Chichibabin, Alexei Yevgenievich

(b. Kuzemino Poltava gubernia [now Ukrainian SSR], Russia, 29 March 1871; d. Paris, France, 15 August (1945),

chemistry

Chichibabin, the son of a lower-echelon government employee, graduated from Moscow University in 1892. From his first year there he studied under Markovnikov, investigaing the reducion of propylbenzene with hydrogen iodide. After graduation he investigated privately, under the direction of M. I. Konovalov, the nitration of alkylpyridines and from then on concentraed his research on pyridine. In 1905–1906, he was assistant professor at the University of Warsaw, and from 1909 to 1930 full professor of chemistry at Moscow Higher technical School. From 1918 to 1923 he was also professor at the University of Moscow. In 1930, after the death of his only daughter in a chemical accident, he moved to Paris, where he worked in the organic chemistry laboratory at the College de France. His fundamental textbook, Osnovnye nachala organicheskoy khimii, has gone through seven editions since 1924 and has ben translated into English, French, spanish, Czech, Slovak, Hungarian, and Chinese.

After the beginning of World War I, Chichibabin organized the production of pharmaceuticals in Russia; he was reponsible for the construction of the first Russian alkaloid plant and the production of opium, morphine, codeine, atropin, cocaine, caffine, aspirin, phenyl salicylate, and phenacetin.

In 1926 Chichibabin was the first Soviet chemist to receive the Lenin Prize, for his work with pyridines and in pharmaceutical chemistry.

Chichibabin studied naphthenic acids in Caucasian oil (he was the first to find aliphatic acids in this oil). He also worked on phenol alkylation; established the structure of musk ketone and found a new synthesis of amber musk; discovered the synthesis of thiodiglycol by the action of hydrogen sulfide on ethylene oxide; synthesized pilocarpine and santonin. In other areas of chemistry Chichibabin showed that under certain conditions organo-magnesium compounds can react with ortho esters, acetals, and even ethers. He was also concerned with triphenylmethane compounds and the theoretical problems connected with them. To explain the special properties of triarylmethyls, Chichibabin developed the concept of trivalent carbon and even attempted to explain olefins by means of it.

In pyridine chemistry, the field in which he did his most notable work, Chichibabin investigated the rearrangment of 1-benzylpyridine salts and found that they can regroup-with the benzyl radical occupying not only positions 2 and 4, previously believed, but also position 3. His studides of the reaction of aldhyde and acetylne with ammonia led to new methods of synthesizing pyridine or alkylpyridine with the alkyl group in any position. Most important is the synthesis from acetaldehyde and ammonia of 2-methyl-5-ethyl-pyridine, used for the preparation of 5-methyl-5-vinylpyridine (for copolymerization with styrine). Important methods of synthesizing furan, pyrrole, and thiphene from acetylene were also devised.

In 1913 chichibabin and seide discovered that a hydrogen atom in position 2 or 4 of the pyridine nucleus can be directly substituted for an amino group. Later Chichibabin showed that the same was true of a hydroxyl radical. The direct amination, now known as the Chichibabin reaction, is applied to industrial preparation of 2-aminopyridine from pyridine. A study of the Chichibabin amination was extended to different pyridines, natural nicotine, and compounds of the quinoline and isoquinoline series.

Chichibabin investigated the laws governing the introduction of a second substituent into aminopyridines. A new type of amino-imino tautomerism was discovered in aminopyridines and it was shown that, depending on condiktions, alkylation can attack the amino group or the hetero-nitrogen atom. In its reactions with difunctional compounds 2-aminopyridine reacts as an amidine, forming condensed bicyclical structures.

BIBLIOGRAPHY

1.Original Works. Chichibabin’s books include Issledovania po voprosu o rekhualentnom uglerode i stroenii prosteyshikh okrashennykh proizuodnykh trifenilmentana(“Study on Trivalent Carbon and on the Structure of the Simplest Colored Triphenylmethane Derivatives"; Moscow,1912) and Osnovnye nachala organicheskoy khimii (“Basic Principles of Organic Chemistry"; Moscow, 1925). A few of his more than 350 papers are “Novy obshchy method for Preparing Aldehydes";), in Zhurnal Russkago fiziko-khimich-eskago obshchestva, 35 (1903), 1284–1286; “Sintezy piridinovykh osnovany iz aldegidov predelnogo ryada i ammiaka” (“Synthesis of Pyridine Bases from Aldehydes of the Saturated Series and Ammonia”) ibid., 37 (1905), 1229–1253; “Novaya reaktsia soedineny, soderzhashchikh piridinovoe yadro” (“New Reactions of Compounds Containing a Pyridine Nucleus”) uvud, 46 (1914), 1216–1236; “Tautomeria a-aminopiridina” (“Tautomerism of a-aminopyridine”), in Berichte der Deutschen chemische Gesellschaft, 57 (1924), 1168–1172, and in Zhurnal Russkago fiziko-khimicheskago obshchestua, 57 (1925), 299–425; “Sintez pilopovykh kislot i stroenie pilokarpina” (“Synthesis of pilopic Acids and structure of Piocarpine”), in Doklady Akademii nauk SSS, 2 (1930), 25–32; Berichte der Deutschen chemische Gesellschaft, 63 (1930), 460–470; and “Heterocycles hezatomiques avec un atome d’azote. groupes de la pyridine et de la piperidine,” in v. Grignard, ed., Traite de chimie organique, vol. xx (paris, 1953), 33–375.

II. Secondary Literature. On Chichibabin or his work, see M. Delépine, “Hommage de la Société chimique de France a Alexis Tchitchibabine (1871–1945),” in Bulletin de la Société chimique de france (1958), p. 407; Y. S. Musabekov, Istoria organicheskogo sinteza v Rossii (“History of Organic Synthesis in Russia"; Moscow, 1958), which contains material on Chichibabin’s scientific activities; and P. M. Yevteeva, in Trudy Instituta istorii estestuoznaniya i tekhniki (“Transactions of the Institute of Natural Sciences and technological History”), 18 (1958), 296–356, a biography and review of Chichibabin’s scientific work, with a list of 346 writings.

A. N. Kost