D. I. Rossman

Trifluoromethylsulfenylation of Masked Carbonyl Compounds

Abstract Incorporation of fluorine and fluorine containing groups such as trifluoromethyl and trifluoromethylthio moieties considerably enhances the biopharmacological properties of the parent precursors. Trifluoromethylsulfenylation of masked carbonyl functions, such as the enamines using N-(trifluoromethylthio)phthalimide is described in this communication.

Trifluoromethylthiolation of Trimethylsilyl Enol Ethers

The treatment of bis-(1,2-trimethylsilyloxy)-1-cyclobutene, 1-(1-trimethylsilyloxy)cyclpentene and 1-(1-trimethylsilyloxy)cyclohexene with trifluoromethylsulfenyl chloride has been found to furnish trifluoromethylthiolated carbonyl derivatives.

Trifluoromethylthiocopper-mediated oxirane ring opening

Abstract The reaction of styrene oxide with trifluoromethylthiocopper furnishes seven compounds; all arising from the free radical cleavage of the oxirane ring. The mechanism of the formation and mass spectral characterization of the various products are described in this communication.

Reactions of Trifluoromethylsulfenyl Chloride and Trifluoromethylthiocopper with 2-(Trimethylsilyl)thiazole

The treatment of 2-(trimethylsilyl)thiazole with trifluoromethylsulfenyl chloride furnishes the expected 2-(trifluoromethylthio)thiazole in satisfactory yields along with the ring contraction product of the azirine-type. However, the reaction of 2-bromothiazol with trifluoromethylthiocopper gives poor yields of the above compound. The mechanism of formation and the mass spectral characterization of the products are presented in this article.

REACTION OF TRIFLUOROMETHYLSULFENYL CHLORIDE WITH 3-CHLORO- AND 3-HYDROXYPROPYNES

Vinylsulfides are often obtained via the reaction of substituted acetylenes with sulfur-containing reagents. The presence of other functional groups such as the halide or the hydroxyl moieties enhances the usefulness of the vinylsulfide intermediates. To this end, propargyl alcohol and halides have found wide application. With a view to enhance the biological properties of the end products synthesized from the vinylsulfide intermediates, the trifluoromethylthio function has now been incorporated as a part of the vinylic system. This communication presents the free-radical addition of trifluoromethylsulfenyl chloride to 3-chloro- and 3-hydroxypropynes, and the mechanism of the formation of the various products and their spectral characterization.

Photo-Trifluoromethylthiolation of Cyclopropyl Phenyl Propargyl Alcohol

Seven compounds are formed in various amounts when a solution of cyclopropopyl phenyl propargyl alcohol and trifluoromethylsulfenyl chloride in acetonitrile is exposed to UV light. The probable mechanism of formation and the mass spectral characterization of these compounds are described.

Trifluoromethylthiolation of N,O-Bis-(trimethylsilyl)acetamide

The treatment of N,O-bis-(trimethylsilyl)acetamide with trifluoromethyl-sulfenyl chloride furnishes N-mono- and di-trifluoromethylthiolated acetamides.

1-(Trimethylsilyl)-1,2,4-triazene: A novel free radical initiator

The reaction of 1-(trimethylsilyl)-1,2,4-triazene with trifluoromethylsulfenyl chloride in dry n-pentane furnishes a complex mixture containing 11 compounds. All but six of them are derived from the reaction of the thiyl or chlorine radicals with n-pentane. The probable mechanism of their formation and mass spectral characterization are presented in this article.

FORMATION AND GC-MS CHARACTERIZATION OF UNUSUAL CYCLIC SULFIDES

Abstract connection with another project involving the cleavage of the thiirane ring of cyclohexene episulfide in the presence of trifluoromethylthiocopper, the presence of several unusual cyclic sulfides (5–10, Fig. 1) was observed both in the reaction product and the starting material itself. The formation of these compounds has been rationalized on the presence and participation of the thiyl radical species. Details pertaining to their formation and characterization based on their mass spectral fragmentation behavior are presented in this communication.

Reaction of 1,3-dithiane with trifluoromethylthiocopper

The 1,3-dithiane ring undergoes cleavage even under mild neutral reaction conditions when heated in the presence of trifluoromethylthiocopper. The free-radical nature of the reaction was confirmed by the characterization of bis-(trifluoromethyl)disulfide as one of the products.