87974-07-0

Basic information

• Product Name: (Z)-1-phenyl-2,2-dimethylpropane-1-thione S-oxide
• CAS NO: 87974-07-0
• Molecular Weight: 194.298
• Mol File: 87974-07-0.mol

Chemical Properties

• CAS DataBase Reference: (Z)-1-phenyl-2,2-dimethylpropane-1-thione S-oxide(CAS DataBase Reference)
• NIST Chemistry Reference: (Z)-1-phenyl-2,2-dimethylpropane-1-thione S-oxide(87974-07-0)
• EPA Substance Registry System: (Z)-1-phenyl-2,2-dimethylpropane-1-thione S-oxide(87974-07-0)

Safety Data

• Hazardous Substances Data: 87974-07-0(Hazardous Substances Data)

Upstream product

• 40920-09-0 tert-butyl phenyl thioketone 
• 187847-76-3 6-tert-butyl-6-phenylpentathiane 
• 938-16-9 2,2-dimethylpropiophenone 

Relevant articles and documents

Oxidation of cis- and trans-3,5-Di-tert-butyl-3,5-diphenyl-1,2,4-trithiolanes: Isolation and Properties of the 1-Oxides and the 1,2-Dioxides

Oxidation of trans-3,5-di-tert-butyl-3,5-diphenyl-1,2,4-trithiolane with dimethyldioxirane (DMD) or m-chloroperbenzoic acid (MCPBA) gave two stereoisomeric (1S*,3S*,5S*) - and (1R*,3S* ,5S*)-1-oxides (16 and 17, respectively). Oxidation of 16 with DMD gave the (1S*,2R*,3S*,5S*)-1,2-dioxide (18) and the 1,1-dioxide 19, and that of 17 yielded the (1R*,2R*,3S* ,5S*)-1,2-dioxide (20) mainly along with 18 and 19. The structures of the 1,2-dioxides 18 and 20 were determined by X-ray crystallography. 1,2-Dioxides 18 and 20 isomerized to each other in solution, and the equilibrium constant K (20/18) is 19 in CDCl3 at 295 K. The kinetic study suggested a biradical mechanism for the isomerization. Isomerization of 16 and 17 to cis-3,5-di-tert-butyl-1,2,4-trithiolane 1-oxides by treatment with Me 3O+BF4- is also described.

Structure elucidation of 6-t-butyl-6-phenylpentathiane monoxides by X-ray crystallography and DFT calculations

6-t-Butyl-6-phenylpentathiane was oxidized with trifluoroperacetic acid (CF3CO3H) or dimethyldioxirane (DMD) at -20°C. Oxidation with CF3CO3H yielded pentathiane 3-oxide as the main product, whereas that of DMD gave 1- and 3-oxides. The structures of 1- and 3-oxides were finally determined by X-ray crystallographic analysis. DFT calculations of the NMR chemical shifts were performed on the chair and twist forms of the pentathiane and sixteen isomers of the monoxides with the GIAO method at the B3LYP/6-31G* level. The calculated chemical shifts were verified to be in practical agreement with the experimental data of the pentathiane and the isolated 1- and 3-oxides.

An S-oxide of 6-tert-butyl-6-phenylpentathiane. Structure in the crystalline state and in solution and thermal decomposition

Oxidation of 6-tert-butyl-6-phenylpentathiane with trifluoroperacetic acid gave the pentathiane 3-oxide mainly as the monooxide. The 3-oxide takes a twist conformation both in the crystalline state and in solution. Thermal decomposition of the 3-oxide in the presence of 2,3-dimethyl-1,3-butadiene yielded both S2O- and S2-transferred products.

MECHANISM OF OXIDATION OF α,β-UNSATURATED THIONES BY SINGLET OXYGEN

Photo-oxidation of α,β-unsaturated thiones yields the corresponding ketones as the only product.Studies carried out three systems, namely thioketones, α,β-unsaturated thiones and thioketenes, have revealed that there exists a similarity in their mechanism of oxidation.It has been suggested that the thiocarbonyl chromophore is the site of attack by singlet oxygen in α,β-unsaturated thiones and that the adjacent C-C double bond is inert under these conditions.Absence of sulphine during the oxidation of α,β-unsaturated thiones is attributed to the electronic factors operating on the zwitterionic / diradical intermediate.While α,β-unsaturated ketones are poorly reactive, α,β-unsaturated thiones are highly reactive toward singlet oxygen.

Photochemical Oxidation of Thioketones: Steric and Electronic Aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts.A zwitterionic/diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine.While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine.This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Mechanistic Investigations into the Photochemical Oxidation of Thioketones

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.