56956-25-3Relevant academic research and scientific papers
Preparation of 3,3-di-tert-butylthiirane trans-1,2-dioxide and its reaction with a platinum(0) complex to give a (disulfenato)platinum(II) complex: Regioselectivity of the oxidation of a related (sulfenato-thiolato)platinum(II) complex
Ishii, Akihiko,Ohishi, Masayuki,Nakata, Norio
, p. 5199 - 5206 (2008/09/17)
A three-membered vic-disulfoxide, 3,3-di-tert-butyldithiirane trans- 1,2-dioxide (8), was synthesized by oxidation of the corresponding dithiirane 1-oxide 15 in high yield. Treatment of 8 and 15 with a platinum(0) complex, [(Ph3P)2Pt(η2-C2H4)], yielded the (disulfenato)PtII complex 18 and the (sulfenato-thiolato)PtII complex 14, respectively, in high yields. Oxidation of the sulfenato-thiolato complex 14 with an acetone solution of dimethyldioxirane (DMD) took place at the sulfenato sulfur atom to yield the (sulfinato-thiolato)PtII complex 19, while the oxidation with CF 3CO3H occurred at the thiolato-sulfur atom leading to the disulfenato complex 18. Oxidation of 14 with MCPBA formed both 18 and 19. The position of oxidation on 14 with DMD was dependent on the acidity of a coexisting acid. Thus, oxidation of 14 with DMD/CF3CO2H provided 18 and that with DMD/PhCO2H gave 19. Oxidation of 14 with an excess amount of DMD yielded the (disulfonato)PtII complex 20. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
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.
Oxidations of Thioketones by Singlet and Triplet Oxygen
Rao, V. Jayathirtha,Muthuramu, K.,Ramamurthy, V.
, p. 127 - 131 (2007/10/02)
Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutyl thioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradical peroxide is believed to be a common primary intermediate for both sulfine and ketone.Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate.Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2.Singlet oxygen is also generated through energy transfer from the triplet state of thioketones.These excited states also directly react with oxygen to yield ketone.
STERIC ASPECTS OF THE OXIDATION OF THIOKETONES BY SINGLET OXYGEN
Ramnath, Narayan,Jayathertha, Vaidhya Rao,Ramesh, Varadaraj,Ramamurthy, Vaidhyanathan
, p. 89 - 92 (2007/10/02)
Singlet oxygen oxidation of dialkyl thioketones yields the corresponding ketones and in some cases sulfoxides in varying amounts.Steric considerations on the reactive zwitterionic/diradical intermediates have been invoked to rationalise the product distribution.
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).
Mechanistic Investigations into the Photochemical Oxidation of Thioketones
Ramnath, N.,Ramesh, V.,Ramamurthy, V.
, p. 112 - 114 (2007/10/02)
Singlet-oxygen reaction with dialkyl, aryl alkyl, and diaryl thioketones is found to give the corresponding sulphines and ketones in proportions depending on the nature of the thioketone.
Photochemical Oxidation of Thiones: Di-t-butyl Thioketone
Rao, V. Jayathertha,Ramamurthy, V.
, p. 143 - 144 (2007/10/02)
Di-t-butyl thioketone (1) exhibits an anomalous behaviour towards triplet oxygen and yields the corresponding sulphine (3) and the ketone (2) upon irradiation in aerated solutions.Oxidising reagent is suggested to be singlet oxygen in the conversion of thioketone to sulphine and the reactive state of oxygen and thioketone in the formation of ketone (2) is not clear.Mechanism of these conversions is being investigated.
