Journal of the Chemical Society. Perkin transactions II p. 1206 - 1211 (1980)
Update date:2022-08-02
Topics:
Carlsen, Lars
Egsgaard, Helge
Schaumann, Ernst
The unimolecular gas-phase thermolytic decomposition of 1,1,3,3-tetramethyl-2-thiocarbonylcyclohexane S-oxide (3) has been studied as a function of temperature by a flash vacuum thermolysis (f.v.t.) technique.The products detected are the carbenes (4) and (5), the ketone (6), the keten (7), the thioketone (8), and the thioketen (9).The product ratio is highly dependent on the thermolysis temperature.The thermolysis of (3) is mechanistically rationalized by assuming the existence of only two concurrent primary processes, which are (a) extrusion of atomic oxygen, leading to the thioketen (9), and (b) electrocyclic ring closure into the corresponding three-membered oxathiiran (10).The latter is dominant at lower temperatures, whereas higher thermolysis temperatures favour atomic oxygen extrusion.At further elevated temperatures additional concurrent primary reactions, i.e. extrusions of SO and CSO leading to the carbenes (5) and (4), respectively, are observed.Owing to an apparently very short half-life of the oxathiiran (10), only the decomposition products of the three-membered ring compound have been detected.These are the thioketone (8), formed by rearrangement of (10) into the α-thiololactone (11) followed by loss of CO, minor amounts of the ketone (6), formed analogously, and the keten (7), as a result of simple sulphur extrusion.
View MoreTianjin SPHINX SCIENTIFIC LAB.
Contact:+86-022-66211289
Address:Tianda high-tech Park. No.80,the 4th Avenue
Contact:27-792-602929
Address:SIDNEY MUFAMADI STREET 009949 X44 0700 POLOKWANE,LIMPOPO
Yingkou Sanzheng Organic Chemical Co. Ltd.
Contact:+86-417-3638818
Address:25 Gengxinli Village, Daqing Road, Yingkou, Liaoning, China
Guangzhou PI & PI Biotech Inc. Ltd.
Contact:+86-20-81716320
Address:13th Floor, Xinbao Technology Industrial Park, No. 2 Ruixiang Road, Huangpu District, Guangzhou,Guangdong,China
ZhangJiaGang YaRui Chemical Co.,Ltd.
Contact:0512-58360968
Address:China JiangSu Province Zhang Jia Gang City YangShe Oriental Plaza Building 10 B307
Doi:10.1081/SCC-120027232
(2004)Doi:10.1016/j.tet.2004.05.020
(2004)Doi:10.1246/bcsj.53.197
(1980)Doi:10.1021/je60044a054
(1970)Doi:10.1134/S0023158417060052
(2017)Doi:10.3987/COM-11-12203
(2011)
