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Quantum Chemical Study of Mechanisms of Organic Reactions: XIII. Reaction of Propargyl Chloride with Dipotassium Ethane-1,2-bis(thiolate) in the System Hydrazine Hydrate–Potassium Hydroxide. Heterocyclization Pathways

  • E. A. Chirkina,
  • V. A. Grabelnykh,
  • N. A. Korchevin,
  • L. B. Krivdin,
  • I. B. Rozentsveig

摘要

Abstract

The reaction of propargyl chloride with ethane-1,2-bis(thiolate) in the system hydrazine hydrate–potassium hydroxide has been simulated using the combined CCSD(T)/6-31+G*//B3LYP/6-311++G** approach. Elementary steps of the process and possible heterocyclization pathways of the primary intermediates have been identified. Under experimental conditions (40–42°C, 6 h), the title reaction produced 25% of 2-methyl-5,6-dihydro-1,4-dithiine and 24% of 4,7-dithiadeca-2,8-diyne. No cyclic products were formed at –10 to –15°C.