The University of Kazan-Provincial Cradle of Russian Organic Chemistry Part I: Nikolai Zinin and the Butlerov School David E. Lewis South Dakota State University, Box 2202, Brookings, SD 57007
Most organic chemistry instructors and the authors of most organic chemistry textbooks make quite clear (and justifiably so) the contributions of the great German masters of the science to modern oreanic chemistrv. " Oreanic chemistry is full of German names and German name reactions, many of which we expect our students to learn. In part, this may stem from the fact that most English-speaking chemists trace their "professional genealogy" to the German schools of Liebig, Bunsen, Erlenmeyer, Kolbe, von Baeyer, Kekul6, or Hofmann (who was brought to London to introduce the German way of teaching organic chemistry), so that their mentors were much more aware of the German schools and their contributions. However, we tend to overlook the importance of the contributions of the Russian contemporaries of these chemists, despite their names--Saytzeff, Markovnikov, Favorskii and Zelinsky, to name just a few-appearing widely in most undergraduate organic chemistry textbooks. Moreover, relatively few English-speaking organic chemists realize that some chemi s t s who a r e almost universally considered German (Beilstein, Kishner, and Wagner of Wagner-Meerwein rearrangement fame) were, in fact, Russian. I t is the purpose of this article to remedy some of this oversight on the part of English-speaking chemists, and to focus on the contributions of the University of Kazan, in particular. Before beginning t h e historv of the Kazan school of chemistry, the readeraill be wcli served by some pwtinc!nt inlormation about the Russian educational svstem of thc 19th century. Each department was headed b; a professor, who occupied a chair. In order to occupy a chair of chemistry, one had to obtain the degree of doctor of chemistry by writing and defending a dissertation. However, the scope of the oral examination was not restricted to the subject of the dissertation, as are most modem oral examinations, and the candidate was required to demonstrate a knowledge of chemistry in all its sub-disciplines. Prior to obtaining the doctoral degree, a student wrote dissertations for the degree of "kandidat" and for the degree of master of chemistry. The degree of kandidat was somewhere between a modern master's and doctoral degree in level. The m a s t e r of chemistry was a higher qualification (the master's dissertation had to be defended orally), and it was a necessary pre-requisite for obtaining the rank of professor a t a Russian university. Until the end of the 19th century, by which time there were many eminent Russian chemists, i t was tradition for students to write their kandidat dissertation and to leave Russia for a period of study abroad, after which they would return to write their master's and doctoral dissertations.
-
The University of Kazan: Some Background
The Universitv of Kazan was founded in 1804. The courses of study were divided into four faculties PhysicsMathematics, Law, Medicine and Histow-Philoso~hv. Despite i t s status, it has numbered among its
chemistry graduates and faculty some of the finest minds of Russian oreanic chemistrv. What mav be sumrisine to the reader is tbe fact that a t m a n y of these chegists @ladimir Vasilevich Markovnikov. Aleksandr Mikhailovich Zaitsev, and Egor Egorevich ~ a h etor name just three) actually began their undergraduate studies as law or economics students in the faculty of law. At the University of Kazan, any student studying law or finance was required to take two years of chemistry a s part of the course of study. The professor of chemistry held his chair in the PhysicsMathematics Academy of the university, and much of the notable research carried out by the chemists a t Kazan appeared first in the Bulletin of the Physics-Mathematics Academy. There was no separate Chemistry Department until aRer the turn of the 20th centurv. D e s ~ i t ethe hich caliber of the research carried out dy the'chemists i t Kazan, the university remained small, and its reputation remained overshadowed by those of the Universities of St. Petershurg and Moscow. Conseauentlv, most of the eminent ~ u & n chemist.; ofthe 19f'h ceniur). became so only after they moved from Kazan: Rutlerov to St. Prtrrshnre. Markovnikov to Moscow, Vagner to Warsaw, an; Reformatsky to Kiev. Zinin and the Rise of the Chemistry School
The rise of the chemistry school a t Kazan may be attributed to one man, Nikolai Nikolaevich Zinin (1812-1880) ( 11, who graduated from Kazan in 1836, and who was appointed professor oftechnical chemistry there in 1841after spending three years studying abroad in western Europe (including a year spent in the laboratories of Justus Liehig in Giessen). His colleague a t Kazan was Karl Karlovich Klaus. the discoverer of ruthenium. However. the two men were df completely different mind when i t came to chemistry. Klaus was a conservative, and he held strongly to the views of Berzelius. On the other hand, Zinin had been introduced to the ideas of Gerhardt and Laurent while in Europe, and he imparted them to his own students. His vitality was in stark contrast to Klaus' stodginess, and i t was Zinin who was largely responsible for the growth of the chemistry school at Kazan. While in Liebie's laboratories Zinin studied the reactions of henzoyl wmp&mds. His first paper there concerned the henzilic acid from benzil(2). whose synthesis from benzoin he also described. In f a d , it was while in Liehig's lahoratones that Zinin wrote his doctoral dissertation on the benzoin condensation, which he defended a t the University of St. Petersburg in 1841. In 1848, Zinin was appointed to a professorship a t the Academy of Medicine and Surgery of the University of St. Petershurg, where he continued to attract bright young students, among them the renowned chemist-composer Aleksandr Porfirevich Borodin (18331887). discoverer of the aldol(3) and Hunsdiecker-Borodin (4) reactions. Volume 71 Number 1 January 1994
39
Figure 1. N. N. Zinin (1812-1880).
Zinin studied the reduction of benzoin to hydrobenzoin, and of benzil to benzoin in the presence of a dissolving metal (a reaction attributed to "nascent" hydrogen a s late a s the 1940's). His discovery of a method for the synthesis of a wide variety of aromatic amines by ammonium sulfide reduction of the corresponding aromatic nitro compounds led to a long series of papers published in the journals of the St. Petersburg academies (5);these papers were all translated into German by the abstractors of Liebig's Annalen (6).This work, which included the first synthesis of aniline, was pivotal to the later development of the aniline dye industry, and its importance was recognized and commented upon by no less a n m i n e chemist than A. W. von Hofmann himself, who said of this work, "If Zinin had done nothing more than to convert nitrobenzene into aniline, even then his name should be inscribed in eolden letters in the history of c h e m i s w (7).
-
40
Journal of Chemical Education
Butlerov and His Influence at Kazan While a t Kazan, Zinin and Klaus educated one of the most influential chemists of the next generation, Aleksandr Mikhailovich Butlerov (1828-1886) (8).Butlerov was a student a t the Universitv of Kazan from 1844 to 1849, where %ininpersuaded him to study chemistry. However, alter Zinm left for St. Petersbura. -. Butlt~rovlost inrerest i'n chemistry in large part because he was not inspired by t h e extremelv traditional Berzelian views held bv f i a u s . In fact, ~ i t l e r o vwrote his kandidat thesis in ent; mo1o.m ("Diurnal Butterflies of Volga-Ural Fauna," based on the results of a n excursion to the Volga-Ural region of Russia). One of his life-long interests was apiculture, and his articles on the subject were published after his death (9).However, following his graduation from Kazan in 1849, Butlerov beean to teach chemistrv there. His master's thesis, which h i defended in 1851, gave little indication of the highly creative and original individual responsible for it, although it did give the first report of his work on osmic acid oxidation of organic compounds (10). His doctoral thesis, likewise, was mainly a historical summary of essential oils: however. it was sufficient for him to obtain his doctor of chemistryfrom the University of Moscow in 1854 (although not aRer a fight it had orieinallv been submitted to the ?niversirs of ~ a ~ abut n , on" of the thrco t:xaminrm did not feel that it was of suffirient merit to warrant the award of the degree). Following his graduation, he was promoted to professor. From 1852, when Klaus moved to Dorpat, Butlerov taught all the chemistry courses a t the University of Kazan. On two occasions during his last three years a t Kazan, Butlerov was Rector of the University. From 1857 to 1858, Butlerov travelled abroad. During his travels he met Kekul6, whom he much admired from the beeinnine of their friendshiv. and Erlenmever. For six month; ( ~ e c e m b e 1857-May r fa581 he workedin the laboratories of Charles Adolphe Wurtz in Paris, where he may have had the opportunity to interact with Wurtz' student, Archibald S w t t Couver. At this time. Paris was a vibrant center of organic cGemistry research, and it was during this trip that Butlerov was exposed to the new ideas of structure in organic chemistry. He embraced them avidly (11).By 1860, Butlerov had developed his own structural theor\ of organic chemistry, which, according to Markwnikov, he had begun expounding in h ~ lecturw s by 1860. It was ilutlerov who first used the term ~ h c r n ; < n l structure with its modem meanlng. In addition 111 his theoreriral work, Butlerov alsn c;irrird out research in organic synthesis. The rcacllon between acid chlorides and dialkylnncs to give tertiary alcohols, the l3utlerov reaclion, was discovered in 1864 r 12 ,and was the first reaction to permit the synthesis of ;I tertiarv alrnhol. whose exlste&e had been predicted by ~ e r m k Kolbe n in 1860 based on the type theory of Dumas. Until the diswvery of the
Grignard reaction over three decades l a t e r (13). t h e ~ u t i e r o vsynthesis was the only reliable method for the svnthesis of these comvounds. One eathers from bioera;hies of Butlerov and hys students that Butlerov's lectures and laboratory courses were nothing short of electrifying. He rapidly drew some of the finest young minds in Russia to him, including two leaders of the next generation. Among the leaders of the "Butlerov School" were Aleksanir Mikhailovich Za~tscv11811-1910,. who is better known by the Gt~rmansprll~ngof his name ~Saytzeff,, and
sity courses for women and regularly gave public lectures on chemical topics. He also relished a fight: in 1874, and again in 1880, h e and Zinin jointly proposed Mendeleev for membershio in the Russian Academv of Sciences. When Vendelcev was denied membership on both occnsions, Rutlerot did not hesitate to use oublic o o i ~ o to n hl~xkthe candidacy of the opposing factioI;'s nominee, Beilstein, and he wrote an oven letter in the onblic newsoaoers to ~ a i n popular supPo& for his point of kew. In later life, ~ u t l e r o v became a devotee of spiritualism (16). Markovnikov: Butlerov's Successor
Figure 2. A. M. Butlerov (1828-1886) Vladimir Vasilevich Markovnikov (1837-1904), both of whom succeeded Butlerov to the chair of organic chemistry a t Kazan. I n order to disseminate his theory of structure more widely, Butlerov wrote a textbook of organic chemistry (14) which was edited by his colleague and personal assistant Mikhail Dmitrievich Lvov (18461899). This book, which subsequently appearedinGerman (13b), was the first textbook to be based entirely on structural theory I t was one of the most influential textbooks of its day and had much to do with the general acceptance of structural theory. For 10 months during 1867 and 1868, Bntlerov again went abroad, ostensibly to promote the German edition of his textbook, hut also to defend his claims to priority in the development of structural theory. At t h a t time, Kekult. alone was receiving the credit for the development of this milestone in organic chemistry (Couper's claims were ignored until quite recently). Butlerov's claims of priority led to a long dispute over just who did first develop structural theory (15). While he was absent, his lectures in organic chemistry were delivered by Markovnikov, who substituted for his mentor. I n May 1868, Butlerov was appointed a s Professor of Chemistry a t the University of St. Petersbur~,a l t h o u ~ ha, t the request of the board of governors of the-university of Kazan, he did not actually leave until January of the following year. At St. Petersburg, he continued to attract "disciples" of t h e h i g h e s t caliber, among t h e m Alexei Evmafovich Favorskii (1860-1945). A man ahead of his times in many ways, Hutlerov promoted the highcr cducatlon of women and knew the Importance of maintaimng a good rapport with the general p;blic. He organized mi&-
Butlerov's senior student a t Kazan was Vladimir Vasilevich Markovnikov. Markovnikov (17) b e ~ a nhis studies a t the University of Kazan as a student in iaw, but he was captivated by the lectures of Butlerov, and immediately atter his graduation in 1860 with a degree in economics he became Butlerods assistant. In 1865, Markovnikov took his master's degree and then lett Russia on a fellowship for foreign study, where he spent two years in Germany, mainly in the laboratories of Richard Erlenmeyer, in Heidelberg, and Hermann Kolbe, in Leipzig. He was, therefore, in Kolbe's laboratories immediately atter his fellow student Zaitsev. I n 1867, Markovnikov returned to Kazan a s a junior faculty member i n chemistry, a n d h e immediately began work on his doctoral dissertation. His degree of doctor of chemistry was awarded in 1869 with Butlerov as the formal opponent (chief examiner). Markovnikov's status a s Butlerov's assistant, and the fact that he had substituted for him in the lecture caurses i n organic chemistry while Butlerov was abroad, made Markovnikov the logical choice to succeed his mentor a t Kazan. However. his irascible nature and his vroeressive . ideas were some cause for concern to the university administration (to the extent that they decided to appoint two professors to replace Butlerov instead of one). His biographers all point out his willingness to participate in scientific arguments with his conservative mentor, Kolbe. Anyone who would venture to argue with the European dean of organic chemistry was likely to prove to be a formidable opponent, indeed. Despite their misgivings, the University Council appointed Markovnikov a s extraordinary professor of chemistry in 1868 and promoted him to ordinary professor in 1870. They had planned to appoint a fellow Butlerov student, Aleksandr Nikolaevich Popov (d. 18811, as his colleame. even before he had written his master's thesis. I n 18Y69 ~ o p o vwrote a brilliant master's thesis on structural theory, but he was not of robust health, and the t h o u g h t of a c t i n g a s a buffer between t h e forceful Markovnikov and the university administration may have daunted him. Despite MarkovnikoJs strong support for him. He a c c e ~ t e dthe chair of chemistry a t the University ofwarsaw, instead (18).In many ways, this may have been fortunate for the University of Kazan because Popov accomplished nothing further of note after his a m v a l in Warsaw (although he did begin the long and fruitful association between the University of Kazan and universities in Poland). During his time a s professor a t Kazan, Markovnikov becan the research into orientation effects in addition reaciions t h a t led to h i s formulation of w h a t we call Markovnikov's Rule (19). Interestingly, much of Markovnikods work, especially his theoretical papers, appeared only in Russian. He was intensely nationalistic, and although he frequently bemoaned the backwater conditions under which Russian scientists worked, h e never considered takine a n aooointment in anv other countrv. Bv publishing his best wi;k only in ~ u s s i &journals he believed that he was helping the cause of Russian chemistry. Volume 71 Number 1 January 1994
41
his colleames who u r ~ e dhim not to leave the path of "pure chemistry". In 1881, his report of the sy&hesisof a cvclobutane derivative (20)helped to dispel the extant belief that carbocyclic rings othe; than six-membered could not be formed, while his synthesis of a cycloheptane derivati\.e 21, fiwn sub6:rone i n 1890 the sume .yt;;~r 221 that Willi:~mllrnly I'rrkin. .lr synthesized ;I (:y(:luheptanederivative from 2.A-nonanrdi~~ne~ helnrrl to disoel thr belief that rings larger than six-membered could ndt exist
Literature Cited 1. For biographies of Zinin, see: IaJLeicester, H. M. J. Cham. Educ 1940,17,303-306. IbJButlerov A. M.; Bomdin, A. P BPI DOUI rhem. Gea. 1881, 14,28879908, 2. Zinin,N.Ann. Chem Phonn. 1839.31.329332; 1840.34, 186192. 3. Borodin, A. Bcr Deur, chem Gel873.6.982-985. His earlier repoN to the Chem~ ieal SoeietyofSt. Peterrburgwerereported as correspondence:Richter. V vonBer h u t . chem Gea 1869.2.552-554; 1870,3,421428; 1872.5.477.482. 4. (sJ Borodine, A.Ann. Chem Pharm. 1861, 119, 121-123. !bJ Hunsdieeker, H.; Hunsdiecker, C. Chem B w 1942. 75,291-297. i c i Hunadiecker, C.; Hunsdiecker, 1940.34.1885. H.;Vogt.E. U S P o L 2,176,181(1939):Chem.Abtr 5. Early papers: Zulul, N . Bull. Sci. Aced St. Pelemburg 1842. 18; Bull. Phys. Math. Aeod St. Peiersburg 1852.348 6. Early papers: Zulul. N . Ann. Chem. P h o m . 1842.44.283-287; 1844.52.361462; 1%.9 85 21R124
zaitsev. V. V . Markovniko", amongothers. 9. Butlemv,A.hiieie~onApicuIlum(Kaan, 18911. l o . Butlerov. A. Bull Phys. Moth. Amd. St. Pdersburg 1852, 177: Ann. Chrm. Pharm., 1853.84,27&280. 11Douper's theory ofstruchlre and Butlemv's commentary ofit were published together in 1859: la1Couper.A. S A n n . Chem. Phorm. 1&59.110.465I.!b1Butlero~A A n n .
Figure 3. V. V. Markovnikov (1837-1904). As t h e university administration had feared, Markovnikov's progressive views led to conflict, and his tenure a t Kazan was short-lived. In 1871 he resiened his position along with six colleagues to protest the actions of the Universitv Rector. He was immediatelv offered the chair of chemktry a t the University of ~ d e s s awhich , he accepted, and then, in 1873, he was asked to assume the chair of chemistry a t the University of Moscow, where he spent the remainder of his professional career, becoming mentor to several well-known organic chemists, among them Nikolai Yakovlevich Demyanov (1861-19381, Alexei Yevgenievich Chichibabin (1871-19451, and Nikolai Matveyevich Kizhner (1867-19351. At Moscow, Markovnikov turned his attention to the chemistry of petroleum and alicyclic compounds, in spite of protests from
-
42
Journal of Chemical Education
. .
.
14. IaJ Butlerov, A. lritmduction to the Study o f Or#anic Chemistry IKazan, l 8 M J lbl Butlerov, A. LPhrbuch der o r p n i s c h ~ nChemv xu, Einfuhrung in doa specidla Sludium derselbm (Leipzip, 18671.
M.J. Chem ~ d ~1953.36.328-328, c . 16. But1erov.A. Articles on Mediumism. (St. Petemburg, 1889). 17. For biographies of Maikovnikov, see: !a) Leiester, H. M. J Chem. Educ, 1941, 18, 5&57. lbi Decker, H . B e &ut, cham. Ges. 1906,38.424%4262. 18. 1sJArburov.A.E A B r k f S k d d h hftite D O w l i p m ~ ~oIf O r g ~ n k C h h h i i f r y i i R ~ ~ i i ; (Academy of Science USSR. Leningrad. 19481. pp 187-188 [In Russianl. ibJ Klyuchev?ch, A. S.: Bykov, 0.Y AleksandrMikhoilouich Zoriseu: (ScientificPublications: Moscow, 19801 p 20 Iln Russianl. 19. Msrkovnikov, V. Ann. Chsm. Phorm. 1870, 153, 22&2593 Compt. rend. 1875, 82. 668-671.728-730,776-779, 20. Markovnikov V : Krestovnikos A. Ann. Pharm. C h s m 1881.208.333449.
