A General Procedure for the Conversion of a Carbonyl Group into a Thione Group with Tetraphosphorus Decasulfide

Scheeren, J. W.; Ooms, Pieter H. J.; Nivard, R. J. F.

doi:10.1055/s-1973-22150

Cited by 193 publications

(77 citation statements)

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“…The thioketones were prepared from the corresponding ketones using previously reported methods (23).…”

Section: Thioketone Preparationsmentioning

confidence: 99%

Thione photochemistry. Dual pathways in aralkyl thione cyclizations

Basu¹,

Couture²,

Ho³

et al. 1981

Can. J. Chem.

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It is shown that aralkyl thiones, which possess an oxygen atom at the δ position in the side chain, can therefore not undergo the preferred δ insertion, and insert at the γ and ε positions. Although ε insertion occurs only from the 1(π,π*) state, γ abstraction (followed by cyclization or cleavage) occurs from both 1(π,π*) and 3(n,π*) states. The quantum yields of photocyclization of 2c, 2d, and 2g change little with solvent polarity, which suggests that a thione–ether charge transfer interaction contributes little to the cyclization. Fluorescence and product quenching studies are reported which support this.

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“…The thioketones were prepared from the corresponding ketones using previously reported methods (23).…”

Section: Thioketone Preparationsmentioning

confidence: 99%

Thione photochemistry. Dual pathways in aralkyl thione cyclizations

Basu¹,

Couture²,

Ho³

et al. 1981

Can. J. Chem.

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“…The solvent was evaporated under reduced pressure, and the oily residue was purified by fractional distillation. N,N-Diethyl chlorofluoroacetamide was isolated as an oily liquid (bp 95°C/14 torr; 1 torr = 133 Pa) and was treated with phosphorous pentasulfide in the presence of sodium bicarbonate (16) tan. The reaction mixture was cooled to -40'C, and chlorotrifluoroethylene was slowly passed through the mixture for 4 hr.…”

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confidence: 99%

Bioactivation mechanism of the cytotoxic and nephrotoxic S-conjugate S-(2-chloro-1,1,2-trifluoroethyl)-L-cysteine.

Dekant

Lash

Anders

1987

Proc. Natl. Acad. Sci. U.S.A.

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The bioactivation of S-(2-chloro-1,1,2-trifluoroethyl)-L-cysteine (CTFC) was studied with purified bovine kidney cysteine conjugate beta-lyase and with N-dodecylpyridoxal bromide in cetyltrimethylammonium bromide micelles as a pyridoxal model system. The beta-lyase and the pyridoxal model system converted CTFC to chlorofluoroacetic acid and inorganic fluoride, which were identified by 19F NMR spectrometry. 2-Chloro-1,1,2-trifluoroethanethiol and chlorofluorothionoacetyl fluoride were formed as metabolites of CTFC and were trapped with benzyl bromide and diethylamine, respectively, to yield benzyl 2-chloro-1,1,2-trifluoroethyl sulfide and N,N-diethyl chlorofluorothioacetamide, which were identified by gas chromatography/mass spectrometry. The bioactivation mechanism of CTFC therefore involves the initial formation of the unstable thiol 2-chloro-1,1,2-trifluoroethanethiol, which loses hydrogen fluoride to form the acylating agent chlorofluorothionoacetyl fluoride; hydrolysis of the thionoacyl fluoride affords the stable, terminal metabolites chlorofluoroacetic acid and inorganic fluoride. The intermediate acylating agent and chlorofluoroacetic acid may contribute to the cytotoxic effects of CTFC.

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“…From 10 h or 18 h reaction, a small decrease in product yield occurred, which may be due to the incompletion of the reaction and the degradation of the product, respectively (entries 5-6). Encouraged by Scheeren's report 18 on the sulfurization of carbonyl groups in the presence of sodium hydrogen carbonate (NaHCO 3 ) as an activator, we tested this in several experiments, but the addition of sodium hydrogen carbonate (6 equiv) did not accelerate the transformation nor reduce the requirement of phosphorus pentasulfide (entries 7-9). We also investigated the influence of solvents (entries 10-14).…”

Section: Resultsmentioning

confidence: 99%

A One-Pot Domino Synthesis of 5-(Trifluoromethyl)-2-thiazolamine

Bao¹,

Qiao²,

Hou³

et al. 2016

Journal of the Brazilian Chemical Society

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5-(Trifluoromethyl)-2-thiazolamine is a key intermediate for manufacturing numerous pharmaceuticals and chemicals. Here, a low-cost, one-pot multicomponent domino synthetic route has been reported for the synthesis of 5-(trifluoromethyl)-2-thiazolamine, which was successfully prepared from 3-bromo-1,1,1-trifluoro-2-propanone, phosphorus pentasulfide and cyanamide in the presence of sodium carbonate with the yield of 56%.

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A General Procedure for the Conversion of a Carbonyl Group into a Thione Group with Tetraphosphorus Decasulfide

Cited by 193 publications

References 0 publications

Thione photochemistry. Dual pathways in aralkyl thione cyclizations

Thione photochemistry. Dual pathways in aralkyl thione cyclizations

Bioactivation mechanism of the cytotoxic and nephrotoxic S-conjugate S-(2-chloro-1,1,2-trifluoroethyl)-L-cysteine.

A One-Pot Domino Synthesis of 5-(Trifluoromethyl)-2-thiazolamine

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