Grignard, François Auguste Victor

(b. Cherbourg,. France, 6 May 1871; d. Lyons, France, 13 December 1935)

chemistry.

Grignard developed the reaction that became one of the most fruitful methods of synthesis in organic chemistry. The son of Marie Hébert and Théophile Henri Grignard, foreman and sailmaker at the marine arsenal, Grignard attended the lycée at Cherbourg, the École Normale Spéciale’ at Cluny, and the University of Lyons. After fulfilling his military service from 1892 to 1893, he completed his studies in mathematics at Lyons and, influenced by a classmate from Cluny, overcame his dislike of chemistry and became an assistant in the chemistry department. He soon began a long association with Philippe Antoine Barbier, the head of the department, who in 1898 investigated the conversion of an unsaturated ketone into the corresponding tertiary alcohol by using methyl iodide and magnesium instead of zinc as called for by the Saytzeff method. When Grignard was looking for a doctoral thesis topic, Barbier recommended that he take up the study of this variation on the Saytzeff reaction.

A survey of the literature on organomagnesium compounds convinced Grignard that such an intermediate compound was formed in Barbier’s reaction. He also learned of the difficulties other workers had experienced with organomagnesium compounds which ignite spontaneously in air or in carbon dioxide ide. He found, however, that E. Frankland in 1859 and J. Wanklyn in 1861 had solved a similar problem with zinc alkyls by keeping them in anhydrous ether. Adapting their method, Grignard treated magnesium turnings in anhydrous ether with methyl iodide at room temperature, preparing what came to be known as the Grignard reagent, which could be used for reaction with a ketone or an aldehyde without first being isolated. On hydrolyzing with dilute acid, the corresponding tertiary or secondary alcohol was produced in much better yield than Barbier had been able to obtain.

Grignard’s discovery was reported in a short paper at a meeting of the Académie des Sciences in May 1900. Although he was frequently opposed, Grignard held to the view throughout his life that the organomagnesium compounds he prepared had the formula RMgX and that in anhydrous ether they existed as the etherate which most likely had the formula (C₂ H₅)₂^O (R) MgX.

Grignard submitted his thesis on organomagnesium compounds and their applications in synthesis and received the doctor of physical sciences degree at Lyons on l8 July 1901. The complete thesis was published by the university, and within the year a full abstract appeared in Chemisches Zentralblatt. Grignard’s method of synthesis thus became widely known and firmly established. By 1908 more than 500 papers dealing with the Grignard reaction had been published. In his thesis Grignard described the preparation of carboxylic acids by the action of carbon dioxide on his reagent; secondary alcohols from aldehydes or formic esters; tertiary alcohols from ketones, esters, acid halides, or anhydrides; and unsaturated hydrocarbons in place of tertiary alcohols. He reported that alcohols react with organomagnesium compounds, as does water, to produce hydrocarbons and that aromatic bromides lead to products analogous to the aliphatic compounds.

Grignard was awarded the Cahours Prize of the Institut de France in 1901 and the Berthelot Medal in 1902. He became lecturer in chemistry at Besançon in 1905, returned to Lyons in 1906 and moved to Nancy in 1909 where he became professor of organic chemistry in 1910. That year he married Augustine Marie Boulant, and Roger, the first of two children, was born in 1911.

In November 1912 the Nobel Prize for chemistry was awarded jointly to Grignard, for his 1900 discovery of the role or organomagnesium compounds in synthesis, and Paul Sabatier, for his discoveries in catalytic hydrogenation made fifteen years earlier. Continuing his research on organomagnesium compounds, Grignard investigated their reactions with epoxides, glycols, and with cyanogen to produce nitriles. In army service from 1914 to 1919 he worked primarily on toluene production and war gases. He succeeded Barbier at Lyons in the fall of 1919, remaining there the rest of his life.

In addition to his organometallic researches, Grignard investigated terpenes; structure determination by ozonization; the condensation of carbonyls; and the cracking, hydrogenation, and dehydrogenation of hydrocarbons.

In recognition of his monumental contributions to chemistry, Grignard was a member or honorary member in the world’s major chemical and scientific societies. Honorary doctorates were conferred on him by Louvain in 1927, Brussels in 1930, and an honorary professorship by Nancy in 1931.

BIBLIOGRAPHY

I. Original Works. Grignard announced the discovery of his method of synthesis in “Sur quelques nouvelles combinaions organométatliques du magnésium et leur application è des synthéses d’alcools et d’hydrocarbures,” in Comptes rendus de l’Académie des sciences, 126 (1898), 1322. His doctoral thesis, “Sur les combinaisons organomagnésiennes mixtes et leur application à des synthèses d’acides, d’alcools et d’hydrocarbures,” in Annales de l’Université de Lyon, 6 (1901), 1–116, was also published in Paris later in 1901. Toward the end of his life Grignard began editing a handbook, Traité de chimie organique, 23 vols. (Paris, 1935–1954), and his son, Roger, in collaboration with Jean Cologne published his lectures as Précis de chimie organique (Paris, 1937).

Lists of Grignard’s publications, positions, and honors appear in Charles Courtot, “Notice sur la vie et les travaux de Victor Grignard (1871-1935),” in Bulletin, Société chimique de France, 5 , no. 3 (1936), 1433-1472. A collection of addresses by and about Grignard was published by A. Rey, Victor Grignard (In Memoriam) (Lyons, 1936).

II. Secondary Literature. Biographical details and evaluations of Grignard’s work are given by Charles Courtot in his paper listed above; Henry Gilman, “Victor Grignard,” in Journal of the American Chemical Society, 59 (1937), 17-19; and Heinrich Rheinboldt, “Fifty Years of the Grignard Reaction,” in Journal of Chemical Education, 27 (1950), 476-488. For a more recent treatment of the Grignard reaction see Rudolph M. Salinger, “The Structure of the Grignard Reagent and the Mechanism of Its Reactions,” in Arthur F. Scott, ed., Survey of Progress in Chemistry (New York. 1963), pp. 301–324.

A. Albert Baker, Jr.