Alexander Mikhailovich Zaitsev
Encyclopedia
Alexander Mikhaylovich Zaitsev , also spelled as Zaitsev, Saytzeff, and Saytzev (1841 – 1910), was a Russian chemist from Kazan
. He worked on organic compounds and proposed the Zaitsev's rule
, which predicts the product composition of an elimination reaction
.
Early on, Zaitsev began working with Butlerov, who clearly saw in him an excellent laboratory chemist, and whose later actions showed that he felt that Zaitsev was an asset to Russian organic chemistry
. On the death of his father, Zaitsev took his diplom in 1862, and immediately went to western Europe to further his chemical studies, studying with Hermann Kolbe at Marburg, and with Charles Adolphe Wurtz in Paris. This went directly against the accepted norms of the day, which had the student complete the kandidat degree (approximately equivalent to today's doctor of philosophy's degree), and then spend two or three years in study abroad (a komandirovka) before returning to Russia
as a salaried laboratory assistant studying for the doctorate.
From 1862-1864, he studied with Kolbe at Marburg, and here Zaitsev discovered the sulfoxide
s and trialkylsulfonium salts. In 1864, he moved to Paris
, where he worked for a year in the laboratories of Wurtz before returning to Marburg in 1865. At this time, Kolbe accepted the call to Leipzig, and Zaitsev, now out of money, returned to Russia. On his return, Zaitsev again joined Butlerov as an unpaid assistant. During this time, he wrote a successful kandidat dissertation.
(on March 1866 the Kazan University board voted for this appointment.) Two years later, Zaytsev was awarded his M. Chem. degree, and, the following year (1869) was appointed as Extraordinary Professor of Chemistry, the junior colleague of another Butlerov student, Vladimir Vasilyevich Markovnikov (1838–1904). Zaytsev submitted his Dr. Chem. dissertation in 1870, and was awarded the degree over the indirect objections of Markovnikov (as second examiner of the dissertation, Markovnikov had written an overtly positive assessment that was meant to be read between the lines). The same year, he was promoted to Ordinary Professor of Chemistry. This may have been one of the final straws for Markovnikov, who left Kazan' university in 1871 for Odessa. Zaytsev continued at Kazan' university until his death in 1910.
s. The first of these reactions had been reported by Butlerov in 1863, who prepared tert-butyl alcohol from dimethylzinc
and phosgene
. Zaytsev and his students Egor Egorevich Vagner (Georg Wagner, 1849–1903) and Sergei Nikolaevich Reformatskii (1860–1934) extended this reaction to a general synthesis of alcohols using alkylzinc iodides. This synthesis was the best way to make alcohols until the advent of the Grignard reaction
in 1901. Reformatskii's work, which used the zinc compounds from alpha-bromoesters, led to the discovery of a synthetic reaction (the Reformatskii reaction
) that is still used today. Zaitsev's Rule
was reported in 1875, and appeared just as his arch-nemesis, Markovnikov, (who had made a prediction which the rule contradicts) was taking the Chair at Moscow University. Zaytsev received several honors: he was elected as a Corresponding member of the Russian Academy of Science, an honorary member of Kiev University, and he served two terms as President of the Russian Physical-Chemical Society.
Kazan
Kazan is the capital and largest city of the Republic of Tatarstan, Russia. With a population of 1,143,546 , it is the eighth most populous city in Russia. Kazan lies at the confluence of the Volga and Kazanka Rivers in European Russia. In April 2009, the Russian Patent Office granted Kazan the...
. He worked on organic compounds and proposed the Zaitsev's rule
Zaitsev's rule
In chemistry, Zaitsev's rule, Saytzeff's rule or Saytsev's rule named after Alexander Mikhailovich Zaitsev is a rule that states that if more than one alkene can be formed during dehalogenation by an elimination reaction, the more stable alkene is the major product...
, which predicts the product composition of an elimination reaction
Elimination reaction
An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one or two-step mechanism...
.
Early years
Zaitsev was the son of a tea and sugar merchant, who had decided that his son should follow him into the mercantile trades. However, at the urging of his maternal uncle, the physicist Lyapunov, Zaitsev was allowed to enroll at Kazan' university to study economics. At this time, Russia was experimenting with the cameral system, meaning that every student graduating in law and economics from a Russian university had to take two years of chemistry. Zaitsev was thus introduced to Aleksandr Mikhailovich Butlerov.Early on, Zaitsev began working with Butlerov, who clearly saw in him an excellent laboratory chemist, and whose later actions showed that he felt that Zaitsev was an asset to Russian organic chemistry
Organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, composition, reactions, and preparation of carbon-based compounds, hydrocarbons, and their derivatives...
. On the death of his father, Zaitsev took his diplom in 1862, and immediately went to western Europe to further his chemical studies, studying with Hermann Kolbe at Marburg, and with Charles Adolphe Wurtz in Paris. This went directly against the accepted norms of the day, which had the student complete the kandidat degree (approximately equivalent to today's doctor of philosophy's degree), and then spend two or three years in study abroad (a komandirovka) before returning to Russia
Russia
Russia or , officially known as both Russia and the Russian Federation , is a country in northern Eurasia. It is a federal semi-presidential republic, comprising 83 federal subjects...
as a salaried laboratory assistant studying for the doctorate.
From 1862-1864, he studied with Kolbe at Marburg, and here Zaitsev discovered the sulfoxide
Sulfoxide
A sulfoxide is a chemical compound containing a sulfinyl functional group attached to two carbon atoms. Sulfoxides can be considered as oxidized sulfides...
s and trialkylsulfonium salts. In 1864, he moved to Paris
Paris
Paris is the capital and largest city in France, situated on the river Seine, in northern France, at the heart of the Île-de-France region...
, where he worked for a year in the laboratories of Wurtz before returning to Marburg in 1865. At this time, Kolbe accepted the call to Leipzig, and Zaitsev, now out of money, returned to Russia. On his return, Zaitsev again joined Butlerov as an unpaid assistant. During this time, he wrote a successful kandidat dissertation.
Career
In order to teach, he required either a master's degree from a Russian university, or a Ph. D. from a foreign university, so he wrote up his work on the sulfoxides and submitted it to the University of Leipzig where (probably thanks to Kolbe's influence) he was awarded the Ph. D. in 1866. With Zaytsev now holding the Ph. D., Butlerov was able to secure his appointment as an assistant in agronomyAgronomy
Agronomy is the science and technology of producing and using plants for food, fuel, feed, fiber, and reclamation. Agronomy encompasses work in the areas of plant genetics, plant physiology, meteorology, and soil science. Agronomy is the application of a combination of sciences like biology,...
(on March 1866 the Kazan University board voted for this appointment.) Two years later, Zaytsev was awarded his M. Chem. degree, and, the following year (1869) was appointed as Extraordinary Professor of Chemistry, the junior colleague of another Butlerov student, Vladimir Vasilyevich Markovnikov (1838–1904). Zaytsev submitted his Dr. Chem. dissertation in 1870, and was awarded the degree over the indirect objections of Markovnikov (as second examiner of the dissertation, Markovnikov had written an overtly positive assessment that was meant to be read between the lines). The same year, he was promoted to Ordinary Professor of Chemistry. This may have been one of the final straws for Markovnikov, who left Kazan' university in 1871 for Odessa. Zaytsev continued at Kazan' university until his death in 1910.
Research
His research at Kazan was primarily concerned with the development of organozinc chemistry and the synthesis of alcoholAlcohol
In chemistry, an alcohol is an organic compound in which the hydroxy functional group is bound to a carbon atom. In particular, this carbon center should be saturated, having single bonds to three other atoms....
s. The first of these reactions had been reported by Butlerov in 1863, who prepared tert-butyl alcohol from dimethylzinc
Dimethylzinc
Dimethylzinc, also known as Zinc methyl, DMZ, or DMZn is a colorless mobile liquid Zn2, formed by the action of methyl iodide on zinc at elevated temperature or on zinc sodium alloy....
and phosgene
Phosgene
Phosgene is the chemical compound with the formula COCl2. This colorless gas gained infamy as a chemical weapon during World War I. It is also a valued industrial reagent and building block in synthesis of pharmaceuticals and other organic compounds. In low concentrations, its odor resembles...
. Zaytsev and his students Egor Egorevich Vagner (Georg Wagner, 1849–1903) and Sergei Nikolaevich Reformatskii (1860–1934) extended this reaction to a general synthesis of alcohols using alkylzinc iodides. This synthesis was the best way to make alcohols until the advent of the Grignard reaction
Grignard reaction
The Grignard reaction is an organometallic chemical reaction in which alkyl- or aryl-magnesium halides add to a carbonyl group in an aldehyde or ketone. This reaction is an important tool for the formation of carbon–carbon bonds...
in 1901. Reformatskii's work, which used the zinc compounds from alpha-bromoesters, led to the discovery of a synthetic reaction (the Reformatskii reaction
Reformatskii reaction
The Reformatsky reaction is an organic reaction which condenses aldehydes , 1, with α-halo esters, 2, using a metallic zinc to form β-hydroxy-esters, 3...
) that is still used today. Zaitsev's Rule
Zaitsev's rule
In chemistry, Zaitsev's rule, Saytzeff's rule or Saytsev's rule named after Alexander Mikhailovich Zaitsev is a rule that states that if more than one alkene can be formed during dehalogenation by an elimination reaction, the more stable alkene is the major product...
was reported in 1875, and appeared just as his arch-nemesis, Markovnikov, (who had made a prediction which the rule contradicts) was taking the Chair at Moscow University. Zaytsev received several honors: he was elected as a Corresponding member of the Russian Academy of Science, an honorary member of Kiev University, and he served two terms as President of the Russian Physical-Chemical Society.