16797-76-5Relevant academic research and scientific papers
REACTIONS OF THIOKETEN S-OXIDES WITH DIAZO COMPOUNDS A NOVEL SYNTHESIS OF HETEROCYCLIC SULFINES
Schaumann, E.,Behr, H.,Adiwidjaja, G.,Tangerman, A.,Lammerink, B. H. M.,Zwanenburg, B.
, p. 219 - 226 (1981)
Thioketen S-oxides 1 react with 2-diazopropane (2a) to give 1-pyrazoline-4-thione S-oxides 3.Addition of diazomethane to 1 yields a stable 1:1-adduct only from the S-oxide 1c.The constitution of both types of cycloadducts (3, 11) was proven by X-ray diffraction.Irradiation of 3 leads to loss of nitrogen to afford the alkylidene thiirane S-oxides 12.
Reaction of 3,3-di-tert-butylthiirane-2-thione S-oxide (α-dithiolactone S-oxide): synthesis of thiolato sulfinato-platinum and palladium complexes
Shigetomi, Toshiyuki,Shioji, Kosei,Okuma, Kentaro,Inoue, Tohru,Yokomori, Yoshinobu
, p. 5161 - 5166 (2007)
Thermolysis of 3,3-di-tert-butylthiirane-2-thione S-oxide 4 gave di-tert-butyl ketone 5 and carbon disulfide (CS2). Treatment of α-dithiolactone S-oxide 4 with excess m-CPBA or triphenylphosphine gave di-tert-butylthioketene S-oxide 3 almost quantitatively. Treatment of 4 with (η2-ethylene)bis(triphenylphosphine)platinum(0) 13 or tetrakis(triphenylphosphine) palladium 17 resulted in the formation of thiolato sulfinato-platinum complex 15 or palladium complex 18, respectively. The structure of complex 15 was determined by X-ray crystallographic analysis.
Synthesis and reaction of α-dithiolactone
Shigetomi, Toshiyuki,Soejima, Hiroe,Nibu, Yoshinori,Shioji, Kosei,Okuma, Kentaro,Yokomori, Yoshinobu
, p. 7742 - 7748 (2007/10/03)
Treatment of di-tert-butylthioketene S-oxide (5a) with Lawesson reagent at room temperature resulted in the formation of 3,3-di-fert-butylthiirane-2-thione (4a) in high yield. The oxidation of 4 a with mCPBA (mCPBA = m-chloroperbenzioc acid) gave 3,3-di-ferf-butylthiirane-2-thione S-oxide (6) almost quantitatively. The reactions of 4 a with dimethyl acetyle nedicarboxylate (DMAD) and benzyne afforded dimethyl 2-(2,2,4,4-tetramethylpentan-3-ylidene)-1, 3-dithiole-4,5-dicarboxylate (13) and 2-(2,2,4,4-tetramethylpentan-3-ylidene) benzo[d] [1,3]-dithiole (15), respectively, in high yields, suggesting that 4 a is an excellent 1,3-dipole. The reaction of 4 a with ethylenebis(triphenylphosphine)platinum (16) gave dithiolato-platinum complex (22) in high yield. The structure of 22 was determined by X-ray crystallographic analysis.
Oxidation of Thioketenes by Singlet Oxygen
Rao, V. Jayathirtha,Ramamurthy, V.,Schaumann, E.,Nimmesgern, H.
, p. 615 - 621 (2007/10/02)
Oxidation of di-tert-butylthioketene (1) and 1,1,3,3-tetramethyl-2-(thiocarbonyl)cyclohexane (2) by singlet oxygen has been investigated and has been found to exhibit a unique behavior different from that of ketenes and ketenimines.Oxidation of 1 in methylene chloride yielded the corresponding thioketene S-oxide (3), thioketone S-oxide (4), and trans-2,2,7,7-tetramethyl-4-octene-3,6-dione (5), and that in methanol gave 3, 4, methyl 1-tert-butyl-3,3-dimethyl-2-oxobutanesulfinate (6), and 1-methoxy-3,3-dimethylbutanone (7).Similar oxidation of 2 in methylene chloride gave 1,1,3,3-tetramethyl-2-(thiocarbonyl)cyclohexane S-oxide (8), 2,2,6,6-tetramethylcyclohexanethione S-oxide (9), and 2,2,6,6-tetramethylcyclohexanone (10), and in methanol methyl 3,3,7,7-tetramethyl-2-oxocycloheptanesulfinate (11) and 10 were formed.Formation of the above products has been rationalized to arise through the involvement of zwitterionic intermediates (12) resulting from the attack of singlet oxygen on the sulfur lone pair of the thioketene functionality.The difference in behavior between 1 and 2 is suggested to be due to the difference in the nature of cleavage of the suspected intermediate α-peroxythiolactone.Reasons for the variation in the product distribution with respect to temperature and solvent are yet to be understood.
Oxidation of Thioketens by Singlet Oxygen and Ozone
Rao, V. Jayathirtha,Ramamurthy, V.
, p. 638 - 639 (2007/10/02)
Di-t-butylthioketen (1) readily reacts with singlet oxygen to yield unexpected products (based on the behaviour of other heterocumulenes) and reacts with ozone to give, quantitatively, the corresponding sulphoxide (2).
