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Victor Grignard Ancestor of Organic Synthesis: Victor Grignard was a brilliant French chemist who became famous at age 29 for the discovery of the organomagnesium halides and their versatility in chemical synthesis. (Feature/Chronique).

Francois Auguste Victor Grignard was born in Cherbourg, France on May 6, 1871. He was the son of a foreman and sailmaker who worked at the nearby marine arsenal [1]. The young Grignard attended the local Ecole primaire and then the College de Cherbourg, which became a Lycee during his time there. He was a conscientious, hard-working student characterized by modesty and a friendly disposition, and had a great talent for mathematics. His superior intelligence enabled him to win the Prix d'excellence each year from 1883 to 1887, and he graduated bachelier de l'enseignement special in 1887 [2].

Grignard passed the entrance examination for the Ecole Normale Speciale de Cluny, a preparatory school for secondary level teachers, in 1889, and was there for two years until that institution closed. He, along with other scholarship students, was then transferred to the Faculte des Sciences in Lyon, where he studied for the Licence es sciences mathematiques; but at first failed. Grignard then completed one year of military service and in 1893 returned to the Faculte des Sciences in Lyon to try again for the Licensiate in mathematics [2]. He was successful in this endeavour in 1894, and then had to earn a living. Although initially not favourably impressed with chemistry, due in part to Marcellin Berthelot's resistance to the application of the atomic theory [3], he was persuaded to accept the post of preparateur-adjoint in general chemistry in the Faculte des Sciences in Lyon, which he took up on December 1, 1894. There, he worked closely with Professors Louis Bouveault (1864-1909) and Francois Philippe Anto ine Barbier (1848-1922) [4]. In 1898, Grignard became Chef des travaux pratiques en chimie generale. In the same year, he obtained a Licence es sciences physiques, and published his first research paper with Barbier.

In 1905, Grignard was appointed maitre de conferences de chimie appliquee at the Universite de Besancon, but stayed there for only 12 months before returning to Lyon as maitre de conferences de chimie generale in the service of his mentor Barbier. Three years later he attained the rank of professeur adjoint, but, alas, there were no possibilities for further advancement in Lyon. Between 1908 and 1909, faculty positions opened up in Toulouse, Rennes, and Paris; however, Grignard was passed over for these. Then, in November 1909, he was appointed Charge de Cours de Chimie Organique in the Faculte des Sciences at the Universite de Nancy, where just one year later, and while not yet 40 years old, he was promoted to professeur titulaire [2]. In 1912, Grignard received the Nobel Prize in Chemistry for his outstanding research work on organomagnesium compounds.

In World War I (1914-1918), Victor Grignard served France initially in the army and then as a research scientist who made important contributions (see later). At the end of the war, he returned to his post at the Universite de Nancy, and later on twice turned down offers of chairs of studies at the College de France in Paris. However, within six months Barbier retired and Grignard was invited to replace him. He accepted the offer and became professeur de chimie generale in Lyon. In 1921, Grignard was named Directeur de l'Ecole de Chimie Industrielle, and eight years later was appointed Dean of the Faculte des Sciences, a demanding position that he was to occupy until his death on December 13, 1935. Unfortunately, these increasing administrative duties eventually made it impossible for him to personally carry out research work.

Organomagnesium Halides and the Nobel Prize

In 1898, at the Universite de Lyon, Barbier had tried, unsuccessfully, to synthesize dimethylheptenol from methylheptenone by reaction with zinc and methyl iodide, and decided to substitute magnesium for zinc. This change brought about some positive results, but the yields of the desired product were low. Barbier then suggested to Grignard that he pursue this line of research for a doctoral dissertation [5]. In subsequent work, Grignard heated a mixture of magnesium turnings and isobutyl iodide and added dry ethyl ether, which gave rise to rapid reaction together with dissolution of the metal. The resulting ethereal solution containing, according to Grignard, RMgI was found to react with benzaldehyde to give phenylisobutylcarbinol in excellent yield [1]. Trials using organic bromides and iodides with other aldehydes and also ketones, produced the corresponding secondary and tertiary alcohols in equally good yields. Grignard found that these reactions took place readily at room temperature and under ordinary p ressure. Using the same method, he later prepared alcohols from esters, unsaturated hydrocarbons from tertiary alcohols, and carboxylic acids by reaction with carbon dioxide. Thus, Grignard had discovered a rapid and highly versatile method for the synthesis of numerous organic compounds of different types and in high yields, which would be widely exploited [6].

On May 14, 1900, Henri Moissan (1852-1907, Nobel laureate 1906) presented to the Academie des Sciences a note having Victor Grignard as sole author and entitled 'Sur quelques nouvelles combinaisons organometalliques du magnesium et leur application a des syntheses d'alcools et d'hydrocarbures.' This first announcement of Grignard's successful research was published in the Comptes Rendus of the Academie [7], and the work was quickly noticed by organic chemists, some of whom even tried to claim the discovery! Fortunately, Moissan and Marcellin Berthelot (1827-1907) supported Grignard and encouraged him to continue his research as rapidly as possible [2]. Indeed, Grignard ended his note with the revealing sentence, "Je poursuis l'etude des applications de ces nouveaux composes organometalliques" [7]. On July 18, 1900, he defended his doctoral thesis in the Faculte des Sciences, Universite de Lyon, before a jury presided over by professor Barbier. Grignard received his Docteur es sciences physiques degree in 1901 , and in the same year published a series of detailed papers on his research [8].

Such was the importance of Grignard's discovery that his name soon became very well-known, and even entered the French language in terms like 'Grignardisation; 'Un Grignard; un derive magnesien' [9]; 'Reactif de Grignard,' 'Reaction de Grignard; 'faire un Grignard' [10]. Professor Georges Urbain (1872-1938) neatly summed up the significance of the accomplishment in the following statement:

"La 'Reaction de Grignard' circule dans la Chimie organique tout entiere comme le sang dans l'organisme, Elle l'a vivifiee. Et tous les chimistes organiciens grignardent a qui mieux mieux" [2]. The great impact of the discovery of the organomagnesium halildes and their synthetic value is clearly shown by the statistics given in Table 1.

The 1912 Nobel Prize for Chemistry was announced on November 13 and the news appeared in the morning editions of newspapers. However, Grignard did not learn of his award until colleagues informed him of it when he entered his laboratory! He was surprised at such early recognition since he was only 41 years old, although Ernest Rutherford (1871-1937) had received the Nobel Prize for Chemistry in 1908 at age 37. He thought that the Prize should have been awarded firstly to his compatriots Paul Sabatier (1854-1941) and Jean-Baptiste Senderens (1856-1936), for their research on catalytic hydrogenation, and then subsequently to himself and professor Barbier [4]. After some initial frustration at being excluded from the honour, Philippe Barbier, who after all had started the study on organomagnesium compounds [11], bore no ill- will toward Grignard, and in fact the two remained on good terms.

After the announcement of the Nobel Prize, Grignard was showered with congratulatory messages from colleagues around the world, and particularly from many in his own country, including professors Albin Haller and Georges Urbain (Universite de Paris, Sorbonne), as well as Paul Sabatier (Universite de Toulouse), co-recipient of the 1912 Prize. Just before Grignard left France in the company of Paul Sabatier to journey to Sweden to receive the Nobel Prize, it was realized that he had not yet been awarded his country's highest recognition, namely, the Legion d'Honneur! Pressure was immediately brought to bear on the appropriate authorities, and on December 5, by presidential decree, Grignard was made Chevalier in the National Order. He learned of this late decision on arrival in Stockholm on December 8, only two days before the Nobel Prize ceremonies were to take place [2].

Service in the First World War

At the beginning of World War I in 1914, Grignard was mobilized, recalled to the colours with the rank of corporal, and then ordered to guard a railway bridge near Cherbourg! In that capacity he served with the 77th Regiment Territorial and was then assigned to the Laboratoire de Chimie de la Marine in Cherbourg, where he was called upon to carry out routine tests and analyses. He also did some work on petroleum cracking in his own laboratory in Nancy (1). Fortunately, through the influence of colleagues who knew that Grignard could better serve the war effort, in July 1915 he was assigned to the Direction du Materiel Chimique de Guerre in Paris, by the Ministere de la Guerre, and joined the Laboratoire des Services Techniques de I'Artillerie, whose director was Urbain. Thus began more than three years of war work of a scientific nature at the Sorbonne (2).

In Paris, Grignard directed, with his usual zeal, the research activities of a small group of devoted colleagues who were called upon to tackle a wide range of important problems. The main mission was to provide counter-measures against war gases used by the enemy and to determine their composition and method of manufacture. Grignard was expected to furnish rapid solutions to all problems referred to him by the Service Central des Etudes et Experiences Chimiques de Guerre. Very soon after the first use of gas by the Germans at Ypres the chemical substance involved was identified by Grignard's group as dichloroethyl sulphide (yperite or mustard gas) and its method of preparation was deduced. A small apparatus for the detection of low quantities of mustard gas was also devised and proved to be highly effective on the battlefields (2, 4). Chemical products withdrawn from the tanks of flame-throwers employed by the Germans were analyzed. Substances such as phosgene, N-ethyl carbazole, and hexanitrodiphenylamine a lso underwent analysis, and synthetic work included the preparation of tetranitromethane, nitrophenols (from benzene), trinitrophenylnitramine, 2,4,6-trinitrobenzene, and organic perchlorates. In addition, the decomposition of petroleum hydrocarbons using aluminium chloride, so as to obtain aviation gasoline, was studied.

Besides his task as director of a research group, Grignard became a member of the Tardieu Mission which twice journeyed to the United States (1917, 1918) to seek cooperation in research and the production of explosives and other war materials (1). During these trips, he visited some important industrial plants and returned to France with a considerable amount of information of use in the struggle against Germany. While overseas, Grignard met many academic colleagues and industrialists. In New York in 1917, he attended a banquet at the Chemist's Club, during which he received the Diploma of Club Member in honour of the 'mission scientifique francasie (2). He also addressed the Mellon Institute on the subject of war industries and the links between science and industry, while stressing the great need for collaboration.

Other Research Activities and Publications

Starting in 1905 Grignard worked for several years with Barbier on the chemistry of terpenes and their efforts led to a series of publications. After World War I and the return to the Universite de Lyon, following his brief stay in Nancy, he was involved in other research areas, such as condensation reactions of aldehydes and ketones, catalytic hydrogenation and dehydrogenation under reduced pressure, and quantitative ozonolysis. As well as producing many papers relating to these themes, Grignard published important works on chemical nomenclature (4).

In 1930, Grignard accepted an invitation from Masson et Cie publishers of Paris to act as editor of a handbook of organic chemistry (Traite de chimie organique), which turned out to be a daunting task involving 100 collaborators (2). Volume I, which appeared in 1935, was assembled by Grignard and nine colleagues, and included the following topics: organic analysis, crystalline and colloidal states, open and closed chains, functional groups, isomers, and nomenclature. This volume also contained a history of organic chemistry written by Grignard (11). Before his death In late 1935, Grignard witnessed the appearance of Volumes I and III and also authorized the proofs of Volumes II and IV. This massive publication endeavour, which eventually ran to 23 volumes, was completed under the direction of colleagues Georges Dupont and Rene Locquin; the final volume was published in 1954.

Contributions to Teaching

Victor Grignard was a demanding and kind professor who taught chemistry in each of the three universities previously mentioned here. As late as 1933, and while bearing the burden of his multiple duties as Director of l'Ecole de Chimie Industrielle and Dean of the Faculte des Sciences in Lyon, he still taught organic chemistry to four classes each week the year round (2). His lectures were usually accompanied by interesting experimental demonstrations, and also contained historical references.

In 1937, Grignard's son Roger, also a chemist, in collaboration with Jean Colonge, one of Victor Grignard's former students, published his father's organic chemistry course notes in the form of a 746-page volume entitled Precis de Chimie Organique. An updated fourth edition of this work appeared in 1958 (2).

Interestingly, even Grignard's laboratory research notebook has become a source of inspiration for teaching and learning purposes. Annually, students attending l'Institut National des Sciences Appliquees de Lyon have been provided with a copy of page 103, which records the first observation of the formation of an alkylmagnesium halide; so as to be able to study it and appreciate the detailed content, as well as the need to follow precise procedures (12).

Honours and Recognition

Before and after the attribution of the 1912 Nobel Prize for Chemistry, Victor Grignard received many honours. A number of these distinctions are listed in chronological order in Table 2. Scientific societies in the United States, the United Kingdom, Sweden, and Belgium honoured him. During the 1920s, societies in Romania, Poland, and Holland followed suit. In 1927, Honorary doctorates were bestowed on Grignard by l'Universite de Louvain and l'Universite libre de Bruxelles.

The street in Cherbourg where Grignard was born, rue des Carrieres, was renamed 'rue Victor-Grignard, Prix Nobel, 1871-1935', and in 1937 the Lycee de Cherbourg became 'Lycee Victor Grignard.' In May 1950, the fiftieth anniversary of the presentation of the famous research note before the Academie des Sciences was celebrated in Lyon.

The year 1971 was marked by impressive manifestations highlighting the birth of Victor Grignard. The Societe Chimique de France held a prestigious conference entitled 'Centenaire Victor-Grignard' in May at the Faculte des Sciences de Lyon (12). The centenary of Grignard's birth was also celebrated in other countries, including Spain, Belgium, and the United States. The Fifth International Conference on Organometallic Chemistry, held in Moscow, August 16- 21, 1971, was dedicated to Victor Grignard. The same year, a commemorative French postage stamp with the citation "1871 Victor Grignard 1935, Prix Nobel de Chimie 1912, RMgX organomagnesiens" went on sale in Lyon and Cherbourg. It shows Grignard, his chemical apparatus, and the Nobel Medal. Grignard also appears, together with Paul Sabatier, on a Swedish postage stamp that commemorates their shared Nobel Prize.

Conclusion

Victor Grignard's greatest contribution to chemistry was most certainly his discovery of the organomagnesium halides and their use in synthesis. The importance of this achievement has been ranked with that of the Diels-Alder reaction (diene synthesis) for which the 1950 Nobel Prize for Chemistry was awarded (6). Grignard's works in organic synthesis have also been favourably compared to those of his countrymen Charles Friedel (1832-1899), Jean-Baptiste Senderens and Paul Sabatier (1,4).

Grignard will also be remembered as the dynamic director of highly successful chemical research laboratories in both Nancy and Lyon, where he mentored many doctoral candidates.

Acknowledgements

Sincere thanks are expressed to Roger Grignard for the gift of a signed copy of his award- winning book, "Ouvrage couronne par l'Institut -- Prix Claude-Berthault" (see Ref. 2), as well as two unused 1971 French commemorative postage stamps.

Brian Newbold, FCIC, is emeritus professor of chemistry at the Universite de Moncton, where he still teaches an organic chemistry course and remains active in historical research. He served as the founding editor of the journal Canadian Chemical Education from 1965 to 1975, and has been a member of the editorial board of The Journal of Chemical Software since 1995.

References

(1.) James, L.K., Ed., Nobel Laureates in Chemistry 1901-1992, History of Modern Chemical Sciences, American Chemical Society & The Chemical Heritage Foundation, USA, pp. 83-87, 1993.

(2.) Grignard, R., Centenaire de la naissance de Victor Grignard (1871-1971), Audin, Lyon, France, 1972.

(3.) Newbold, B.T., 'Pierre Eugene Marcellin Berthelot: An Illustrious Pioneering French Chemist,' ACCN, 51(2):27, 1999.

(4.) Hodson, D., 'Victor Grignard (1871-1935); Chem. in Brit., 23(2):141-142, 1987.

(5.) Farber, E., The Evolution of Chemistry, 2nd ed., The Ronald Press Co., New York, NY, p. 346, 1969.

(6.) Leicester, H.M., Source Book in Chemistry 1900-1950, Harvard University Press, Cambridge, MA, pp. 254-256, 1968.

(7.) Grignard, V., 'Sur quelques nouvelles combinaisons organometalliques du magnesium et leur application a des syntheses d'alcools et d'hydrocarbures,' Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 130:1322-1324, 1900.

(8.) Grignard, V., 'Combinaisons organomagnesiennes mixtes et leur application a la synthese d'acides, d'alcools et d'hydrocarbures,' Ann. Chim., 24:433-490, 1901.

(9.) Dictionnaire Usuel, Editeurs Quillet-Flammarion, Paris, France, p. 638, 1960.

(10.) Arnaud, P., Cours de chimie organique, Gauthier-Villars, Paris, France, p. 209, 1983.

(11.) Partington, J.R., A History of Chemistry, Vol. 4, Macmillan & Co. Ltd., New York, NY, pp. 857-858, 1964.

(12.) Latreille, H. and M. Chavance, 'An Excellent Laboratory Notebook,' J. Chem. Educ., 48:846, 1971.
Table 1

Growth in the number of research. papers relating to organomagnesium
halides (1,2,4).

Year Number of Papers

1905 200
1908 500
1912 700
1914 900
1926 1,800
1950 4,000
1972 10,000+
Table 2.

Some honours received by Victor Grignard.

Year Honour

1901 Shared Prix Cahours (Academie des Sciences)
1902 Shared Prix Cahours (Academie des Sciences)
1902 Medaille Berthelot (Academie des Sciences)
1905 President Section de chimie, Association francaise pour
 I'avancement des sciences)
1906 Prix Jecker Academie des Sciences)
1909 Elected Member Royal Society of Sciences, Sweden)
1912 Shared Nobel Prize for Chemistry
1912 Made Chevalier, I'Ordre National de la Legion d'Honneur
1913 Medaille Lavoisier (Societe Chimique de France)
1913 Membre correspondant de chimie (Academie des Sciences)
1917 Honorary Member (American Chemical Society)
1918 Honorary Member (Mellon Institute, USA)
1918 Honorary Member (Chemist's Club, New York, NY)
1920 Honorary Member (Chemical Society of London)
1920 Membre d'Honneur (Societe Chimique de Belgique)
1926 Membre de I'Institut de France
1927 Membre d'Honneur (Societe de Chimie Industrielle de France)
1929 Membre d'Honneur (Societe Chimique de France)
1933 Promoted to Commandeur, I'Ordre National de la Legion d'Honneur
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Publication:Canadian Chemical News
Date:Oct 1, 2001
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