Bull. Hist. Chem., VOLUME 42, Number 2 (2017)112A. YE. ARBUZOV:FATHER OF ORGANOPHOSPHORUSCHEMISTRY IN RUSSIADavid E. Lewis, Department of Chemistry, University of Wisconsin-Eau Claire,Eau Claire WI 54702-4004, USA; [email protected] year 2016 marked the 110th anniversary ofthe first publications by Kazan chemist, AleksandrYerminingel’dovich Arbuzov (1) (Арбузов, , 1877-1968, Figure 1), describingthe reaction that now bears his name (2). Arbuzov becamea major pioneer of organophosphorus chemistry—he wasnominated for the Nobel Prize in Chemistry four times(3)—and his long career at Kazan established it as a worldcenter for research in that field (4).Figure 1. Aleksandr Yerminingel’dovich Arbuzov (18771968, left) and Aleksandr Mikhailovich Zaitsev (1841-1910,right).The city of Kazan is 600 miles east of Moscow,on the Volga River. Today, it is the capital city of theTatarstan Republic of the Russian Federation and theeighth-largest city in Russia, but in 1804 it was effectivelythe easternmost European outpost of the Russian empire.In fact, to many Russians resident in the western capitalsof Moscow and St. Petersburg, Kazan was not a Europeancity but an Asiatic one, and this made recruiting facultymembers rather more difficult than the same task in thecontemporary new universities at Dorpat (now Tartu, inEstonia) and Khar’kov (now Kharkiv, in Ukraine), whichwere much closer to western Russia and therefore viewedautomatically as European. This difficulty in recruitingfaculty members was a major reason why it took anunusually long time—a decade—for Kazan to becomea full, independent university, rather than subordinate tothe local Gymnasium.Despite this less-than-auspicious beginning, by theturn of the twentieth century, Kazan had risen to becomeone of the pre-eminent universities in Russia (5). In fact,at the turn of that century, almost half the Professors ofChemistry in the Russian empire had a connection withthe Kazan School of Chemistry, either by receiving partor all of their education there, or by studying under oneof the graduates of the Kazan school.Arbuzov’s Early Life and EducationArbuzov was born to a member of the lesser nobility in the village of Arbuzov-Baran, in Kazan Province;his father’s estate was next to that of the great Russianorganic chemist, Aleksandr Mikhailovich Butlerov

Bull. Hist. Chem., VOLUME 42, Number 2 (2017)(Бутлеров, Александр Михайлович, 1828-1886). Hebegan his schooling in the one-room schoolhouse in thevillage; shortly after Butlerov died, he was enrolled in theclassical Gymnasium in Kazan. He graduated in 1896 andimmediately entered the Physics-Mathematics faculty ofKazan University. Here he met Aleksandr MikhailovichZaitsev (Зайцев, Алкксандр Михайлович, 1841-1910,Figure 1) (6).As a student, he taught himself to blow glass, andover time, he became a true virtuoso glassblower—one ofthe few chemists who did not need a professional glassblower in his laboratory. His skills as a glassblower wereparticularly invaluable in Novo-Aleksandriya, for theInstitute did not have a glassblower (Figure 2). In 1912,he published a self-study guide to learning glassblowing(7a). Two decades later, while fractional distillation wasstill the only recourse for separating mixtures of liquids,Arbuzov published at least one paper on particularlyeffective fractionating columns/reflux condensers fordistilling turpentine (7b).Figure 2. Two views of Arbuzov at the glassblowing table.Arbuzov earned his diplom in 1900. One monthlater, he passed the examinations for the degree of kandidat in the natural sciences, and he prepared to undertakehis research for the degree of Magistr Khimii (M. Chem.).113Scheme 1. The final synthesis at Kazan of a homooallylicalcohol by the Zaitsev method.Figure 3. Yegor Yegorovich Vagner (Georg Wagner, 18491903, left) and Sergei Nikolaevich Reformatskii (1860-1934,right).During the year that Arbuzov graduated, VictorGrignard (1871-1935, Figure 4) published his methodfor the synthesis of alcohols (10). This completely revolutionized alcohol synthesis, because it did not requirethe strong experimental skills that the Zaitsev synthesisrequired. With the lone exception of the Reformatskiireaction (9), the use of organozinc nucleophiles fell intoan eight-decade decline. The synthesis of secondary alcohols by means of organozinc nucleophiles was eventuallyresurrected by the work of Ryoji Noyori (1938-, Figure4) in the asymmetric synthesis of secondary alcoholswith organozinc nucleophiles (11).Zaitsev had continued the work of his own mentor,Butlerov, in developing methods for the synthesis of tertiary alcohols based on organozinc nucleophiles (Scheme1); his students Yegor Yegorovich Vagner (Вагнер, ЕгорЕгоревич, Georg Wagner, 1849-1903, Figure 3) and Sergei Nikolaevich Reformatskii (Реформатский, СергейНиколаевич, 1860-1934, Figure 3) further extendedZaitsev’s work to the synthesis of secondary alcohols(8) and b-hydroxyesters (9).Figure 4. Victor Grignard (1871-1935, left) and RyojiNoyori (1938-, right).

114The Grignard method required much less experimental skill than the organozinc approach, and so alkylmagnesium halides, which are inherently more reactivenucleophiles than the corresponding zinc species, quicklydisplaced alkylzinc halides or dialkylzinc reagents as thepreferred nucleophiles for this purpose. Arbuzov thus hasthe distinction of being the last Zaitsev student to carryout an alcohol synthesis (2-phenylpent-4-en-2-ol) usingallylzinc iodide (12). However, the timing of Grignard’sdiscovery placed the young Arbuzov in a difficult position, since the proposed research problem for his M.Chem. degree was now rendered obsolete. In fact, inthe same paper (12), Arbuzov described carrying out thesame synthesis with magnesium by adding a mixture ofallyl iodide and acetophenone dropwise to magnesiumturnings in ether. This general reaction had been reportedin 1899 (13) by Grignard’s mentor, Philippe AntoineBarbier (1848-1922), but organomagnesium reactionsdid not achieve popularity until after Grignard’s papershad appeared.Arbuzov’s Early Independent CareerImmediately following his graduation as kandidat,it had been Zaitsev’s intent to retain Arbuzov at Kazan totrain for the professoriate, and Zaitsev had submitted thepaperwork for him to do so, to St. Petersburg for action.At the same time, Arbuzov had moved to the Petrovskii(now Timiryazev) Agricultural Academy, where heenrolled in the third course. Then, before his stipend asAspirant could be approved, the Professor of Inorganicchemistry at Kazan, Flavian Mikhailovich Flavitskii(Флавитский, Флавиан Михайлович, 1848-1917,Figure 5), urged kandidat Arbuzov to follow Zaitsev’sstudent, Wagner, to the Novo-Aleksandriya Institute ofAgriculture and Forestry (Figure 6) as Assistant in theDepartment of Organic Chemistry and Chemical Analysis. On his arrival there, Arbuzov sought out Wagner, andpassed on greetings from their mutual mentor, Zaitsev.Figure 5. Flavian Mikhailovich Flavitskii (1848-1917, left)and Karl Arnold August Michaelis (1847-1916, right).Bull. Hist. Chem., VOLUME 42, Number 2 (2017)Figure 6. The Novo-Aleksandriya Institute of Agricultureand Forestry, in the Pulavski Palace.Today, Novo-Aleksandriya is the Polish city ofPuławy. In 1842, after the November uprising of 18301831 had been quashed, it was renamed Novo-Aleksandriya. Poland had long been a thorn in the side of theRussian government, and after this uprising, a deliberate move was made to Russify Poland and to suppressPolish culture; the renaming of Puławy was one part ofthis effort. Following World War 1, after the defeat of anumerically much larger Soviet army and the restorationof Polish sovereignty, it reverted to Puławy.At Novo-Aleksandriya, Arbuzov’s duties wereto manage the department and the practical classes ofstudents in a large and complex laboratory—he was theonly assistant for a laboratory with 80 student places. Inthe Fall, students studied quantitative analysis, and in theSpring they studied the analysis of soils and fertilizers.In addition, his duties included assisting in lectures onorganic chemistry. And still, he found time for research.The head of the department, F. F. Selivanov, proposedthat he carry out the synthesis of tert-butylacetic acid,but this project proved to be much more difficult than Selivanov had envisaged. Arbuzov’s progress on the projectwas agonizingly slow, especially for such a meticulousexperimenter. Selivanov had an excellent and expansivemind, but Arbuzov reported that his experimental technique was so sub-standard, that he was a poor leader inthe laboratory (4c). Certainly, he had little grasp of thepractical difficulties that young Arbuzov would encounter. Although Selivanov wanted to publish their meagerresults, Arbuzov withheld his permission, so the workremained unpublished.With the failure of this initial project, Arbuzovradically changed the focus of his research, and beganto study phosphorous acid and its derivatives, largely as

Bull. Hist. Chem., VOLUME 42, Number 2 (2017)115a result of studying Mendeleev’sthat the structure of phosphorousOsnovy Khimii during his preparaacid was, in fact, not P(OH)3, buttion for the M. Chem. degree. ThisHPO(OH)2, as had been proposedwas a much more daring move thanearlier by Michaelis. His studiesit might seem, since it meant thatwere also much more wide-ranghe would be pursuing research foring. The Arbuzov rearrangementthe M. Chem. without a formalhad the advantage that it requiredresearch supervisor and in a totallyonly one formal step (unlike thenew field. Nonetheless, he obtainedMichaelis reaction, which requiredenough results (2a) to prepare anda base hydrolysis to complete thesubmit his M. Chem. dissertationrearrangement), and that it did notScheme 2. The Michaelis rearrangement of(14) to Kazan University in 1905. Inrequire such extreme es.this dissertation, Arbuzov discussed(his reactions were typically carthe structure of phosphorous acidried out between 100 and 130 C).and its derivatives, and he investigated the nature of theAt the same time, Arbuzov discovered the catalyzedhydrogen that is not replaced by metals. His first indeversion of the reaction.pendent research results were presented in 1903, at themeeting of the Society of Naturalists at the Universityof Warsaw (15), and concerned the use of copper(I) saltsto distinguish tricoordinate phosphite esters, P(OR)3,from tetracoordinate “phosphite” esters, RP( O)(OR)2,Scheme 3. The Arbuzov rearrangement of trialkyl phosphites(which he later showed were actually dialkyl alkylphosto dialkyl esters of alkylphosphonic acids.phonates).As a result of the successful defense of his M.Arbuzov’s dissertation research extended earlierChem.dissertation at Kazan, Arbuzov was appointed towork by August Michaelis (1847-1916, Figure 5) attheChairof Organic Chemistry at Novo-AleksandriyaRostock. In 1876, as part of a lengthy article (16), Miin1906,andin 1907, he was awarded a komandirovkachaelis had proposed that the structure of phosphorous(ratherlikeamodernsabbatical), which he spent in westacid was HPO(OH)2, and in a later paper (17), he studiedern Europe, working with Emil Fischer in Berlin, andthe reactions of phosphorous acid esters, and noted thatBaeyer in Munich. Many years later, Arbuzov recalleddiethyl ethylphosphonate, prepared by reaction of diethylhow Fisher asked him, referring to Arbuzov’s discoveryphosphite and sodium metal, followed by alkylation withof the catalytic effect of copper(I) salts on the conversionethyl iodide, was in fact, identical to the triethyl phosphiteof phenylhydrazones to indoles (20), “Have you patentedreported by Zimmermann (18).your discovery?” When he received a negative answer,A year later, Michaelis and his student, KaehneFischer was terribly surprised at his selflessness and,published the paper describing the reaction of triarylperhaps, at the naiveté of his Russian colleague (4e).phosphites with methyl iodide. They reported that theArbuzov returned to Novo-Aleksandriya in 1910—theinitial reaction gave a methyl(triaryloxy)phosphoniumyear that his mentor, Zaitsev, died.iodide that decomposed on boiling in water or dilutebase to give the diaryl methylphosphonate. If the sameArbuzov’s Return to Kazansalt were simply heated above 200 C, the diaryl methylphosphonate, the phenol, and hydrogen iodide (19)Two candidates were initially considered to replacewere obtained (Scheme 2). Interestingly, Michaelis didZaitsev at Kazan: Vladimir Vasil’evich Chelintsevnot follow up on this particular discovery—this was his(Челинцев, Владимир Васильевич, 1877-1933), aonly report of the reaction—but shifted his research morestudent of Zelinskii, and Aleksandr Nikolaevich Retoward the chemistry of nitrogen heterocycles, especiallyformatskii (Реформатский, Александр Николаевич,the pyrazolones and their phosphonyl derivatives.1864-1937, Figure 7), a student of both Zaitsev andArbuzov’s discoveries nicely complemented thoseof Michaelis. During the course of his M. Chem. research,he had discovered the reaction that now carries hisname (Scheme 3) (2), and had obtained strong evidenceMarkovnikov. Reformatskii, in particular, had strongties to Kazan through his mentor, Zaitsev. Nevertheless,both declined to compete for the position, and chose toremain at Moscow.

116Bull. Hist. Chem., VOLUME 42, Number 2 (2017)In 1914, with his student, A. A. Dunin, he reportedthe reactions of triethyl phosphite with ethyl a-bromocarboxylates and with ethyl chloroformate (24) (Scheme4). The resultant phosphonocarboxylate esters and similarphosphonic acid derivatives have become stock reagentsfor the synthesis of E-a,b-unsaturated esters by theHorner-Wadsworth-Emmons reaction (25).Figure 7. Aleksandr Nikolaevich Reformatskii (1864-1937)Once again, Flavitskii stepped forward, this time tochampion Arbuzov as a candidate for the vacant chair.He actively promoted his nominee by describing Arbuzov’s work and potential in glowing terms in his writtenassessment (21):In all these studies, A. Ye. Arbuzov has proved to bea careful and skilled experimenter. All his works aredistinguished by the ingenious formulation of thequestions and the comprehensiveness of his investigations of them. Questions about isomerizationsor rearrangements involving catalysts are currentlyvery common in chemistry, and the results of A. Ye.Arbuzov in this area witness to his general initiative and are what we are entitled to expect from thehead of a scientific school. This is exactly what thetraditions of the Chair of Organic Chemistry at ourUniversity, established by Butlerov, Markovnikovand, most recently, Zaitsev, demand.Arbuzov became Extraordinary Professor of Chemistry at Kazan in September 1911, with the conditionthat he write and defend a dissertation for the degree ofDoktor Khimii (Dr. Chem.) within three years. In February 1915, his Dr. Chem. dissertation (22), containingfull descriptions of the reaction he had developed, waspresented to the University Council by Flavitskii andapproved.Arbuzov’s career at Kazan was long and distinguished, culminating in his election to the USSR Academy of Sciences and the establishment of the Institute ofOrganic and Physical Chemistry that bears his name; hewas the first Director of the Institute. During his entirecareer, he continued his work with organophosphoruscompounds, and with his rearrangement. In the ensuingfive decades, he published 73 papers in Russian and fourin German in the area of organophosphorus chemistry(23).Scheme 4. The Arbuzov rearrangement of trialkyl phosphitesto dialkyl esters of alkylphosphinic acids and the alkylationof dialkyl phosphites with a-haloesters.Around the same time, with his student A. A. Ivanov,he reported further investigations of the isomerization oftrialkyl phosphite esters to the isomeric dialkyl alkylphosphonates by the alkyl halide (26).There is a hiatus of eight years in Arbuzov’s publication record, between 1915 and 1923, a period thatencompassed both World War I and the Russian Revolution. Although there were no refereed publications byArbuzov during this time, an abstract (27) of a talkgiven by him to the Third Mendeleev Congress of Pureand Applied Chemistry, held at the National ChemicalTechnological Institute in Kazan, detailing the activitiesof the Laboratory of Organic Chemistry at Kazan for theperiod 1915-1921, was published in 1923.A Russian-German commercial agreement of 1904prohibited Russia from refining coal tar, meaning thatGermany held a monopoly on the raw materials for manyimportant medications in Russia. Early on, the pioneering pyridine chemist, Aleksei Yevgen’evich Chichibabin(Чичибабин, Алексей Евгеньевич, 1871-1945), sawthe danger for Russia posed by shortages of essentialmedicines. He was one of the organizers of the MoscowCommittee for the Development of the Chemical Pharmaceutical Industry and became its first head.In 1915, Arbuzov had just been promoted to Ordinary Professor, the same year that Chichibabin launcheda public appeal to enlist the help of chemists for the production of medicines (28). Arbuzov answered the call,and he began consulting with the Krestovnikov Brotherschemical plant in Kazan (Figure 8). This plant, which

Bull. Hist. Chem., VOLUME 42, Number 2 (2017)was noted for its production of soap and high-qualityglycerine (suitable for conversion to nitroglycerine anddynamite), had been founded in 1855 with the aid of theProfessor of Chemical Technology at Kazan, ModestYakovlevich Kittary (Киттары, Модест Яковлевич,1825-1880). The plant was nationalized by the Sovietgovernment in 1919.117Before the Russian Revolution, rosin and turpentine,obtained from the gum resin produced by Scots pine(Pinus sylvestris), were imported—despite the abundanceof this species in Russia. This was due, in large part, tothe belief that the severity of the Russian climate wouldrender the process unprofitable. In 1924, the SupremeCouncil of the National Economy sought to test this.Under the leadership of Arbuzov and his son, Boris Aleksandrovich Arbuzov (Арбузов, Борис Александрович,1903-1991, Figure 10), an acre of the Raifa forest nearKazan was set up for experiments to investigate this in theVolga region, and to develop the most rational methodsof producing gum-resin. After numerous experiments,Arbuzov showed that it was, in fact, possible to extractgum resin from conifers in forests in the middle of Russia(29). Thanks, in part, to B. A. Arbuzov’s continuation ofthis work, Russia became a large producer of turpentinebefore World War II (4c).Figure 8. Arbuzov (front row, third from left) with theworkers and specialists of the Krestovnikov Brothers plant.It was Arbuzov’s task to direct the production ofphenol, salicylic acid and aspirin from benzene, itselfobtained from local crude oil. The aspirin produced therewas an essential medicine, and in quality it proved tobe the equal of the important Bayer product that it wasintended to replace. As an aside, a sample of Arbuzov’sphenol is kept at the Butlerov Museum of the KazanSchool of chemistry, and above a pool of dark liquid, itconsists of the only pure white, crystalline sample of thiscompound that this author has ever seen.Figure 10. Boris Aleksandrovich Arbuzov (1903-1991)In 1929, Arbuzov published two papers reportingthe synthesis of ethyl phosphonoacetate by alkylationof the sodium salt of diethyl phosphite with ethyl abromoacetate (30). This was an extension of the earlyindependent work of Swedish chemist, Paul Nylen(1892-1976) who had formed a-phosphonocarboxylateesters by the alkylation of the sodium or potassium salt ofphosphonoacetate esters with methyl iodide and benzylchloride (31) (Scheme 5).Figure 9. An aspirin kettle at the Krestovnikov Brothersplant (left) and the aspirin box designed by Arbuzov (right).Scheme 5. The alkylation of the sodium salt of dialkylphosphites, and salts of a-phosphonocarboxylate esters.

118The same year, he reported two important observations on the reaction of triphenylmethyl derivatives withtrivalent phosphorus compounds. In the first (32), Arbuzov and his son reported studies aimed at elucidating thestructure of “Boyd’s acid chloride,” a compound reportedby Boyd and Chignell to have predominantly (78%) thetrivalent phosphorus structure, Ph3CO–PCl2 (33) ratherthan the phosphonyl dichloride, Ph3C–P(:O)Cl2.One key observation leading to this deduction wasthe fact that, on boiling in ethanol, triphenylmethyl ethylether was obtained from this acid chloride. The Arbuzovsproposed that the product was, in fact, the phosphonyldichloride. In 1933, Hatt (34) provided evidence that theArbuzovs had been correct, and also suggested a mechanism involving the triphenylmethyl cation, that rationalized the formation of the ethyl ether. In 1947, Arbuzovand Nikonorov provided evidence that the phosphonylstructure was, in fact, correct (48).As part of their analysis, the Arbuzovs suggestedthat a free radical reaction may be required to rearrangethis product. Their study of the reaction between thesodium salt of a dialkylphosphite and a triarylmethylhalide, published the same year (35), revealed that thisdid, indeed, provided a useful method for the generationof free radicals (Scheme 6). The formation of the triphenylmethyl radical was demonstrated by the isolation ofbis(triphenylmethy) peroxide from the product mixture.Bull. Hist. Chem., VOLUME 42, Number 2 (2017)Arbuzov in World War IIIn June 1941, when Arbuzov was already 63 yearsold, Operation Barbarossa began, bringing Russia intothe war on the Allied side. The German advance causedmajor interruptions to the scientific life of the SovietUnion. As the Nazis advanced towards Moscow andLeningrad during July 1941, the decision was taken toevacuate the Academy of Sciences from those two citiesto Kazan. A total of eleven Institutes and the Academylaboratories were evacuated from Moscow to Kazan bythe middle of July.From the beginning, Arbuzov was the key individualat Kazan during these evacuations, finding places for theevacuated scientists to live and work. During this time,beds were so scarce in Kazan that the scientists weresleeping in shifts (36), and all were assigned to a termof work in the fields during the summers (37) to helpfeed the ballooning population. Less than a year after theevacuation, he received the news that he had been electeda Full Academician of the USSR Academy of Sciences.Arbuzov continued his research during the war, andin 1943 he personally developed and perfected a methodof obtaining dipyridyl. He also led a team of scientistswho were seconded to carry out secret, war-relatedresearch. Not surprisingly, there are no contemporaryaccounts of this work. Beginning during this period, andcontinuing for the remainder of his life, Arbuzov devotedconsiderable effort to recording the history of organicchemistry in Russia, including his 1948 classic book (38).The Post-war YearsScheme 6. The generation of triarylmethyl radicals fromtriarylmethyl halides and sodium dialkylphosphites.Arbuzov served as Professor of Chemistry at KazanUniversity until 1930, the last eight of those years asDean of the Physico-Mathematical Faculty. In 1930, hebecame Professor of Chemistry and Director of the KazanTechnical Institute of the USSR Academy of Sciences.Two years later, in 1932, he was elected a CorrespondingMember of the USSR Academy of Sciences.After the war, in 1945, Arbuzov was named thepermanent Director of the Kazan Technical Institute ofthe USSR Academy of Sciences. This may have been arecognition of his performance during the administrativenightmare that was the evacuations from Moscow andLeningrad. His strong administrative skills were evidentin this position, and in 1959 he was appointed as Head ofthe Institute of Organic Chemistry of the USSR Academyof Sciences. In 1965, the two Institutes merged, and thenew body was named the A. Ye. Arbuzov Institute of Organic and Physical Chemistry in his honor; it celebratedits 50th anniversary in 2015.Arbuzov rose to a position of great prominencetowards the end of his life. He was five times a Deputyto Convocations 2-6 of the Supreme Soviet—the SovietUnion’s highest legislative body—between 1946 and

Bull. Hist. Chem., VOLUME 42, Number 2 (2017)1191966. He was awarded the Stalin Prize, second class, in1943, and first class in 1947, and he received the Orderof Lenin five times. In 1957, he was awarded the Heroof Socialist Labor medal, the highest civilian decorationof the Soviet Union.Arbuzov the ManThere were three passions in Arbuzov’s life: chemistry, music, and painting. He often said: “I cannot imaginea chemist who is not familiar with the heights of poetry,with pictures of masters of painting, and with good literature.” The walls of the Dom-muzei (Home-museum)of the Academicians Arbuzov (Figure 11) are adornedwith his paintings.Figure 12. The string quartet of Kazan scientists. (l-r) V.V. Yevlampiev, A. E. Arbuzov, Prof. Burgsdoror and L. N.Parfent’ev. Arbuzov’s son, Boris, is in the background.Figure 11. The Dom-muzei (Home-museum) of theAcademicians Arbuzov.There is a grand piano in the Dom-muzei, whichwas played by his wife, Yekaterina Petrovna (Krotova),and his granddaughter, Marina Borisovna (1935-1997).Arbuzov’s favorite instrument was the violin, and he hadgone to the length of taking lessons from a professionalteacher. He organized an amateur string quartet of Kazan scientists in which he played second violin (Figure12). One of Arbuzov’s favorite pieces was one writtenby the chemist-composer, Aleksandr Porfir’evich Borodin (1833-1887): the nocturne from String Quartet #2.Arbuzov’s copy of the music for this piece is still keptat the Dom-Muzei in Kazan. During World War II, heorganized concerts in Kazan for the military personneland scientists assembled there.Figure 13. Arbuzov’s family: (back) Ekaterina Petrovna;(front, l-r) Boris, Yurii and Irina.Arbuzov had three children: Boris, Yurii Aleksandrovich (1907-1971) and Irina Aleksandrovna (19051989) (Fig, 13). All three became chemists. Boris followed his father into the Chair of Organic Chemistry, andwas himself elected to the USSR Academy of Sciences.Yurii became a Professor at Moscow State University;Irina began her research career with her father, and thenmoved to Leningrad (St. Petersburg), where she workedin the Institute of Organic Chemistry, and, later, theInstitute of Macromolecular Compounds of the USSRAcademy of Sciences.Arbuzov died on January 21, 1968, and was buriedin the Arsk Kazan cemetery (Figure 14); his children andgranddaughter are buried with him.

Bull. Hist. Chem., VOLUME 42, Number 2 (2017)120Figure 14. The graves of Arbuzov and his family at the ArskKazan cemetery, June 2017.Arbuzov’s Scientific LegacyLike some his predecessors at Kazan (Butlerov,Markovnikov and Zaitsev, at least), Arbuzov inspiredgreat loyalty in his students, and he was admired by hiscolleagues.Arbuzov’s legacy in organophosphorus chemistrywas ensured by the continuing work of his students,among whom were his son, Boris Aleksandrovich,Gil’m Khairovich Kamai (Камай, Гильм Хайревич,1901-1970, Figure 15), and B. A. Arbuzov’s student,Arkadii Nikolaevich Pudovik (Пудовик, АркадийНиколаевич, 1916-2006, Figure 15), whose careers wereall at Kazan State University, and Vasilii SemyonovichAbramov (Абрамов, Василий Семёнович,1904-1968,Figure 15), whose career was spent at Kazan ChemicalTechnological Institute.Boris Aleksandrovich Arbuzov faithfully continuedhis father’s legacy of organophosphorus chemistry atKazan, as well as expanding the research into naturalproducts (especially terpenes), petroleum chemistry andpolymer chemistry. His important contributions to thedevelopment of the turpentine industry in Russia havealready been alluded to.Figure 15. Top: Gil’m Khairevich Kamai (1901-1970).Bottom (l-r): Arkadii Nikolaevich Pudovik (1916-2006) andVasilii Semyonovich Abramov (1904-1968).In a series that eventually rose to a total of 40 papersbetween 1950 (39) and 1969 (40), Abramov reportedthat dialkyl phosphites react with aldehydes and ketonesto give a-hydroxyalkylphosphonate esters (Scheme 7).Scheme 7. The Abramov reaction.Pudovik modified the reaction by incorporating abase, and this allowed the reaction to be used with iminesto generate a-aminoalkylphosphonate esters (Scheme8) (41). The Pudovik reaction has been used to generatechiral a-hydroxyalkyl- and a-aminoalkylphosphonateesters with good enantioselectivity (42).

Bull. Hist. Chem., VOLUME 42, Number 2 (2017)121Scheme 9. The Arbuzov-Fischer reactionScheme 8. The Pudovik reaction.After early work with his mentor (43) in the areaof organophosphorus chemistry, Kamai (who becamethe youngest Rector in the history of Kazan University)moved his research focus to organoarsenic chemistry(44).The contributions of Arbuzov and his son inorganophosphorus chemistry are celebrated by theaward of the International Arbuzovs Prize in the fieldof organophosphorus chemistry (Figure 16). The awardhas been presented biennially on the anniversary of A.Ye. Arbuzov’s birth since 1997.Scheme 10. The conversion of aldehyde phenylhydrazonesto nitriles and aniline.Photo and Image CreditsFigures 1, 3, 5 (left), 6, 7, 8, 9, 10, 12, 15 and 16: the ButlerovMuseum of the Kazan School of Chemistry, Kazan Federal University—reproduced by permission.Figures 2 and 13: the Dom-muzei of the Academicians A. Yeand B. A. Arbuzov, Kazan—reproduced by permission.Figure 4: (right), Wikimedia Commons— public domain.Figure 5 (right): Offizielles Portrait des Rektors der UniversitätRostock, August Michaelis—public domain.Figure 11: Deborah A. Lewis—reproduced by permission.Figure 14: the author—reproduced by permission.References and Notes1.Russia uses the Cyrillic alphabet, and transliterationsare a perennial problem. In this manuscript, the BGN/PCGN romanization system for Russian has been used asthe most intuitive for English speakers,

Rostock. In 1876, as part of a lengthy article (16), Mi-chaelis had proposed that the structure of phosphorous acid was HPO(OH)2, and in a later paper (17), he studied the reactions of phosphorous acid esters, and noted that diethyl ethylphosphonate, prepared by reaction of diethy