Works of the Department of Organic Chemistry of SKhTI

The political and economic situation of the USSR poses with particular urgency to the chemical industry the task: to obtain from the raw materials available to us all the products we need, and to obtain them with the highest yield and by the cheapest methods. From the reserves we possess—coal, oil, wood, and agricultural products—we must at times prepare, by means of very complex chemical transformations, what in other countries nature itself provides, for example, rubber from potatoes through alcohol, etc. The chemical industry must, therefore, be concerned not only with the extraction and purification of natural products, but also with their profound chemical processing.

In the plan of the second five-year period, among the branches of the organic chemical industry, a very large place is occupied by the processing of coal tar into aniline dyes, pharmaceuticals, and other products; the processing of heavy petroleum fractions into gasoline by cracking, with the chemical utilization of the gases formed; the production of artificial petroleum from hard coals and sapropelic coals; and the conversion of waste from the timber industry into artificial fiber, sugar, alcohol, and plastics. Only by developing fine chemistry, by developing synthetic industries, shall we be able truly to raise the national economy to a height unprecedented in the capitalist world, to catch up with and surpass technically the countries that are at present the most advanced, and to become economically entirely independent of them.

In accordance with the principles of socialist construction, organic chemistry as a science must at the present stage concern itself primarily not with the investigation of particular substances, as has mainly been done up to now, but with the study of the processes by which these substances are obtained, in order to learn to control chemical processes and direct them in the most advantageous direction.

For this it is necessary to study:

a) the mechanism of the processes themselves;
b) the strength of the bonds between atoms;
c) the influence, on the course of a process, on its direction and rate, of various conditions—above all the influence of adding catalysts.

In the laboratory of organic chemistry of SKhTI, work is being carried out in the following directions:

1) The mechanism of reactions involving the splitting off of halides from molecules of organic halogen compounds and the strength of the bond of carbon with halogens.

2) The mechanism of esterification and saponification reactions of esters and the strength of the bond between carbon and oxygen.

3) The mechanism of oxidative processes in organic chemistry and the strength of the bond between carbon and hydrogen.

4) The mechanism of catalytic substitution reactions in the benzene series (nitration, and the synthesis of hydrocarbons and ketones by Friedel and Crafts).

5) The strength of the bonds of hydrogen with oxygen and nitrogen in organic compounds.

Of the recent works of the Department of Organic Chemistry printed here, three:

B. V. Tronov, L. P. Kulev, and V. N. Orlova

“Activity of halides in halogen-substituted ketones”;

B. V. Tronov and N. Kh. Sibgatullin

“Activity of halides in certain derivatives of benzene hydrocarbons with a halogen in the side chain”;

L. N. Dyakonova-Shults

“On the action of tertiary amines on halogen-substituted esters”

concern the question of the strength of the bond between carbon and halogens and the mechanism of cleavage of halogen atoms under the action of various reagents. The results of these works provide further substantiation of the electronic theory of this reaction developed by us. The basic idea of this theory is confirmed: that a halide can be detached from carbon either in the form of a negative ion or in the form of a neutral atom. The type of decomposition (more precisely: the predominant direction of decomposition, since the reaction in each case, one must suppose, proceeds in both directions) depends both on the nature of the halide compound and on the reagent acting upon it. The position of the halide in a primary unit, and, among the reagents, for example, amines, favor the cleavage of a neutral halogen atom; under the action of alkalis or alcoholates, and when the halide is attached to a tertiary carbon, the molecule decomposes predominantly into ions.

In two articles:

B. V. Tronov and L. P. Kulev

“Determination of the activity of hydrogen in organic compounds from the electromotive force of the reaction with sodium”;

B. V. Tronov and L. P. Kulev

“Comparison of the activity of alcohols and carboxylic acids under various conditions”

a method is proposed for determining chemical activity that makes it possible to compare all substances with sufficiently mobile hydrogen atoms. Measurements showed a very sharp difference in the activity of the hydroxyl hydrogen of alcohols depending on their structure and the size of the molecule. Still more interesting results were given by the comparison of alcohols with carboxylic acids. Acids in the free state proved less active than alcohols with the same number of carbon atoms and the same skeletal structure. The results of all the experiments lead to the conclusion that the acidity of carboxylic acids and other compounds depends on the formation of complexes with the solvent (and sometimes also with other molecules of the substance under investigation itself). In recent years many scholars have expressed the idea that, in general, electrolytic dissociation is conditioned by complex formation. In this, not only the very fact of complex formation is significant, but

and the structure of the complex formed. The nature of the solvent not only increases or decreases acidity in general, but even changes the very order of distribution of the substances under investigation according to the mobility of the hydrogen in them. In the pure state and in benzene solution, primary alcohols of the saturated series with 3–6 carbon atoms gave a greater electromotive force than carboxylic acids, while the acids gave a greater one than phenols. In pyridine, at low concentrations the greatest electromotive force was found for phenols, and at high concentrations—for acids.

The articles “On the Mechanism of the Perkin Reaction” and “On the Method of Obtaining Cinnamic Acid” examine one of the rather important condensation processes in the benzene series, one that is significant for the perfume industry. A critical review of the literature on the Perkin synthesis is given, and a simpler scheme of this reaction is proposed. A formulation has also been developed that makes it possible, with a shorter heating time, to obtain a higher yield of cinnamic acid.

The article “On the Origin in Nature of Optically Active Compounds” concerns a question whose clarification leaves no room in organic chemistry for vitalistic theories. In this work an explanation is proposed according to which the synthesis of optically active compounds in living organisms must have been a direct consequence of the very process by which life arose, if one accepts that the protoplasm of a living cell is essentially a single molecule; and this becomes ever more probable with the expansion of our knowledge of the structure of protein substances.