Divinyl sulfide. Communication 12. Kinetics of the reaction of acetylene with sodium hydrosulfide in aqueous DMSO
- 56 Downloads
The rate-determining step in the formation of divinyl sulfide in the reaction of acetylene with NaSH in aqueous DMSO is the addition of hydrosulfide ion to acetylene with the probable formation of sodium vinylthiolate; the addition of a second molecule of acetylene proceeds considerably more rapidly.
The rate constants for various temperatures and activation parameters for the formation of divinyl sulfide were measured.
An increase in the concentration of water in DMSO leads to a decrease in the NaSH concentration and an increase in the Na2S concentration; the yields of divinyl sulfide and 2,5-dimethyl-4-methylene-1,3-oxathiolane depend similarly on the water concentration.
In the reaction of acetylene with Na2S in aqueous DMSO divinyl sulfide is formed via two pathways, viz., from both SH− and S2− ions.
KeywordsSodium Sulfide DMSO Acetylene Water Concentration
Unable to display preview. Download preview PDF.
- 1.S. V. Amosova, V. I. Gostevskaya, G. M. Gavrilova, E. I. Enikeeva, and B. A. Trofimov, Zh. Org. Khim.,20, 2521 (1984).Google Scholar
- 2.A. M. Vasil'tsov, B. A. Trofimov, S. V. Amosova, and V. K. Voronov, Izv. Akad. Nauk SSSR, Ser. Khim., 2447 (1982).Google Scholar
- 3.B. A. Trofimov and S. V. Amosova, Divinyl Sulfide and Its Derivatives [in Russian], Nauka, Novosibirsk (1983), pp. 10–56.Google Scholar
- 4.S. N. Istomina, B. A. Trofimov, A. M. Vasil'tsov, and S. V. Amosova, Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk,3, No. 7, 134 (1982).Google Scholar
- 5.E. T. Denisov, Kinetics of Homogeneous Chemical Reactions [in Russian], Vysshaya Shkola, Moscow (1978), pp. 32–52.Google Scholar
- 6.J. I. Dickstein and S. I. Miller, in: The Chemistry of the Carbon-Carbon Triple Bond, edited by S. Patai, Part 2, Wiley-Interscience, New York (1978), p. 813.Google Scholar
- 7.E. S. Vasserman and A. B. Bedrintseva, Dokl. Akad. Nauk SSSR,33, 34 (1941).Google Scholar
- 8.S. I. Miller and G. Shkapenko, J. Am. Chem. Soc.,77, 5038 (1955); S. I. Miller and R. Tanaka, in: Selective Organic Transformations, edited by B. S. Thyagarajan, Vol. 1, Wiley-Interscience, New York (1970), p. 143.Google Scholar
- 9.A. M. Vasil'tsov, B. A. Trofimolv, and S. V. Amosova, Summaries of Papers Presented at the 6th All-Union Conference on the Chemistry of Acetylene and Its Derivatives [in Russian], Part II, Baku (1979), p. 117.Google Scholar
- 10.B. A. Trofimov, G. K. Musorin, and S. V. Amosova, Zh. Prikl. Khim.,51, 1190 (1978).Google Scholar
- 11.S. V. Amosova, B. A. Trofimov, V. V. Kryuchkov, and V. I. Parygina, Zh. Org. Khim.,14, 48 (1978).Google Scholar
- 12.S. A. Miller, Acetylene-Its Properties, Preparation, and Applications [in Russian], Khimiya, Leningrad (1969), p. 82.Google Scholar
- 13.E. M. Arnett and L. E. Small, J. Am. Chem. Soc.,99, 809 (1977).Google Scholar
- 14.A. M. Vasil'tsov, B. A. Trofimov, S. V. Amosova, V. K. Stankevich, I. S. Zhikharev, and V. V. Kuzin, Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim.,6, No. 14, 127 (1982).Google Scholar