Nikolai Menshutkin
Encyclopedia
Nikolai Aleksandrovich Menshutkin was a Russian chemist who discovered the process of converting a tertiary amine to a quaternary ammonium salt via the reaction with an alkyl halide, now known as the Menshutkin reaction
.
, as he was still under the prescribed age of 16. He studied at the faculty of physics and mathematics and was nearly expelled in the autumn of 1861 due to some political disturbances. Nevertheless, by the spring of 1862 he attained the master degree. During the last years he became interested in chemistry, which he studied under Dmitri Mendeleev
. While he acquired a sufficient knowledge of theory he was lacking practice, as at that time the entire laboratory of the university consisted of only two small rooms. Therefore, he went abroad, and in the following three years spent two semesters with Adolph Strecker
at the University of Tübingen, a year (1864–5) with Charles-Adolphe Wurtz
at the University of Paris
, and a semester with Adolph Wilhelm Hermann Kolbe
at the University of Marburg.
In the meantime, many changes were introduced into the constitution of the Russian universities. In 1863 the universities obtained academic freedom, they chose for themselves the professors,
deans, and rectors, at the same time the means of teaching improved, and, owing to Mendeleev’s efforts, the laboratory at St. Petersburg University was enlarged. In 1865 Menshutkin returned to St. Petersburg, just after his PhD thesis was published in the Comptes Rendus of the French Academy under the title “Action du chlorure d’acetyle sur l’acide phosphoreux”. He defended it in March 1866 against Aleksandr Butlerov
and Dmitri Mendeleev and in autumn began teaching a course on organic nitrogen compounds. On 6 April 1869, he defended his habilitation
on “The Synthesis and Properties of the Ureides” and shortly was appointed as professor of analytical chemistry. In connection with his teaching he proceeded to rearrange the course of instructions and in 1871 brought out his well-known textbook, which survived 16 editions up to 1931 and had been translated into German and English. In 1871, Menshutkin became secretary of the faculty of physics and mathematics and in 1879 was appointed as dean, an office which he held until 1887.
The assassination of the Emperor Alexander II
in 1881 was followed by the adoption of severe measures, from the effects of which the universities suffered in many ways. The autonomy granted in 1863 was revoked and all officials could only be appointed by the Minister of Public Instruction; the admission of students was hindered by accepting them only from certain schools, the fees were raised and the number of professorships reduced. The discontent by professors and students resulted in disturbances in 1887-8, which were followed by the resignation of the rector and several key officials. As a result, Menshutkin had to add teaching of organic chemistry to his duties. About this time he prepared his large handbook of organic chemistry, which appeared in three successive editions, and in 1888 he published a history of the development of chemical theory. Both books were written in Russian and not translated. One of Menshutkin’s most serious undertakings of the time was the building of the new chemical laboratories of the University. Only by 1890 money could be found for this purpose and in this year Mendeleev resigned his chair, leaving Menshutkin in the position of senior professor of the university. Menshutkin managed to build the laboratories by October 1894 and worked there for eight years.
In 1902 Menshutkin was transferred to the new Polytechnic Institute, about 6 km north of St. Petersburg, while retaining the professorship in the university. There he acted as professor of analytical and organic chemistry and dean of the mining division. From the establishment of the Russian Chemical Society in 1868, and until 1891, Menshutkin served as its secretary and became its president in 1906. As deputy of a province he was able to improve popular education and help establishing several new schools. At the end of 1905 he took an active part in the elections for the first Duma
, and was one of the founders of the Party of Democratic Reform
. Menshutkin had suffered for many years from disorder of the kidneys. He survived an attack at the end of 1906, but then suddenly died in February 1907.
atoms in the molecule are equivalent and therefore the formula HP(O)(OH)2 is more likely than P(OH)3. In 1890 Menshutkin discovered that a tertiary amine can be converted into a quaternary ammonium salt by reaction with an alkyl halide.
Menshutkin further studied the influence of isomerism among alcohol
s and acids on esterification and showed that, both in respect of rate and limit, the primary
, secondary, and tertiary alcohols differ from one another, and that unsaturated differ from saturated alcohols. The molecular weight of the alcohol concerned has also a considerable influence on the result, the limit rising generally with molecular weight, although the rate is diminished. The first series of experiments were made with acetic acid
and alcohols and were extended to a variety of acids. Subsequently the rate of chemical change was studied in the case of the formation of amide
s and anilides by the action of ammonia
and aniline
on acids by means of the same method as was employed in the esterification experiments. Here again the influence of isomer
ic differences was equally manifest. These researches led on to others, such as the study of the mutual displacement of bases
in homogeneous
systems, and the influence of temperature on the rate of several reactions.
Menshutkin further studied the effect of different solvents on the reaction rate
s. Although the solvent
is unaltered after the reaction, its influence on the reaction rate was significant. The stabilization of the reactants, products and intermediate phases or transition states depended strongly on the polarity of the solvent, and therefore this polarity had a large influence on the reaction rate. Because of the formation of ionic products, the effect was especially strong in the Menshutkin reaction
making it an ideal tool to study the effect of solvent on the reaction rate. The Menshutkin reaction is still used for this purpose.
Between 1889 and 1895 Menshutkin focused on amines, on the kinetics of their interaction
with alkyl halogen
compounds and its dependence on the isomerism. Continuing these investigations down to the end of his life, he succeeded in establishing a large number of other relations between the structure or constitution and chemical activity, as well as physical properties, such as boiling point, melting point and specific gravity
. He is regarded
as a pioneer in chemical kinetics
, not for the priority, but for systematic development of this field.
Menshutkin reaction
The Menshutkin reaction in organic chemistry converts a tertiary amine to a quaternary ammonium salt by reaction with an alkyl halide:The reaction has been named after its discoverer, the Russian chemist Nikolai Menshutkin, who described the procedure in 1890...
.
Biography
Menshutkin was born in a merchant family as the sixth son of Alexander Nikolaevitch Menshutkin. He graduated with honors from gymnasium in December 1857, but only by autumn 1858 managed to enroll to the Saint Petersburg State UniversitySaint Petersburg State University
Saint Petersburg State University is a Russian federal state-owned higher education institution based in Saint Petersburg and one of the oldest and largest universities in Russia....
, as he was still under the prescribed age of 16. He studied at the faculty of physics and mathematics and was nearly expelled in the autumn of 1861 due to some political disturbances. Nevertheless, by the spring of 1862 he attained the master degree. During the last years he became interested in chemistry, which he studied under Dmitri Mendeleev
Dmitri Mendeleev
Dmitri Ivanovich Mendeleev , was a Russian chemist and inventor. He is credited as being the creator of the first version of the periodic table of elements...
. While he acquired a sufficient knowledge of theory he was lacking practice, as at that time the entire laboratory of the university consisted of only two small rooms. Therefore, he went abroad, and in the following three years spent two semesters with Adolph Strecker
Adolph Strecker
Adolph Strecker was a German chemist who is remembered primarily for his work with amino acids.- Life and work :...
at the University of Tübingen, a year (1864–5) with Charles-Adolphe Wurtz
Charles-Adolphe Wurtz
Adolphe Wurtz was an Alsatian French chemist. He is best remembered for his decades-long advocacy for the atomic theory and for ideas about the structures of chemical compounds, against the skeptical opinions of chemists such as Marcellin Berthelot and Etienne Henri Sainte-Claire Deville...
at the University of Paris
University of Paris
The University of Paris was a university located in Paris, France and one of the earliest to be established in Europe. It was founded in the mid 12th century, and officially recognized as a university probably between 1160 and 1250...
, and a semester with Adolph Wilhelm Hermann Kolbe
Adolph Wilhelm Hermann Kolbe
Adolph Wilhelm Hermann Kolbe was a German chemist. He never used the first two of his given names, preferring to be known as Hermann Kolbe.-Life:...
at the University of Marburg.
In the meantime, many changes were introduced into the constitution of the Russian universities. In 1863 the universities obtained academic freedom, they chose for themselves the professors,
deans, and rectors, at the same time the means of teaching improved, and, owing to Mendeleev’s efforts, the laboratory at St. Petersburg University was enlarged. In 1865 Menshutkin returned to St. Petersburg, just after his PhD thesis was published in the Comptes Rendus of the French Academy under the title “Action du chlorure d’acetyle sur l’acide phosphoreux”. He defended it in March 1866 against Aleksandr Butlerov
Aleksandr Butlerov
Aleksandr Mikhailovich Butlerov was a Russian chemist, one of the principal creators of the theory of chemical structure , the first to incorporate double bonds into structural formulas, the discoverer of hexamine , and the discoverer of the formose reaction.The...
and Dmitri Mendeleev and in autumn began teaching a course on organic nitrogen compounds. On 6 April 1869, he defended his habilitation
Habilitation
Habilitation is the highest academic qualification a scholar can achieve by his or her own pursuit in several European and Asian countries. Earned after obtaining a research doctorate, such as a PhD, habilitation requires the candidate to write a professorial thesis based on independent...
on “The Synthesis and Properties of the Ureides” and shortly was appointed as professor of analytical chemistry. In connection with his teaching he proceeded to rearrange the course of instructions and in 1871 brought out his well-known textbook, which survived 16 editions up to 1931 and had been translated into German and English. In 1871, Menshutkin became secretary of the faculty of physics and mathematics and in 1879 was appointed as dean, an office which he held until 1887.
The assassination of the Emperor Alexander II
Alexander II of Russia
Alexander II , also known as Alexander the Liberator was the Emperor of the Russian Empire from 3 March 1855 until his assassination in 1881...
in 1881 was followed by the adoption of severe measures, from the effects of which the universities suffered in many ways. The autonomy granted in 1863 was revoked and all officials could only be appointed by the Minister of Public Instruction; the admission of students was hindered by accepting them only from certain schools, the fees were raised and the number of professorships reduced. The discontent by professors and students resulted in disturbances in 1887-8, which were followed by the resignation of the rector and several key officials. As a result, Menshutkin had to add teaching of organic chemistry to his duties. About this time he prepared his large handbook of organic chemistry, which appeared in three successive editions, and in 1888 he published a history of the development of chemical theory. Both books were written in Russian and not translated. One of Menshutkin’s most serious undertakings of the time was the building of the new chemical laboratories of the University. Only by 1890 money could be found for this purpose and in this year Mendeleev resigned his chair, leaving Menshutkin in the position of senior professor of the university. Menshutkin managed to build the laboratories by October 1894 and worked there for eight years.
In 1902 Menshutkin was transferred to the new Polytechnic Institute, about 6 km north of St. Petersburg, while retaining the professorship in the university. There he acted as professor of analytical and organic chemistry and dean of the mining division. From the establishment of the Russian Chemical Society in 1868, and until 1891, Menshutkin served as its secretary and became its president in 1906. As deputy of a province he was able to improve popular education and help establishing several new schools. At the end of 1905 he took an active part in the elections for the first Duma
State Duma of the Russian Empire
The State Duma of the Russian Empire was a legislative assembly in the late Russian Empire, which met in the Taurida Palace in St. Petersburg. It was convened four times between 1906 and the collapse of the Empire in 1917.-History:...
, and was one of the founders of the Party of Democratic Reform
Party of Democratic Reform (Russia)
The Party of Democratic Reform was a liberal-monarchist political party in the Russian Empire, founded at the beginning of 1906 during the elections to the First Duma, from elements who found the Cadet programme too Left. The party had merged with the Party of Peaceful Renovation in 1907....
. Menshutkin had suffered for many years from disorder of the kidneys. He survived an attack at the end of 1906, but then suddenly died in February 1907.
Research
For his PhD thesis, Menshutkin studied the reactions of phosphonic acid and was able to prove that not all three hydrogenHydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
atoms in the molecule are equivalent and therefore the formula HP(O)(OH)2 is more likely than P(OH)3. In 1890 Menshutkin discovered that a tertiary amine can be converted into a quaternary ammonium salt by reaction with an alkyl halide.
Alcohol
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 and acids on esterification and showed that, both in respect of rate and limit, the primary
Primary alcohol
A primary alcohol is an alcohol which has the hydroxyl radical connected to a primary carbon. It can also be defined as a molecule containing a “–CH2OH” group.Examples include ethanol and butanol....
, secondary, and tertiary alcohols differ from one another, and that unsaturated differ from saturated alcohols. The molecular weight of the alcohol concerned has also a considerable influence on the result, the limit rising generally with molecular weight, although the rate is diminished. The first series of experiments were made with acetic acid
Acetic acid
Acetic acid is an organic compound with the chemical formula CH3CO2H . It is a colourless liquid that when undiluted is also called glacial acetic acid. Acetic acid is the main component of vinegar , and has a distinctive sour taste and pungent smell...
and alcohols and were extended to a variety of acids. Subsequently the rate of chemical change was studied in the case of the formation of amide
Amide
In chemistry, an amide is an organic compound that contains the functional group consisting of a carbonyl group linked to a nitrogen atom . The term refers both to a class of compounds and a functional group within those compounds. The term amide also refers to deprotonated form of ammonia or an...
s and anilides by the action of ammonia
Ammonia
Ammonia is a compound of nitrogen and hydrogen with the formula . It is a colourless gas with a characteristic pungent odour. Ammonia contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or...
and aniline
Aniline
Aniline, phenylamine or aminobenzene is an organic compound with the formula C6H5NH2. Consisting of a phenyl group attached to an amino group, aniline is the prototypical aromatic amine. Being a precursor to many industrial chemicals, its main use is in the manufacture of precursors to polyurethane...
on acids by means of the same method as was employed in the esterification experiments. Here again the influence of isomer
Isomer
In chemistry, isomers are compounds with the same molecular formula but different structural formulas. Isomers do not necessarily share similar properties, unless they also have the same functional groups. There are many different classes of isomers, like stereoisomers, enantiomers, geometrical...
ic differences was equally manifest. These researches led on to others, such as the study of the mutual displacement of bases
Base (chemistry)
For the term in genetics, see base A base in chemistry is a substance that can accept hydrogen ions or more generally, donate electron pairs. A soluble base is referred to as an alkali if it contains and releases hydroxide ions quantitatively...
in homogeneous
Homogeneity
Homogeneity, homogeneous, or homogenization may refer to:-Science:* Homogeneity , translational invariance or compatibility of units in equations* Homogeneous , a property of a mixture showing no variation in properties...
systems, and the influence of temperature on the rate of several reactions.
Menshutkin further studied the effect of different solvents on the reaction rate
Reaction rate
The reaction rate or speed of reaction for a reactant or product in a particular reaction is intuitively defined as how fast or slow a reaction takes place...
s. Although the solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...
is unaltered after the reaction, its influence on the reaction rate was significant. The stabilization of the reactants, products and intermediate phases or transition states depended strongly on the polarity of the solvent, and therefore this polarity had a large influence on the reaction rate. Because of the formation of ionic products, the effect was especially strong in the Menshutkin reaction
Menshutkin reaction
The Menshutkin reaction in organic chemistry converts a tertiary amine to a quaternary ammonium salt by reaction with an alkyl halide:The reaction has been named after its discoverer, the Russian chemist Nikolai Menshutkin, who described the procedure in 1890...
making it an ideal tool to study the effect of solvent on the reaction rate. The Menshutkin reaction is still used for this purpose.
Between 1889 and 1895 Menshutkin focused on amines, on the kinetics of their interaction
with alkyl halogen
Halogen
The halogens or halogen elements are a series of nonmetal elements from Group 17 IUPAC Style of the periodic table, comprising fluorine , chlorine , bromine , iodine , and astatine...
compounds and its dependence on the isomerism. Continuing these investigations down to the end of his life, he succeeded in establishing a large number of other relations between the structure or constitution and chemical activity, as well as physical properties, such as boiling point, melting point and specific gravity
Specific gravity
Specific gravity is the ratio of the density of a substance to the density of a reference substance. Apparent specific gravity is the ratio of the weight of a volume of the substance to the weight of an equal volume of the reference substance. The reference substance is nearly always water for...
. He is regarded
as a pioneer in chemical kinetics
Chemical kinetics
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes. Chemical kinetics includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition...
, not for the priority, but for systematic development of this field.