Trichloromethanesulfonyl chloride

Application

Trichloromethanesulfonyl chloride can be used as a pharmaceutical synthesis intermediate. Perfluoroiodoalkanes and bromoalkanes undergo sulfinization-deiodination and debromination reactions with sodium dithionite under appropriate conditions, while perfluorochloroalkanes do not react under similar conditions. However, carbon tetrachloride and 1,1,1-trichloropolyfluoroalkanes can undergo sulfinization-dechlorination reactions with sodium dithionite. Trichlorobromomethane and trichloroiodomethane react under similar conditions to yield sulfinized debromination and deiodination products, respectively.

Uses

Trichloromethanesulfonyl chloride is an efficient free radical chlorinating agent. It reacts with pent-4-enylcobaloximes in inert solvent under tugsten lamp irradiation to yield 2-(β,β,β- trichloroethyl)sulfolanes. It also reacts with trimethylsilyl enol ethers of acetophenones in the presence of a ruthenium (II) phosphine complex to yield 1-aryl-3,3-dichloropropen-1-one and α-chloroacetophenones.

General Description

Trichloromethanesulfonyl chloride is an efficient free radical chlorinating agent. It reacts with pent-4-enylcobaloximes in inert solvent under tugsten lamp irradiation to yield 2-(β,β,β- trichloroethyl)sulfolanes. It also reacts with trimethylsilyl enol ethers of acetophenones in the presence of a ruthenium (II) phosphine complex to yield 1-aryl-3,3-dichloropropen-1-one and α-chloroacetophenones.

Synthesis

Step 1); reaction at 25C, under nitrogen atmosphere, 4.0g (26mmol) la, 4.6g (26mmol) sodium thiosulfate, 2.2g sodium bicarbonate, 18mL of water and 6mL of ethyl ether, stirred at 25C for 6h and then replenished with 2.3g of sodium thiosulfate, 1.1g of sodium bicarbonate, and continued to react for l0h, evaporated the solvent under reduced pressure, and extracted the leftover residual with 50mL of ethyl acetate. The solid was extracted three times with 50 mL of ethyl acetate, and the extract was de-esterified to give a white fluffy solid, which was crystallized by isopropanol to give 3.9 g of colorless crystals 2a in 73% yield. Step 2): 3.9g2a was dissolved in 15mL water, reacted with chlorine at 0 for lh, precipitated white solid, filtered, washed, dried, purified by sublimation method, obtained 3.9g of white solid trichloromethylsulfonyl chloride, yield 94%.