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  • Bull. Hist, Chem. 17/18 (1995) 21


    Markovnikov's Conservative Contemporary

    David E. Lewis, South Dakota State University

    Most students in organic chemistry today are familiarwith Saytzeff's Rule for elimination reactions, althoughfew, if any are aware of the Russian chemist, AleksandrMikhailovich Zaitsev (1841-19I0), for whom it isnamed. In part, this may be due to the lack of westernsources concerning his life. All the biographical mate-rial available on Zaitsev is in Russian (1, 2) with theexception of two German sourcesthe brief death no-tice in Berichte (3a) and the minimal information inPoggendorffs biographical bibliography (3b)and twobrief surveys of his work in Englishthe recent thesisby Brooks (3c) and a survey paper in J. Chem. Educ.(3d).

    Zaitsev was born in Kazan' to a mercantile familythat had lived in the region since the time of Ivan theTerrible (1533-1584), and there is evidence that theZaitsev family had been agents of commerce betweenthe Russian Empire and the Orient since that time. Hisfather, Mikhail Savvich Zaitsev, had two sons by hisfirst wife and three sons, of whom Aleksandr was themiddle one, by his second wife, Natalie Vasil'evnaLyapunova. A merchant with control over the tea andsugar trade, Mikhail Savvich Zaitsev resolved early thathis son should join the mercantile guilds and follow inhis footsteps. However, Zaitsev's maternal uncle, theastronomer Mikhail Vasil'evich Lyapunov (later Pro-fessor of Astronomy at Kazan' University), persuadedhis brother-in-law that young Aleksandr should attendthe university, instead. Accordingly, Aleksandr was en-rolled in the Gymnasium.

    Founded in 1804, Kazan' University was the east-ernmost outpost of Russian higher education during thenineteenth century, and yet by the middle of the nine-teenth century it had assumed a pre-eminent position in

    A. M. Zaitsev

    Russian organic chemistry despite its provincial loca-tion and status. This ascendancy of the chemistry de-partment of Kazan' University was achieved under theguidance of such luminaries as Nikolai NikolaevichZinin (1812-I880), Karl Karlovich Klaus (1796-1864),and Aleksandr Mikhailovich Butlerov (1828-1886), andit was maintained under such renowned chemists as

  • Kazan University Chemical Laboratory in Zaitsev's time

    22 Bull. Hist. Chem. 17/18 (1995)

    Vladimir Vasil'evich Markovnikov (1838-I904),Zaitsev himself, and Aleksandr Erminingel'dovichArbuzov (1877-1968).

    In 1858, following his graduation from the Gym-nasium, Zaitsev entered Kazan' University as a stu-dent in economic science in the Faculty of Law. Atthat time, all students entering the Faculty of Law wererequired to pass a qualifying examination in Latin.Because there were no classes in Latin at the Gymna-sium, Lyapunov himself had taught the youngAleksandr the Latin which he needed to pass the en-trance examinations. At that time, also, all students inthe Faculty of Lawwere required to passtwo years of chemistryin order to graduate. Itwas while taking theserequired chemistrycourses that the youngZaitsev came under theinfluence of one of thegreatest organic chem-ists produced by Rus-s i a AleksandrMikhailovichButlerov. By the timethat he had graduated,Zaitsev was no longeran economist, but acommitted chemist.Zaitsev graduated withhis degree in economicscience in 1862.

    Up to this timeRussian tradition pre-scribed a fairly rigidcourse of action fol-lowing graduation.The most immediate concern for most students was toremain in Russia to write the dissertation for the de-gree of Kandidat, without which one could not obtaina salaried position as a laboratory assistant. Today, thedegree of Kandidat at most Russian universities is theapproximate equivalent of the Ph.D.; in the nineteenthcentury, however, it was somewhere between a mod-ern master's degree and a modern Ph.D. Followinggraduation with the degree of Kandidat, most studentsstudied abroad for two to three years, then returned toRussia to submit a dissertation for the degree of Mas-ter of Chemistry (the minimum qualification for ob-taining a teaching post at a university). In order to ob-tain the rank of Professor at a university, one neededthe degree of Doctor of Chemistry, which necessitated

    the submission and defense of a dissertation, as well aspassing an examination over every area of chemistry.

    For whatever reason, whether from impatience anda desire to study under the best in Europe or simplybecause he did not think ahead about his financial secu-rity on his return to Russia, Zaitsev chose to ignore thesetraditions; this very nearly proved to be a fatal mistake.Immediately after his graduation from Kazan' Univer-sity he left for Germany, where he entered the labora-tory of Hermann Kolbe at the University of Marburg.In 1863, after his first year with Kolbe, Zaitsev submit-ted a dissertation to Kazan' University for the degree of

    Kandidat. This 76-page hand-writtendissertation wasentitled, "TheTheoretical Viewsof Kolbe on theRational Consti-tution of OrganicCompounds andTheir Relation-ship with Inor-ganic Com-pounds." It con-tained an over-view of Kolbe'sversion of struc-tural theory(Kolbe viewedthe term "chemi-cal structure" asspecious, and heeschewed it in fa-vor of "rationalconstitution")that had led himto predict the ex-

    istence of, among other compounds, the tertiary alcohols.Ironically, it was Butlerov who was the primary exam-iner of this dissertation. As one of the developers of themodern structural theory of organic chemistry, and asthe chemist who first synthesized tert-butyl alcohol (4),thus confirming Kolbe's predictions, Butlerov was inti-mately acquainted with Kolbe's views (and opposed tothem). Unfortunately for Zaitsev, the dissertation wasneither well written nor novelButlerov characterizedit as "a poor rendering of the German"and the degreewas not awarded.

    Zaitsev's studies continued uninterrupted atMarburg until August, I864. At Marburg, he studied thechemistry of organic sulfur compounds. He made thefirst of his major discoveriesthe sulfoxides, whose

  • Bull. Hist. Chem. 17/18 (1995) 23

    existence and formation he reported in a series of pa-pers (5) during the last half of the 1860'swhile study-ing the oxidation of organic sulfides by nitric acid. Dur-ing the 1864-1865 academic year (August 1864-April1865), Zaitsev moved to Paris, where he studied underCharles Adolphe Wurtz at the Universit de Paris. Hiswork at Paris, primarily concerned with the reactionsof carboxylic acid derivatives (6, 7), was subsequentlythe basis of his successful dissertation for the degreeof Kandidat (8).

    In May, 1865, Zaitsev returned to Marburg to begreeted by the news that Kolbe had accepted the Chair

    Zaitsev as Laboratory Assistant (1871)

    of Chemistry at the University of Leipzig. Choosingnot to follow his mentor to his new post, Zaitsev re-turned to Russia. Here he was unable to work as a sala-ried laboratory assistant because he lacked the degreeof Kandidat. This did not deter Zaitsev, who immedi-ately offered his services "as a private individual" anunpaid, unofficial laboratory assistantto Butlerov. Hequickly impressed his mentor, who urged him to writehis dissertation for the degree of Kandidat. In 1865, hesubmitted his dissertation, "ConcerningDiamidosalicylic Acid," based on the results of his twosemesters of work in Wurtz' laboratory. The papers de-

    scribing this work appeared in both French and Ger-man the same year (6). The degree was awarded and,thanks to the support of Butlerov, Zaitsev obtained aposition as laboratory assistant in agronomy in I866.The university also committed the direction of the labo-ratories in agronomic chemistry to him.

    In order to teach at Kazan', Zaitsev needed a de-gree beyond the Kandidat. The expected degree wasthe Master of Chemistry degree, but it would requiretwo years of study beyond the Kandidat before he couldsubmit a Master's dissertation. Therefore, once againin defiance of Russian tradition, he wrote up the re-sults of his Marburg work and sent them to Kolbe atLeipzig in the form of a PhD. dissertation (9). In 1866he was granted the degree of Ph.D. by the Universityof Leipzig (one may speculate on the extent to whichKolbe's influence affected this outcome). Herein mayalso lie some of the origins of the disdain ofMarkovnikov, Butlerov's student and successor atKazan', towards Zaitsev. When Zaitsev submitted hisPh.D. dissertation to the University of Leipzig,Markovnikov, who was an ardently nationalistic Rus-sian, was a senior student in Kolbe's laboratories, andprobably privy to the fact that Zaitsev had once againflouted Russian tradition by applying for a doctoraldegree from a foreign university.

    The work for which Zaitsev was awarded the Ph.D.by Leipzig appeared the same year as a paper in LiebigsAnnnalen with the same title, "Ueber eine neue Reiheorganischer Schwefelverbindungen." He completed hisdissertation for the degree of Master of Chemistry, "Onthe Action of Nitric Acid on Certain Organic Com-pounds of Divalent Sulfur and on a New Series of Or-ganic Sulfur Compounds Obtained from this Reaction,"in the first half of I867 (I0). Initially, several membersof the faculty of the University did not want to permitZaitsev to submit the dissertation because he alreadyheld a doctoral degree from a foreign university (de-spite the fact that foreign doctoral degrees were notrecognized in Russia at the time); it was only becauseof Butlerov's intervention that he was permitted to doso. He successfully defended the dissertation in Octo-ber, 1868, and was awarded the degree that December.

    In May, 1868, Butlerov accepted the chair ofChemistry at St. Petersburg University. However, heasked for and received permission to delay his depar-ture from Kazan ' until January, 1869, to permit asmooth transition of the chair to his