o f his paper p u b l i s h e d 1 8 9 9 in

Comptes Rendus. H e a d d s that b y t h i s m e t h o d he also o b t a i n e d the secondary methylated alcohol d e r i v i n g from c i t r o n e l l a l . H e e x p l a i n s that he has not published the d e s c r i p t i o n of it. as at the t i m e he h a n d e d the w h o l e p r o b l e m to G r i g nard of r e p l a c i n g z i n c b y m a g n e s i u m in order to find w h e t h e r the r e a c t i o n with magnesium has a general c h a r a c t e r a n d w h e t h e r it is a d v a n t a g e o u s to replace z i n c b y m a g nesium. A d e t a i l e d d e s c r i p t i o n of the r e a c t i o n c a n be f o u n d ( a c c o r d i n g to Barbier) in the e x c e l l e n t thesis of G r i g n a r d p r e s e n t e d to the f a c u l t y o f s c i e n c e in L y o n . T h a n k s to his s u c c e s s G r i g n a r d b e c a m e , a n d is still, a c o - w o r k e r of Barbier. Grignard fully u s e d the opportunity offered to h i m by the p r o b l e m . His a i m w a s first to isolate m a g n e s i u m - o r g a n i c derivatives and then let t h e m react further. T h a n k s to his e x p e r i m e n t a l skill he w a s able to d o s o . T h u s his skill w a s in i s o l a t i n g the ' r e a g e n t s ' w h i c h c a n bear his n a m e . H o w e v e r , Barbier has the right to c o n s i d e r h i m s e l f as b e i n g the a u t h o r of the p r i n c i p l e of the r e a c t i o n . Barbier p o i n t s out that G r i g n a r d a l w a y s recalls the part p l a y e d by Barbier in the d i s c o v e r y of the n e w r e a c t i o n . A l s o a n u m b e r of a u t h o r s — he s a y s — m e n t i o n B a r b i e r next to G r i g n a r d a n d s o m e of t h e m e v e n m e n t i o n Barbier o n l y (Am. Chem. J.. 1 9 0 4 . 3 1 . 6 4 2 ) . T h e a u t h o r finishes his paper w i t h the w o r d s : l'introduction du magnésium dans la synthèse organique est assez féconde pour que chacun de nous ait le droit de revendi­ quer la part qui lui revient et il me semble qu'en toute équité, il conviendrait désormais d'associer nos deux noms pour désigner cette réaction.'

3. V . G r i g n a r d reacted to the a b o v e paper of Barbier in his n o t e

Sur l'emploi du magnesium on chimie organique p u b l i s h e d in Bulletin de la Société chimique de France. 1 9 1 0 . 7, 4 5 3 . G r i g n a r d says that in N o v e m b e r 1 9 0 9 he left L y o n to N a n c y w h i c h d e l a y e d his r e a d i n g the paper b y B a r b i e r p u b l i s h e d in the s a m e j o u r n a l , p 2 0 6 o n the use of m a g n e s i u m in organic synthesis. A n i n s u f f i c i e n t l y i n f o r m e d reader may think that Barbier's paper a t t a c k e d G r i g n a r d , a n d m a y create a belief that he ( G r i g n a r d ) s i l e n t l y a g r e e d w i t h o m i t t i n g the n a m e o f h i s h i g h l y e s t e e m e d master, in the 192

part w h i c h he p l a y e d in d e v e l o p i n g the n e w r e a c t i o n . A l t h o u g h Barbier himself does not b l a m e G r i g n a r d , it s e e m s w o r t h r e c a l l i n g all the d o c u m e n t s w h i c h referred to the p r o b l e m . G r i g n a r d p o i n t e d out m a n y times

{eg Thesis, Ann. /'Univ. Lyon, Ann Chem. Phys. 1901 ; Revue general Science, 1 9 0 3 ) the i m p o r t a n c e , both theoretical a n d p r a c t i c a l , of the s y n thesis by Barbier of d i m e t h y l h e p t e n o l ( i n c i d e n t a l l y S a n d a n d S i n g e r as w e l l

l'honneur que m'ont fait les chemists en attachant mon nom). G r i g n a r d also p o i n t e d out that the d e v e l o p m e n t of m i x e d m a g n e s i u m o r g a n i c c o m p o u n d s p r o d u c e d a great i m p a c t u p o n the d e v e l o p m e n t of mixed zinc organic compounds a c c o r d i n g to B e w a d a n d particularly to Blaise a n d his s c h o o l . 4. T h e last important d o c u m e n t is a h a n d - w r i t t e n letter of V . G r i g n a r d to his friend M e u n i e r ( 1 3 N o v e m b e r 1912).

as Harries a n d W e i l , Chemische Berichte, 1 9 0 2 a n d 1 9 0 4 respectively,

. . . /1 vrai dire et entre nous, j'aurais préféré, quitte à attendre encore un peu, voir partager le prix entre Sabatier et Senderens et le partager ensuite—moi тете avec Barbier, Mais que puit—je contre un tel verdict sinon m'en féliciter! A n u m b e r of authors d e s c r i b i n g Tu sera bien aimable de me donner the use of m a g n e s i u m in o r g a n i c ausitôtque tu le pourras quelques renseigne­ c h e m i s t r y also gave the true picture, ments sur l'état de la santé et sur l'état eg: Valeur, Bulletin des Sciences d'esprit de M, Barbier, Pharmaceutiques, 1902; Kiages. me demande comment il va prendre Chemiker Zeitung. 1 9 0 5 ; Waters, la Jechose. Mais s'il se considère comme American Chemical Journal, 1 9 0 5 ;frustré, je ne pense pas qu'il puisse m'en Schmidt, Ahrens' Sammlung, 1 9 0 5 ; rendre responsable. . . .'

d e s c r i b e d o n c e m o r e this a l c o h o l . E v i d e n t l y they had no k n o w l e d g e of the synthesis of B a r b i e r ) .

Die organischer Magnesium verbindungen und ihre Anwendung zu

T h u s speak the d o c u m e n t s . It s h o u l d be p o i n t e d out that the 1 9 0 8 ; M o i s s a n , Comptes Rendus. c a s e Sabatier—Senderens is not i d e n 1 9 0 6 ; M a c K e n z i e . Chemical News. tical to this of G r i g n a r d - B a r b i e r . 1 9 0 7 ; M e y e r - J a c k o b s o n , Lehrbuch Sabatier carried out his w o r k w i t h der organische Chemische, 1 9 0 7 , S e n d e r e n s a n d the w h o l e idea a n d a n d certainly other a u t h o r s of w h i c h trend of the research derived from G r i g n a r d w a s not a w a r e . Sabatier. In s h o r t — S e n d e r e n s was e x p e r i m e n t i n g under the g u i d a n c e of It w o u l d be difficult n o w to ask Sabatier. In contrast, in the c a s e c h e m i s t s to c h a n g e the n a m e of the of G r i g n a r d - B a r b i e r , the original reaction w h i c h has been a c c e p t e d idea a n d first experiments b e l o n g e d for nearly 1 0 years. to Barbier. Subsequently Barbier Furthermore G r i g n a r d d r a w s a t t e n could claim much more rights t i o n to the fact that a f e w m e t h o d s for p a r t i c i p a t i n g in the prize t h a n exist for u s i n g m a g n e s i u m in o r g a n i c Senderens. (Senderens. a humble synthesis. H e m e n t i o n e d t w o of c a t h o l i c priest, never c l a i m e d s u c h them. a right, a l t h o u g h his friend u s e d T h e first is similar to Saytzeff to raise it a n d Sabatier always reaction but of a m u c h w i d e r s c o p e , loyally stressed the great c o n tribuit c o m b i n e s t w o different c o m p o u n d s t i o n of S e n d e r e n s to the w o r k . ) in the p r e s e n c e of m a g n e s i u m . T h i s

Synthesen. v o l 2 , Stuttgart. 1 9 0 5 a n d

is the m e t h o d of Barbier. It w a s a p p l i e d a n d perfected by a n u m b e r of authors s u c h as H o u b e n , L e s p i e u . J a w o r s k y , Pariselle, n u m e r o u s c h e m ists of the s c h o o l of Reformatsky. Here allyl h a l o g e n i d e s w e r e u s e d . Z e l i n s k y a n d G u t t , Schroeter, Darz e n s . R a s s o w a n d Bauer, Ferrazio u s e d esters of h a l o g e n a t e d acids a n d Sommelet used chloromethylic ethers, etc. T h e s e c o n d m e t h o d derived from the w o r k of F r a n k l a n d , W a n k l y n a n d W a g n e r . It is b a s e d o n d i s c o v e r y of c o m b i n a t i o n of m i x e d m a g n e s i u m o r g a n i c c o m p o u n d s {combinaisons

organomegnésiennes

mixtes)

L o o k i n g b a c k at the problem G r i g n a r d - B a r b i e r o n e c o u l d say that the reaction s h o u l d from the b e g i n n i n g be c a l l e d B a r b i e r - G r i g n a r d R e a c t i o n , but the m a g n e s i u m o r g a n i c reagent c a n be c a l l e d G r i g n a r d reagent b e c a u s e it w a s isolated a n d a n a l y s e d by G r i g n a r d . S o m u c h c a n be said on the basis of official d o c u m e n t s . There are, h o w ever, s o m e u n d o c u m e n t e d stories by c o - w o r k e r s a n d s t u d e n t s of G r i g n a r d a n d Barbier. It s e e m s that Barbier underestimated his d i s c o v e r y a n d i m p o r t a n c e of the r e a c t i o n he d e s cribed 1899.

and

application. G r i g n a r d said that he c o u l d a c c e p t the h o n o u r g i v e n to h i m by c h e m i s t s of c a l l i n g o n l y the s e c o n d r e a c t i o n

Acknowledgements T h e author is m u c h i n d e b t e d to Professor J a c q u e s D r e u x , U n i v e r s i t é C l a u d e B e r n a r d , L y o n , for s u p p l y i n g w i t h his name (c'est pour celle-ci him w i t h d o c u m e n t s q u o t e d in this seulement que je puis acceptor present article.