Sulfide, chloromethyl phenyl

The product from Step 6 (0.0012 mol) was dissolved in 25 ml CH2CI2, containing NBu4Br (0.025 mol) and chloromethyl phenyl sulfide (0.019 mol) dissolved in 15 ml toluene. The mixture was refluxed 16 hours, cooled, diluted with EtOAc, washed, and concentrated. The residue was treated with sulfuryl chloride (0.003 mol) dissolved in CH2CI2 and the product isolated in 100% yield. 

Among other electrophilic reagents ctq>able of twinging about the Pummerer rearrangement are halides of organic and inorganic acids. As these halides transform sulfoxides into a-chlorosulfides they complement the sulfide chlorination route to these compounds. Thionyl chloride reacts readily with sulfoxides and 3-keto sulfoxides methyl phenyl sulfoxide furnishes chloromethyl phenyl sulfide (equation 37). Benzoyl chloride and acetyl chloride behave similarly. d yanuric chloii is transformed into cyanuric acid by dimethyl sulfoxide, which in turn is transformed into methyl chloromethyl sulfide (equation 3g).54,S5... 

Chloromethyl phenyl sulfide, CsHsSCHjCl (1). Mol. wt. 158.66, b.p. 66°/0,2 mm. The sulfide is prepared by chlorination of thioanisole with sulfuryl chloride in ( H2CI2. ... 

METHYLENATION Chloromethyl phenyl sulfide, Chloromethyltrimcthylsilane. Trimethylsclenonium hydroxide. Tri-plicnylstannylmcthy Hit Ilium. 

Chlorosulfides are often used for vicinal functionalization of alkenes. Silyl enol ethers can react with a-chloromethyl phenyl sulfides (5) in the presence of ZnBr2 or TiCU to give the corresponding -keto sulfide, which could be easily transfonned into the a-methylene ketone via sulfide oxidation to sulfoxide, followed by pyrolytic elimination (Scheme 23). 

Chloromethyl phenyl sulfide Sulfide, chloromethyl phenyl (8) ... 

Potassium ert-butoxide, sodium hydride, butyllithium have all been used for this purpose. The alkyl(aryl)sulfanylcarbene (carbenoid) thus generated undergoes addition, often effectively, across the double bond of alkenes, enol ethers, ketene acetals and enamines. The use of chloromethyl phenyl sulfide, oxirane, tetraethylammonium bromide as a catalyst and an alkene gave phenylsulfanylcyclopropanes in rather low yield. For the synthesis of l,l-dimethyl-2-phenylsulfanylcyclopropane, see Houben-Weyl, Vol.4/3, p250 and of endoj exo-7-phenylsulfanylbicyclo[4.1.0]heptane, see Vol. E19b, pl691. 

Chloromethyl phenyl sulfoxide, CoH. SCHaCl. Mol. wt. 174.66, m.p. 35 36°. The sulfoxide is obtained in > 70% yield by oxidation of chloromethyl phenyl sulfide with i-chloroperbenzoic acid. ... 

Chloromethyl ketones, 94-95 Chloromethyl methyl ether, 387 Chloromethyl methyl sulfide, 94 Chloromethyl phenyl sulfide, 94 Chloromethyl phenyl sulfoxide, 94-95 2-ChIoro-l-methylpyridinium iodide, 95-96... 

The preparation of monotritiomethyl iodide by catalytic tritiodehalogenation of bis-chloromethyl ether, chloromethyl 4-phenylbenzoate or chloromethyl phenyl sulfide with tritium gas over 10% Pd/C in ethyl acetate or DMF in the presence of a tertiary amine, and subsequent cleavage of the resulting [ H]methyl ether, ester or sulfide is addressed in Section 4.2.1 Yields are usually in the range of 30-60%. 

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