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4:19 PM
190 лет со дня рождения Александра Михайловича Бутлерова / 190 years since the birth of Alexander Mikhailovich Butlerov
 
Алекса́ндр Миха́йлович Бу́тлеров (3 сентября [15 сентября] 1828, Чистополь5 августа [17 августа] 1886, деревня Бутлеровка, ныне Алексеевский район Татарстана) — русский химик, создатель теории химического строения органических веществ, родоначальник «бутлеровской школы»[4] русских химиков, учёный-пчеловод и лепидоптеролог, общественный деятель, ректор Императорского Казанского университета в 1860—1863 годах.

Родился в семье помещика, офицера в отставке — участника Отечественной войны 1812 года, в Чистополе Казанской губернии. Детство его протекало сначала в деревне Бутлеровке — имении отца, затем в Казани.

Первоначальное образование получил в частном пансионе Топорнина — учителя французского языка 1-й Казанской гимназии, а затем и в самой гимназии, в 1844—1849 годах студент Казанского университета «разряда естественных наук». Получая широкую подготовку в области естествознания, он в первые годы проявил большой интерес к ботанике и зоологии. В 1849 году написал дипломную работу «Дневные бабочки волго-уральской фауны». Эта особенность полученного образования, по-видимому, была одной из причин того, что, уже став химиком с мировым именем, А. М. Бутлеров по-прежнему сохранял интерес к живой природе и, в частности, был одним из организаторов и постоянных сотрудников журнала «Пчеловодный листок».

По окончании университета Бутлеров был оставлен «при университете для подготовки к профессорскому званию». В 1854 году он сдал экзамен и защитил диссертацию на степень доктора химии. В последующие годы А. М. Бутлеров много размышлял над теоретической стороной химии и уже в 1858 году, во время первой поездки за границу, высказал на заседании Парижского химического общества свои теоретические взгляды, которые через три года в более развитом виде стали предметом его известного доклада «О химическом строении вещества».

С 1849 года он — преподаватель, с 1854 года — экстраординарный, а с 1857 года — ординарный профессор химии в Казанском университете; в 1860—1863 годах был ректором университета.

В Петербурге А. М. Бутлеров развернул работы по непредельным соединениям, начатые ещё в Казани, а также продолжил теоретические работы.

В 1885 году вышел в отставку, но продолжал читать в университете специальные курсы лекций. В 1870 был избран адъюнктом, в 1871 — экстраординарным, а в 1874 — ординарным академиком Петербургской АН. В 1878—1882 годах — преемник Н. Н. Зинина на посту председателя Отделения химии Русского химического общества. Почётный член многих других научных обществ в России и за рубежом.

14 мая 1885 г., заканчивая свою последнюю лекцию, А. М. Бутлеров с гордостью говорил о росте русской химической науки и предсказывал ей блестящее будущее. 17 августа 1886 г. А. М. Бутлеров умер в деревне Бутлеровке Казанской губернии. Созданные при его участии крупнейшие русские химические школы — Казанская, Петербургская, Московская (обязанная своим расцветом В. В. Марковникову) — продолжили развитие органической химии, внося достойный вклад не только в отечественную, но и в мировую науку.

Ещё будучи воспитанником пансиона начал интересоваться химией: вместе с коллегами пытались изготовить то порох, то «бенгальские огни». Однажды, когда один из опытов привел к сильному взрыву, воспитатель сурово наказал его. Три дня подряд Сашу выводили и ставили в угол на всё время пока другие обедали. На шею ему вешали чёрную доску, на которой было написано «Великий химик». Впоследствии эти слова стали пророческими. В Казанском университете Бутлеров увлёкся преподаванием химии, профессорами которой были К. К. Клаус и Н. Н. Зинин. С 1852 года, после перехода Клауса в Дерптский университет, Бутлеров возглавил преподавание всей химии в Казанском университете. В 1851 Бутлеров защитил магистерскую диссертацию «Об окислении органических соединений», а в 1854 в Московском университете — докторскую диссертацию «Об эфирных маслах». Во время заграничной поездки в 1857—1858 сблизился со многими видными химиками, в том числе с Ф. А. Кекуле и Э. Эрленмейером, и провёл около полугода в Париже, деятельно участвуя в заседаниях только что организованного Парижского химического общества. В Париже, в лаборатории Ш. А. Вюрца, Бутлеров начал первый цикл экспериментальных исследований. Открыв новый способ получения йодистого метилена, Бутлеров получил и исследовал многочисленные его производные; впервые синтезировал гексаметилентетрамин (уротропин) и тример формальдегида (триоксиметилен). В работе, опубликованной в 1861 году Бутлеров показал, что триоксиметилен при обработке известковой водой переходит в сахаристое вещество (реакция Бутлерова), которое он назвал метиленитаном (позднее Э. Фишер установил, что метиленитан — неоднородное вещество, содержащее α-акрозу и формозу). В этой статье Бутлеров отметил, что получение метиленитана — первый полный синтез сахаристого вещества.

Первое публичное выступление А. М. Бутлерова по теоретическим вопросам органической химии относится к концу 50-х годов: его доклад на заседании Парижского химического общества 17 февраля 1858 г. В нём говорится, что за радикалы следует считать не только органические группы, но и группировки типа OH,NH2, то есть характерные для различных классов органических веществ сочетания атомов, которые впоследствии получили название функциональных групп. В этом же докладе Бутлеров впервые употребил и сам термин «структура», относя к одному типу молекулярной структуры метан, хлористый метил, хлористый метилен, хлороформ, четырёххлористый углерод, метиловый спирт.

Таким образом, уже в 1858 г. А. М. Бутлеров вышел за пределы представлений Ш. Ф. Жерара в весьма существенном пункте: он считал возможным говорить об определённой группировке атомов в сложных частицах, причём причину этой группировки видел в химическом сродстве. В этих словах содержалась, по существу, одна из основных идей теории химического строения.

В более развитой форме идея химического строения была изложена А. М. Бутлеровым три года спустя в докладе «О химическом строении вещества», с которым он выступил, прочитанном в химической секции Съезда немецких естествоиспытателей и врачей в Шпейере (19 сентября 1861) и опубликованном в том же году на немецком и в следующем — на русском языках.

Большое значение для становления теории химического строения имело её экспериментальное подтверждение в работах как самого Бутлерова, так и его школы. Он предвидел, а затем и доказал существование позиционной и скелетной изомерии. Получив третичный бутиловый спирт, он сумел расшифровать его строение и доказал (совместно с учениками) наличие у него изомеров. В 1844 Бутлеров предсказал существование двух бутанов и трёх пентанов, а позднее и изобутилена. Чтобы провести идеи теории химического строения через всю органическую химию, Бутлеров издал в 1864—1866 в Казани 3 выпусками «Введение к полному изучению органической химии», 2-е издание которого вышло в 1867—1868 на немецком языке.

Бутлеров впервые начал на основе теории химического строения систематическое исследование полимеризации, продолженное в России его последователями и увенчавшееся открытием С. В. Лебедевым промышленного способа получения синтетического каучука.

https://ru.wikipedia.org

 

 

Butlerov, Aleksandr Mikhailovich

(b. Chistopol, Kazanskaya [now Tatarskaya, A.S.S.R.], Russia, 6 September 1828; d.a Butlerovka, Kazanskaya, Russia, 17 August 1886)

Butlerov’s father, Mikhail Vasilievich Butlerov, a retired lieutenant colonel, and mother, Sofia Mikhailovna, owned part of Butlerovka village. Butlerovka received his primary education in a private boarding school, later attended a Gymnasium in Kazan, and studied at Kazan University from 1844 to 1849.

Immediately after graduating from the university, Butlerov began teaching chemistry there, at first (1849–1850) part-time, then as Carl Claus’s official assistant; from 1852, after Claus’s transfer to Dorpat University, he taught all the chemistry courses in the university. Between 1860 and 1863 he was twice rector of the university. From 1868 to 1885 Butlerov was a professor of chemistry at St. Petersburg University. In 1885, after thirty-five years of service, he retired but continued to teach special lecture courses at the university.

In 1852 he married Nadezhda Mikhailovna Glumilina, niece of the writer S.T. Aksakov.

In 1870 Butlerov was selected a junior scientific assistant of the St. Petersburg Academy of Sciences; the following year he became an associate member, and in 1874 a full member. From 1857 he was a member of the Chemical Society of Paris, and from 1869 of the Russian Chemical Society. He was chairman from 1878 to 1882 of the chemistry section of the Russian Physics and Chemistry Society, formed in 1878 by the merging of the chemistry and physics societis. Butlerov was also an honorary or foreign member of the Chemical Society of London (from 1876), the American Chemical Society (1876), the Czech Chemical Society (1880), the German Chemical Society (1881), the Russian Physics and Chemistry Society (1882), the Russian Technical Society (1885), and of many others.

In the early 1850’s Butlerov adhered to obsolete theoretical views (he, as well as Claus, taught chemistry from a textbook by C. Löwig, the author of one version of the theory of radicals); but in 1854, on Zinin’s advice, he familiarized himself with the work of Laurent and Gerhardt and became one of their passionate supporters. However, the greatest changes in his work and thought resulted from his trip abroad in 1857–1858. During his travels Butlerov met such eminent young chemists as Kekulé and Erlenmeyer and spent about half a year in Paris, participating in the meetings of the Paris Chemical Society, which had just been formed, and working for two months in Wurtz’s laboratory.

In Wurtz’s laboratory Butlerov began his first series of experimental investigations. Discovering a new way to obtain methylene iodide, he studied many derivatives of methylene and their reactions. As a result, he was the first to obtain hexamethylenetetramine (urotropine) and a polymer of formaldehyde which in the presence of limewater is transformed into a sacchariferous substance (containing, as was established by E. Fischer, α-acrose). This was the first complete synthesis of a sacchariferous substance.

On the other hand, Butlerov did not succeed in obtaining either dihydroxymethylene, CH2 (OH)2, or the free methylene radical itself, instead of which he obtained its dimer—ethylene. However, both of these negative results served as material for future generalizations. These investigations showed the trait characteristic of Butlerov’s work, the effort to study a reaction in full, not neglecting its by-products. They were usually completed with very small quantities of the substances involved and enabled him to perfect his skill in experimentation.

Work on the methylene series ended in 1861, when Butlerov stated the basic ideas of the theory of chemical structure and directed his experimental investigations toward the verification and support of his new theory. He arrived at the theory of chemical structure through continuous research and a recognition of the unsatisfactory state of theoretical chemistry. Although he developed a theory of types similar to Gerhardt’s, defended it in print, and on returning from abroad employed it as the basis of a lecture course in organic chemistry, he clearly recognized that he must go beyond Gerhardt.

Butlerov attempted to develop Dumas’s theory of carbonaceous types, but all conventional viewpoints proved unsatisfactory for the explanation of addition reactions, which he had come across in describing the results of his work on the methylene series. Summing up his research, he arrived at the theory of chemical structure, which, according to Markovnikov, he began to expound in his lectures as early as 1860.

In this paper (Sochinenia, I, 561), Butlerov defined the concept of chemical structure: “Assuming that each chemical atom is characterized by a specific and limited quantity of chemical force [affinity], with which it participates in the formation of a substance, I would call this chemical bond or [this] capacity for the mutual union of atoms into a complex substance chemical structure”.

From this definition it follows that the concept of chemical structure (the term is found in the work of Russian chemists before Butlerov, but it is used in another sense) could be brought forward only after there had been a sufficiently clear definition of the concepts “atom” (the attribute “chemical” left open the question of the possibility of its further separation into “physical” atoms), “valency” (the quantity of an atom’s affinity), and “interatomic bond”. Thus, the following can be considered as the preconditions for the existence of a theory, within chemistry itself, of chemical structure: (1) sufficiently clear concepts of atomic theory and molecular theory—which was achieved at the Congress of Chemists in Karlsruhe (1860); (2) development of the study of valency in the form ascribed to valency by Kekulé (1857–1858); (3) the creation of the concept of interatomic bond, as it was formulated in the works of Kekulé and Couper (1858).

This proposition, as is evident from its wording, broke with the traditional view that the properties of molecules are determined principally by the nature of the space grouping of atoms in the molecules, by the relative position of the atoms, and by the distances separating the atoms; these problems could not be studied by methods then available. All the remaining propositions of the classical theory of chemical structure are directly or indirectly associated with this proposition.

Butlerov noted means for determining the chemical structure of molecules and formulated the rules that should be followed in this determination. He gave primary importance to those synthetic reactions in which the participating radicals retain their chemical structure. He foresaw the possibility of regrouping but believed that after a detailed study of matter from the point of view of chemical structure, the general laws for regrouping would be deduced.

Leaving open the question of the preferred structural formulas, Butlerov explicitly expressed his opinion about their sense: When the general laws of the relationship between the chemical properties of substances and their chemical structure became known, the corresponding formula would be an expression of all these properties.

The only incorrect proposition in Butlerov’s paper was the supposition concerning the possibility of a primordial (i.e., inherent in free atoms) difference in units of affinity (valency). In connection with this hypothesis Butlerov was the first to produce a model of a carbon tetrahedron (it was irregular). Having subjected the hypothesis to experimental verification and having rejected it, he further developed the theory of chemical structure in a long article, “Über die verschiedenen Erklärungsweisen einiger Fälle von Isomerie”. However, the propositions stated in the article were implied in his paper delivered at Speyer.

Guided by the propositions he had formulated, Butlerov explained the existence of isomerism, stating that isomers were compounds possessing the same elementary composition but different chemical structure. Discovery of the facts of isomerism, which did not correspond to this definition, led to the establishment by van’t Hoff and Le Bel of stereochemistry, which Butlerov did not accept immediately and, when he did, only in part; specifically, he accepted only the explanation of the optical activity of organic compounds as the result of the presence of asymmetric carbon atoms.

Butlerov explained the relationship of the properties of isomers—and of organic compounds in general—to their chemical structure by the existence of “the mutual influence of atoms”, which is transmitted along the bonds; as a result of this influence, atoms possess different “chemical values” depending on their structural environment. This general proposition was given concrete expression in the form of many “rules” by Butlerov himself and, especially, by his students Markovnikov and Popov. In this century these rules, as well as the whole concept of atoms” mutual influence, have received an electron interpretation.

Of great importance for the consolidation of the theory of chemical structure was its experimental corroboration in the work of Burtlerov’s school. Butlerov himself deserves credit for the prediction and proof of positional and skeletal isomerism. Having unexpectedly obtained tertiary butyl alcohol, he was able to decipher its structure and predicted (later proving, with the aid of his students) the existence of its homologues; he also predicted (1864) the existence of two butanes and three pentanes and, later, that of isobutylene.

In the second half of the 1860’s the nature of unsaturated compounds was still unexplained. A series of investigations conducted by Butlerov, completed at the beginning of the 1870’s, led to a conclusion supporting the hypothesis that they contain multiple bonds.

Butlerov’s indication that sulfur had a valence of six and his experimental proof of the tetravalence of lead must be considered contributions to the theory of valency. Throughout the 1860’s he gave much attention to organometallic compounds and developed methods, widely used by his school, for synthesizing organic zinc compounds.

In order to promulgate the theory of chemical structure throughout organic chemistry, Butlerov published Vvedenie k polnomu izucheniyu organicheskoy khimy (“An Introduction to the Complete Study of Organic Chemistry”:), the second edition of which was published in German under the title Lehrbuch der organischen Chemie. E. von Meyer, a student of Kolbe’s school (which rejected the theory of chemical structure), considered the work to be a magnificent textbook on organic chemistry that greatly influenced the development and popularization of the structural theory.

Butlerov’s second great service—this time to chemistry in Russia—was the creation of the first Russian school of chemists. After his return from abroad in 1858, he equipped his laboratory with gas and expanded it; his students had to complete required practical work; and his first “disciples” appeared. Of these, V. V. Markovnikov, A. M. Zaytsev, and A. P. Popov occupied professional chairs in universities during Butlerov’s lifetime. Nonetheless, in the 1860’s Butlerov sought to leave Kazan. One reason for this was his unsuccessful term as rector. In March 1860 he had become the last “crown” (i.e., appointed by the imperial government) rector of Kazan University; however, striving not only to institute liberal changes but also to halt student abuse of individual teachers, Butlerov came into severe conflict with the student body. This forced him to request retirement, which was granted in August 1861. Nonetheless, in November 1862 Butlerov became—against his wishes—the first elected rector of the university. The outbreak of a struggle between groups of professors and Butlerov’s clash with a trustee led to his retirement in July 1863. He was bitted about the experience and tried to find a position outside Kazan. Only the insistence of his friends (as well as the birth of a son in April 1864) stopped him from departing immediately.

In May 1868 Butlerov was made professor of chemistry at St. Petersburg University. He continued teaching there until 1885, when he retired on pension but continued to give special lecture courses. His followers at St. Petersburg form a prominent group of Russian organic chemists—the most famous being A. E. Favorski and I. L. Kondakov. At various times G. G. Wagner, D. P. Konovalov, and F. M. Flavitsky worked in his laboratory. Butlerov’s outstanding characteristic as an instructor was that he taught by example; the students could always observe what he was doing and how he was doing it.

Butlerov was an advocate of higher education for women; he participated in the organization of university courses for women (1878) and lectured to them on inorganic chemistry. He also created laboratory courses in Chemistry. In addition, Butlerov delivered in St. Petersburg, as he had earlier done in Kazan, a large number of public lectures, most of which had a chemical-technical basis.

Butlerov was the organizer and propagandist for scientific apiculture in Russia. He published many articles and notices in the Russian and foreign press, and in 1886 founded the Russkii pchelovodnyi listok (“Russian Apiculture Leaflet”).

While in St. Petersburg, Butlerov had yet another unusual interest—spiritualism. He was convinced that “medium” phenomena could be studied by scientific methods and even spoke on this theme at the seventh conference of Russian naturalists (Odessa, August 1883). However, experiments with mediums, conducted in the presence of a scientific commission, ended in complete failure. Mendeleev, who participated in the commission, later wrote, “Our spiritists obviously do not see deception.” P.D. Boborykin, a student of Butlerov’s at Kazan University, defined his passion as an “atavism of religiosity.”

Category: История науки- Нistory of science | Added by: zvonimirveres
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