Bulletin of the Chemical Society of Japan p. 1629 - 1637 (1998)
Update date:2022-09-26
Topics:
Yoshimura, Toshiaki
Ohkubo, Masanori
Fujii, Takayoshi
Kita, Hiroshi
Wakai, Youko
Ono, Shin
Morita, Hiroyuki
Shimasaki, Choichiro
Horn, Ernst
S-Alkoxy-S,S-diarylthiazynes were prepared by two methods: the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines in aqueous alcohols and the reaction of S,S-diaryl-S-fluorothiazynes with sodium alkoxides. The structure of S,S-diphenyl-S-propoxythiazyne was determined by an X-ray crystallographic analysis, which showed a short SN bond length of 1.441(3) A. The thermolysis of S-alkoxythiazynes gave elimination products, which were identified as the corresponding carbonyl compounds and N-unsubstituted S,S-diarylsulfilimines. Kinetic experiments for the thermolysis of the S-alkoxy-S,S-diarylthiazynes were carried out. The first-order kinetic behavior, a large kinetic isotope effect (kHkD = 6.1 ) using S,S-diphenyl-S-[1,1-2H2]propoxythiazyne, a negative activation entropy (ΔS? = -30 J K-1mol-1), and a negative Hammett ρ-value (ρ= -0.35) on the phenyl group were obtained, suggesting that the reaction proceeds via a concerted five-membered cyclic transition state. A deviation from the ideal concerted transition state is discussed in comparison with that for sulfoxides.
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