Quantum chemical approach to calculating the enthalpies of the formation of alkali metal xanthates

Objectives. The aim of this work is to study the possibility of the joint use of quantum chemical methods and correlation analysis to determine the formation enthalpies of metal-containing organic substances using the example of alkali metal xanthates, which are of interest as biologically active substances and effective flotation reagents.

Methods. Semi-empirical methods of quantum chemical calculating (Modified Neglect of Diatomic Overlap, Austin Model 1, Recife model 1 methods) and linear regression analysis were used.

Results. Using the semi-empirical Modified Neglect of Diatomic Overlap, Austin Model 1, and Recife model 1 methods, the enthalpies of formation of 16 potassium and sodium alkyl xanthates were calculated, and the obtained results were compared with experimental data. It was found that the best correlation for potassium and sodium salts of dithiocarbonic acid esters could be observed using the Austin Model 1 method. Using the obtained regression equations, the enthalpies of formation were calculated for 30 xanthates, the organic part of which contained alkyl, cyclic non-aromatic structures, and one or two heteroatoms such as nitrogen, oxygen, and fluorine, and for which there are no experimental data.

Conclusions. As a result of the study, an excellent correlation was established between the experimental and the calculated (by the Austin Model 1 method) values of the enthalpies of formation of potassium and sodium alkyl xanthates. The data obtained can be used to calculate the thermal effect of the xanthogenation reactions of alcohols and to design the production of the corresponding xanthates. 

1. Zauer E.A. Cyclophanes: Simulation of the formation enthalpy by quantum-chemical methods. Russ. J. Gen. Chem. 2017;87:918-922. https://doi.org/10.1134/S1070363217050048

2. Zauer E.A. Enthalpy of formation of five-membered nitrogen-containing aromatic heterocycles. Russ. J. Gen. Chem. 2015:85:2268-2276. https://doi.org/10.1134/S1070363215100084

3. Zauer E.A., Zauer O.A. Calculations of the enthalpies of formation of oxygen-containing adamantane derivatives by quantum-chemical methods. Russ. J. Phys. Chem. 2009:83;582586. https://doi.org/10.1134/S0036024409040128

4. Abramov A.A. Flotatsionnye metody obogashcheniya (Flotation methods of enrichment). Moscow: Moscow State Mining University Publ.; 2008. 720 p. (in Russ.).

5. Melnikov N. N. Pestitsidy. Khimiya, tekhnologiya i primenenie (Pesticides. Chemistry, technology and application). Moscow: Chemistry; 1987. 712 p. (in Russ.).

6. Carta F., Akdemir A., Scozzafava A., Masini E., Supuran C.T. Xanthates and Trithiocarbonates Strongly Inhibit Carbonic Anhydrases and Show Antiglaucoma Effects in Vivo. J. Med. Chem. 2013;56(11):4691-4700. https://doi.org/10.1021/jm400414j

7. Waldman A.I., Panfilov B.I., Waldman D.I., Navrotsky V.A. Xanthogenation of alcohols. Message 1. Investigation of the kinetics of the xanthogenation reaction of aliphatic alcohols C1–C7 of normal structure in an aqueous solution of potassium hydroxide. DEP. ONIITEKHIM. Cherkassy, 1984. No. 476 HP-D84 (in Russ.).

8. Waldman, A.I., Panfilov, B.I., Waldman D.I. Xanthogenation of alcohols. Message 2. Investigation of the kinetics of the xanthogenation reaction of aliphatic alcohols C1–C7 of normal structure in an aqueous solution of sodium hydroxide. DEP. ONIITEKHIM. Cherkassy, 1984. No. 477hp-D84 (in Russ.).

9. Waldman A.I., Panfilov B.I., Waldman D.I., Navrotsky V.A. Xanthogenation of alcohols. Message 3. Kinetic regularities of the reaction of xanthogenation of aliphatic alcohols C3–C5 from oxidation in an aqueous solution of alkali metal hydroxide. DEP. ONIITEKHIM. Cherkassy, 1984. No. 478 HP-D84 (in Russ.).

10. Tsarenko S.V., Waldman A.I., Panfilov B.I., Waldman D.I. Calorimetric study of the kinetics of the reaction of xanthogenation of aliphatic alcohols in an aqueous solution of caustic soda. Izvestiya Vuzov. Seriya khimiya i khimicheskaya tekhnologiya = Russ. J. Chem. Chem. Technol. 1979;26(1):1054-1058 (in Russ.).

11. Hardin A.P., Waldman A.I., Gnatyuk P.P., Panfilov B.I., Waldman D.I., Lisachenko L.A. Investigation of the kinetics of the process of obtaining sodium isopropylxanthogenate. Chemical industry. 1983;28(3):143-144 (in Russ.).

12. Savelyanov V.P., Savelyanova R.T., Utrobin N.P., Rudakova T.V. Method of preparing alkylxanthogenates. USSR Pat. 727641, 15.04.1980 (in Russ.).

13. Tsarenko S.V., Gnatyuk P.P., Zakharova L.A., Nishchenkova N.S., Utrobin N.P. Method of preparing C5– C7 alcohol alkaline alkylxanthogenates. USSR Pat. 737397. 30.05.1980 (in Russ.)

14. Hummel K., Sherm A. Xanthates as antitumor agents: USA Pat. 4981869. 01.01.1991.

15. Trofimov B.A., Ivanova N.I., Amosova S.V., Leonov S.B., Belkova O.N., Roginskaya L.V., Chebotareva E.G. Potassium vinyloxyethylxanthogenate as collecting agent for flotation of polymetallic ores. USSR Pat. 910615. 07.03.1982 (in Russ.).

16. Larionov S.V., Kosareva L.A. Complexing properties of the trifluoroethyl xanthate ion and volatility of its intracomplex compounds. Russian Chemical Bulletin. 1976;25(7):1388-1391 (in Russ.).

17. Bazanova N.M., Gurvich S.M., Livshits A.K. Method for flotation concentration of copper-nickel ores. USSR Pat. 126816. 1960 (in Russ.).

18. Gorgulu A.O., Celikkan H., Arslan M. The Synthesis, Characterization and Electrochemical Behavior of Transition Metal Complexes Containing Nitrogen Heterocyclic Sulphur Donor Ligand. Acta Chim. Slov. 2009;56:334-339.

19. Tomioka M., Hasegawa K. Tricyclodecan-9-yl xanthogenate stereoisomers. RF Pat. 2470915. 27.12.2012 (in Russ.).

20. Popov Yu.V., Dolgachev A.S., Shishkin E.V. Synthesis of diethylaminoethyl potassium xanthate Izvestia VSTU. Chemistry and Technology of Hetero-Organic Monomers and Polymer Materials. 2015;(4):35-37 (in Russ.).