189230-96-4Relevant academic research and scientific papers
First Synthesis and Reactivities of Isolable Dithiiranes and Their 1-Oxides
Ishii, Akihiko,Akazawa, Toru,Ding, Meng-Xin,Honjo, Takanari,Maruta, Teruo,Nakamura, Shin-Ya,Nagaya, Hidenori,Ogura, Miho,Teramoto, Katsuhiko,Shiro, Motoo,Hoshino, Masamatsu,Nakayama, Juzo
, p. 509 - 523 (2007/10/03)
The reaction of the 6-exo-oxide of 2,2,4,4-tetramethyl-1,5-diphenyl-6,7-dithiabicyclo[3.1.1]heptane (2) with 2KHSO5·KHSO4·K2SO4 gave the first isolable dithiirane oxide, (1RS, 3SR)-3-phenyl-3-(1,1,3,3-tetramethyl-4-oxo-4-phenylbutyl)dithiirane 1-oxide (1), while the 6-endo-oxide of 2 gave both 1 and its (1RS, 3RS)-isomer 10. Under similar reaction conditions, 2 yielded the first isolable, unoxidized dithiirane, 3-phenyl-3-(1,1,3,3-tetramethyl-4-oxo-4-phenylbutyl)dithiirane (3). The dithiirane 3 was also obtained by treatment of 2 with NaOCl-NaClO4. The X-ray structure analyses were performed for 1, 3, and 10. Treatment of unsymmetrical 8,8-dimethyl-1,9-diphenyl-10,11-dithiatricyclo[7.1.1.0 2,7]-undeca-2,4,6-triene with NaOCl-NaClO4 gave 3-[1-(o-benzoylphenyl)-1-methylethyl]-3-phenyldithiirane selectively in good yield. However, 1,3-dithietanes, prepared from adamantane-2-thiones, failed to give the corresponding dithiiranes by treatment with 2KHSO5·KHSO4·K2SO4 or NaOCl-NaClO4. The dithiirane 3 thermally isomerized to 2,2,4,4-tetramethyl-1,5-diphenyl-8-oxa-6,7-dithiabicyclo[3.2.1 ]octane probably via 2,2,4,4-tetramethyl-1,5-diphenyl-5-thioxo-1-pentanone S-sulfide.
