The University of Kazan-Provincial Cradle of Russian Organic Chemistry Part II: Aleksandr Zaitsev and his Students David E. Lewis South Dakota State University, Box 2202, Brookings, SD 57007 With the departure of Markovnikov, the chair of organic chemistry and the direction of the chemistry school a t the University of Kazan passed to Aleksandr Mikhailovich Zaitsev, of whom Butlerov had written to the dean of the faculty in 1869, "Based on the results of his work, A. M. Zaitsev occupies one of the first places among young Russian chemists who do not yet have a n academic position. . Like h i s mentor, Butlerov, a n d his contemporary, Markovnikov, Zaitsev was the mentor of several important organic chemists, including Reformatsky, Wagner, and Arbuzov. But, unlike many of his contemporaries (e. g., Markovnikov and Demyanov), Zaitsev did not receive early recognition for his work (even as recently a s the 1960's, few textbooks in organic chemistry bothered to put his name on SaytzefT's rule, and his contributions to the development of chemistry in Russia were overshadowed, perhaps unfairly so, by those of Markovnikov). In part, this may be
Figure 1. A. M. Zaitsev (1841-1910).
due to the fact that he spent his entire career a t Kazan, rather than moving to Moscow or St. Petersburg. A. M. Zaitsev Zaitsev was born to a mercantile family, and his father wanted him to follow in his footsteps. However, Zaitseds maternal uncle, the astronomer Mikhail Lyapnbov, convinced his brother-in-law that Zaitsev should enter the university, and personally taught his nephew the Latin required to enter the study of law. Zaitsev graduated from the University of Kazan in 1862 with a degree in law, although the two years of chemistry required (taught by Butlerov) so captivated him that he decided upon chemistry rather than law a s a career. Immediately following his graduation, he broke with tradition by going abroad to study chemistry before completing his dissertation for the degree of kandidat. His first stop abroad was a t the University of Marburg, where he studied under Hermann Kolbe. I n 1863 he also submitted his kandidat's dissertation (on Kolbe's structural theory) to the Upiversity of Kazan. The degree was not awarded. At Marburg, he began work with the chemistry of organic sulfides that led to his discovery of the sulfoxides (I). In August 1864, he travelled to Paris, where h e spent nine months in the laboratories ofAldolphe Wurtz, studying the nitration of aromatics and the chemistry of cyanoacetic ester (2).He returned to Marburg in May 1865, where he continued his work with organic sulfides. However, when Kolbe accepted the chair of chemistry a t Leipzig, Zaitsev chose to return to Kazan. I n 1866 h e did send his published papers to the University of Leipzig in the form of a dissertation and, thanks to Kolbe's support, he was awarded his PhD by that university. On his return to Kazan, Zaitsev first worked a s a n unpaid laboratory assistant for Butlerov. As soon as he had obtained his kandidat degree, Butlerov secured a junior position for him on the faculty a s a laboratory technologist in agronomic chemistry, although it was fairly obvious that he would assume a position in the chemistry department a s soon a s one became available. His Kandidat's and Master's dissertations a t Kazan were presented in 1865 and 1867. Both clearly showed the influence of his time with Kolbe. They described chemistry of thioethers and their reactions with nitric acid (the first report of the preparation of sulfoxides, ( 1 ) and methyl iodide (3). He presented his doctoral dissertation on the transformations of alcohols in 1870.
As a student of Kolbe and Butlerov, Zaitsev had been exposed to modern chemical theory, so that he should have Volume 71 Number 2 February 1994
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found in Markovnikov a kindred spirit. Scientifically, he did so, but this was not the case socially. Initially, Markovnikov had little regard for his fellow student, possiblv because of his break with tradition bv studvine in ~ e i m a n ybefore submitting his kandidat'sdissekacon, possibly because of his obtaining a foreign PhD degree, or possibly because of Zaitsev's social and scientific conservatism. Where Markovnikov was progressive'in his social views, Zaitsev was equally conservative. hideed, it may well have been his conservative views that gained for him the strong support of the dean of the facultywhen Zaitsev was first proposed for a chair in chemistry. Zaitsev's independent research program after his return to Russia reflected the influence of Butlerov on Russian chemistrv a t this time. Zaitsev remained true to the course set by his mentor (Russian sources speak of the "BntlerovZaitsev school"), and he attracted many of the finest young chemists in Russia. Thus, many of Zaitsev's papers concerned the develo~mentof svnthetic methods based unon the reactions of zihc alkyls &th carbonyl compounds. +he synthesis of tertiary alcohols had been one of Butlerov's early triumphs. With his student Egor Egorevich Vagner, Zaitsev developed a general method for the synthesis of secondary alcohols from aldehydes and zinc alkyls (4).
(%CH,)?n
+CHO
(Vagner. Zaitsev. 1875) OH
Zaitsev was a productive worker. In addition to his discovery of the sulfoxides, he reported the first preparation of butvrolactone (5).However. it was his naner . . (~ublished . under thc German apellingofhis name, Saytrrm in Jtrsfus I . i e h i r s h n o l e n der Chemie in 1875 161that has led to his endukng fame in sophomore organic chemistry textbooks. In 1885. he became a corresnondine member of the Academy of Science, and in 1903 Le wasappointed an honorary member of the faculty of Kiev University, possibly at the urging of his student Aleksandr Nikolaevich Reformatsky, who was professor of chemistry at Moscow University and who probably influenced his more famous brother, Sergei the nomination. Nikolaevich, to support .. Although Markovnikov's departure had left a large - gap - . in the ch&stry research at Kazan, Zaitsev's research uoup continued the Kazan tradition of attracting some of thefinest minds of the next generation. Among these were Sergei Nikolayevich Reformatskii (or Reformatsky), Egor Egorevich Vagner (better known under the German spelling of his name, Wagner), and Aleksandr ErminingeldovichArbuzov. E. E. Vagner Eeor Eeorevich Vamer (1849-1903) was one of the fouiders i f the field ofierpeue chemistry Like his mentor before him, Vagner began his studies a t the University of Kazan as a student in law (1867-1868), where he heard chemistrv lectures bv both Markovnikov and Zaitsev. ARer two years in the st& of law, he transferred to the Physics-Mathematics Department, where he carried out research under ~aitsev(4b).Among his papers was a method for the synthesis of secondary alcohols by the reaction between aidehvdes and zinc alkvls Vagner graduated from Kazan in 1874, and he became an instructor there. In 1875 he was sent to St. Petersburg, where he continued his synthesis of secondaly alcohols under the direction of Butlerov. In 1876, he became a laboratory assistant in analytical chemistry under Menshutkin, and in 1882he moved to Novo-Aleksandr Agricultural Institute in Poland a s professor of chemistry. Here he
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began work on his master's dissertation, which he submitted to the University of St. Petersburg in 1885. In 1886, he moved to the University of Warsaw, where he spent the remainder of his career. He submitted his doctoral dissertation to the University of Warsaw in 1888. During his first independent position, Vagner developed permanganate oxidation of olefins to glycols (7) as a means for locating the position of double bonds in terpenoid hydrocarbons. This work rendered tractable the problems in structure determination of many terpenoid compounds whose structures would otherwise have remained unknown.
Vagner's lasting fame, however, couples his name with that of German chemist Hans Meenvein. in the form of the Wagner-Meerwein rearrangement. Vagner's elucidation of the structures of the cyclic monoterpene hydrocarbons led him to propose relationships between them where there was a shift of bonding from one site to another. The camphene-bornene rearrangement was first elucidated bv him i8, 91, although the details of the mechanism were pronosed bv Meerwein (10). As nart of his work in the bicvclic terpenei, Vagner also f r s t proposed the correct structure for pinene ( l l ) , whose four-membered ring had been a serious stumbling block for more tradition-minded chemists. Vagner's workwas held in great esteem in Germany. One of the first tasks set for a young Vladimir Ipatieff when he joined Adolf von Baeyer's research group was to translate Vagner's work from Russian into German (12).Vagner was
Figure 2. E. E. Vagner (1849-1903)
Figure 3. S. N. Reformatsky (186s1934)
Figure 4. A. E. Arbuzov (1877-1968).
quite a bon vivant,as is revealed by one anecdote told by Ipatieff in his autobiography. At the end of the scientific convention at St. Vladimir University in Kiev in 1898,Vagner led a group of chemists in a dinner at a restaurantkabaret on Trukhanov Island on the Dnieper River. The dinner was accompanied by copious quantities of vodka, tea, and cognac. 'Vagner was the life of the party and I must note that few can achieve the happy and pleasant state of mind that he could. We returned to our hotel at four o'clock in the morning. . ."(12).
dissertation under Zaitsev's direction. He submitted his master's dissertation in 1889. From 1889 to 1890, he studied abroad for two years a t the Universities of mttingen, Heidelberg (under Viktor Meyerj, and Leipzig (under W. F. Ostwaldj. His Doctor of Chemistry degree was granted by the University of Warsaw, where Vagner was then professor of chemistry. Just as Butlerov's work with zinc alkyls had led Zaitsev to continue research into the uses of these reagents in organic synthesis, so Zaitsev's work with zinc alkyls led Reformatsky to study these nucleophiles when he began his first independent research. His doctoral thesis contained the first reports of the Reformatsky reaction between aldehydes and ketones and the organozinc halides derived from a-haloesters (13). Until the develop-
(Wagner, Bndvler, 1899)
S. N. Refomatsky Sergei Nikolayevich Reformatsky (186C~1934)was born in Kostroma, northeast of Moscow. He received his early education a t the Kostroma Spiritual Seminary, from which he graduated in 1878. He then attended the University of Kazan, where he graduated in 1882 with the degree of kandidat. After his graduation, Reformatsky was made curator of the laboratory museum, a position that paid him a stipend while he completed his research for his master's
ment of strong, non-nucleophilic amide bases in the 1970's rendered the formation of preformed lithium enolates practical, the Reformatsky reaction was the major method for forming P-hydroxycarbonyl compounds, and was one of the few such reactions that did not lead to concomitant dehydration of the product. Although the resurgence of the aldol condensation h a s somewhat eclipsed the Volume 71
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Nikolai Nikolaevich Zinin (1812-1880) Kazan years: graduated 1830-1836 1841- 1847 (professor) ;hailovich Butlerov (1828-1886) Kazan years: student 184-1849 1849-1868 (professor) I
I
Favorskii (St. Petersburg)
>emjanov Chichibabin
Kishner (Moscow) (Moscow) (Moscow)
Ipatieff Nazarov (St. Petersburg) (St. Petersburg)
Aleksandr ~ikhailovich~aitsev (1841-1910) Kazan years: student 1858-1862 1865-1910(faculty)
I
Sergei Nikolaevich Reformatsky (1860-1934) K m n years: student 1878-1882 1882-1889(assistant)
I
Egor Egorevich Vagner (1849-1903) Kazan years: sludent 1867-187. 1874.1875 (assistant)
Boris Aleksandrovich Arbuzov (1903-1992) Kazan years: graduated 1926 1938-1961 (faculty) Figure 5. The influence of the University of Kazan chemists over five academic "generations:
-
Chemical-Technological Institute, where he remained for the rest of his professional career. Arbuzov's research work concerned the chemistry of organophosphorus compounds, and as p a r t of his master's thesis in 1905 (17) h e determined t h e structure of phosphorous acid a n d i t s esters. This work resolved the controversy over the number of hydroxyl groups in the acid and showed the structural differences between phosphorus acid (in which the phosphorus is tetracoordinate and has a PH bond) and the trialkyl phosphites (in which t h e phosphorus i s tricoordinate). He subsequently discovered the rearrangement of phosphite esters to phosphonic acid esters (181, a reaction that has assumed major importance with t h e development of t h e Wadsworth-Emmons olefination reaction (19). His name also has become attached to the Michaelis-Arbuzov reaction, which was discovered by Michaelis a n d Kaehne in 1898 (201,but much more intensely studied by Arbuzov in the early decades of the 20th century. In collaboration with his son and student. Boris Aleksandrovich ~ r b u z o ; (himself a prominent Russian chemist), he developed a new method for t h e formation of triarylmethyl radicals from triarylmethyl halides and phosphite anions. During World War 11, the members and laboratory equipment of the Moscow and Leningrad (now St. PetersburcrJ -. Academies of Science were evacuated to Kazan
Reformatsky reaction as the method of choice for the CH, C6H50\ CH31 synthesis of such compounds, the reaction is still C&*P C6H5*P=0 + C5H50H HI (Arbuzw, 1910) used in appropriate circumstances. On his return to / / Russia, in 1891, he was appointed professor of chemc6H50 C6H$0 istw a t the Universitv of Kiev. where he continued hisuresearch into the"reactions of alkylzinc halides (21). The rise of the Kazan Institute as a large research (14, 15).In 1891, he wrote a textbook of organic chemistry institution dates from this time (22). When the 25th annit h a t went through t h r e e editions (16). I n 1928, versary of the Kazan branch of the Soviet Academy of SciReformatsky was made a corresponding member of the ence was celebrated in 1945, Arbuzov was among a USSR Academy of Science. speaker list that included such luminaries as the Joliok Curies, Robinson, Langmuir, and Svedberg. Arbuzov won A. E. Arbruzov numerous awards, including two Stalin Prizes, and he was One of the last students to study under Zaitsev a t Kazan on several occasions a delegate to the Supreme Soviet (the was Aleksandr Erminingeldovich Arbuzov (1877-1968). governing body of the Soviet Union). He was also a histoHe graduated from the University of Kazan in 1900, and rian and wrote a history of chemistry (23) that emphasized then followed the path another former Zaitsev student, the contributions of the Kman school to the development Egor Egorevich Vagner, as assistant in chemistry (19011, of Russian chemistry. and then Adjunct Professor of Chemistry (1906) a t the The influence of the Kazan school went far beyond those Novo-Aleksandria Institute of Apliculture and Forestrv. individuals in this paper and far beyond the Tatar republic In 1911, he succeeded his mentor as professor of chemist& (and yet the first chemist to attain recognition during his a t Kazan. a wsition he held from 1911to 1930. In 1922. he own lifetime while remaining a t Kazan was Arbuzov). was e l e c t ' e d ~ e ~Dean u t ~ of the physics-mathematics faculty In 1930, Arbuzov became professor a t the Kazan Bntlerov was the dominant force of his generation, and
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Journal of Chemical Education
+
through his students he became the dominant force of the next generation, also. At Moscow, Markowikov became a major force in Russian organic chemistry, and he moulded the minds of not only his own students, but also of his colleagues. Similarly, much of the tradition of Polish chemistry at the University of Warsaw can he traced to Butlerov's influence through Popov, and to Zaitsev's influence through Vagner. Reformatsky's students clearly were subject to the influence of Zaitsev (and, through Zaitsev, of Butlerov), and it is clear that Reformatsky held his undergraduate mentor in high esteem. The influence of Kazan may be best gauged by examining the figure, where the genealogy of Russian chemistry beginning at Kazan is traced. All the chemists whose names appear in boldface earned their undergraduate or graduate degrees from the University of Kazan. Only their more well-known students are listed. Literature Cited
6. SaytLeff,A.Ann. Cham. P h r m . 1876,179,296301. 7. Wagner,G.BerDevl cham a s . 18SS,ZI, l23&1240,33433346,33474355,3SS&
a m
~~~~~
8. Vsgner, E. E. J. R u a . Phys. C h . Soc. 1884.26.327362; 1698.28, 56106,206, 398,484-501. 9. W8gner.G.;Brickner, W B m h u t . chem. a s . 1899.32.23022325;19W. 33,2121" 1 1
10. Meerwein, H.; van Emster, K. Ber Lkut chem Dea 1820,538. 1815-1829: I=, 558.2500-2528. 11. (a) Wagner, G. Ber D a d . cham Ges. 1891.24,2187-2190. ibl Wagner, G . ; S l a n 6 n ~ k ~ K Ber h u t . cham. Ge% 1899. 32, 2064-2083. (cI Wagner, G.: Ginzberg, A. Ber Lkirf, chem. Ces. 1896.29.886890. 12. Ipatieff, V N. ThaLife ofa Chamiif: MemfiiiifVIdimiiN. IpatisfI, IStatafmd Ur& venritv Pms: Stanford. CA. 1946).
*-*-
15. 16. 17. 18. 19. 20. 21. 22.
23.
Reformatsky, S.; Plexonossoff, B.Lkr h u t &em. Gas. 1896.28.2838-2841. Reformatsky, S. N. A BqginmrB C C C C C C C ~ OC' k~ m ~ i~i hCy (Kiev, 1891). Arbuzox A. The Stnrctun ofPhosphomusAcidond ifsDeriuofiues(Kazan, 1905). la1 Arbuzov, A. J Russ Phys. Cham. SOC.1910.42,395420,549661; Chem. Zpntr 1910,II. 453454. For s review see: Wadspnrth. W. S.. Jr 01s.RmeL 1977.25.74. Michael!!, k:Ksehne, R.Bex'Deut.'chm.& 1898,3l~l048-10~5. Grechlun, NP;Kuznetsov, V I. Aisksondr Erminiwiiiouich Arbulou 1877.1968; (Science Publications: Moaeow, 19771. [In Russian1 Areviewer has pointed out that Kazan h m e a najm reeaereh center lover 1,OW PhDs in phosphorus chemism) carrying out research into nerve gases, among other work. The author has not been able to verify this, but given A r b u l d r stmngly nstionalisticfeehngs for the S o G t Union, it is probably true. A r b u m ~A. E,A BrGfSkafeh of& Lkzxlopmnf o f o ~ g o n i cChemistry in Russia; (Academy of Stienm USSR, teningad, 1948). [In Russian1
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