Phenylsulphenyl chloride

Compounds 118 could be produced from the reaction of dialkyl esters of 3-monosubstituted-l,2-alkadienephosphonic acids with methylselenenyl chloride. It was established that, along with 118, 2,3-adducts were also formed [113]. Use of phenylsulphenyl chloride in this reaction leads exclusively to the formation of 2,5-dihydro- l,2-oxaphosphole-2-oxide derivatives 117 (Scheme 48) [113, 114]. 

The reaction of dialkyl esters of 1,2-alkadienylphosphonic and phosphinic acids with methyl and phenylsulphenyl chloride, leads exclusively to 2,5-dihydro-l,2-oxaphosphole-2-oxide derivatives [113-115],... 

The substrate 139 reacts with phenylsulphenyl chloride, affording cyclic phos-phonium salt 143 which decomposes on heating to the corresponding 1,3-diene (Scheme 58) [107],... 

The reactions of chiral allylsilanes with electrophiles to give diastereoselective products has recently been extensively reviewed by Masse and Panek166. An example is shown in equation 99. The reaction of the chiral allylsilanes 142 with phenylsulphenyl chloride (PSC) and chlorosulphonyl isocyanate (CSI) takes place with a diastereoselectivity which increases with the increasing steric bulk of the substituent R167. 

Zeifirov s group has reported on the activation of the electrophilic reagents ethyl nitrite and phenylsulphenyl chloride by insertion of S03 into the molecules and has subsequently described their reactions with olefins. The reaction of activated ethyl nitrite (146) with cyclohexene yields ethyl 2-oxocyclohexylsulphate (147) (equation 15)193 while the reaction of activated phenylsulphenyl chloride in acetonitrile with cyclohexene gives the trans amide 148 in 62% yield and 28% yield of the chlorosulphide 149 (equation 16)194. 

Full details have been published of the preparation of 1A, 2,4-benzothiadiazines from N-arylbenzamidines thus treatment of N-phenylbenzamidine (Ph CPhNHg) and phenylsulphenyl chloride (PhSCl) with N-chlorosuccinimide in methylene chloride gives the benzothiadiazine (399). On heating, (399) undergoes a 1,4-sigmatropic shift to give the -benzothiadiazine (4.00) photolysis of (399) yields the benzimidazole (398) (Scheme 88). ... 

At a simpler level, descriptions have been of convenient syntheses of S-alkyl phosphorodichloridothioates from sulphenyl chlorides and methyl phosphorodichloridite in liquid S02 " of dialkyl S-phenyl phosphorothioates from trialkyl pho.sphites and phenylsulphenyl chloride of S -[2-(dialkylamino)ethyl] dialkyl phosphorothioates by a... 

Two-way addition of phenylsulphenyl chloride occurs with ethyl tx-fluoroaciylate. ... 

Other methods for the selective preparation of thiophenyl derivatives have eiIso been described [20]. 2-Alkyl-3-sulfolenes were converted to 3-thiophenyl derivatives (135) by treatment with phenylsulphenyl chloride in the presence of Et3N, and 3-thiophenylsulfolenes were alkylated selectively via their lithium anions, providing (136a-d) (Scheme 6.40). 

Reaction with iodine monochloride or phenylsulphenyl chloride also results in co-substituted products (120, 121) (74). Longifolene reacts with oxides of nitrogen to furnish, like camphene, the co-nitrolongifolene... 

A sequence for the regiospecific production of the allylic alcohols (37) from terminal isopropylidene groups (Scheme 17), involving phenylsulphenyl chloride addition, was reported last year (3,140). More recently, extension of this work (also Scheme 17)" has provided a route to the internal alcohol isomer (38), and a new alternative scheme" leads either to (37) or to the cw-terminal isomer (39) this latter depends on a stereoselective Wittig reaction modification. 

Trimethylsilylallylic alcohols of the type (81) react with phenylsulphenyl chloride to give unstable allylic sulphoxides which rearrange spontaneously at room temperature hydrolysis then furnishes a,unsaturated aldehydes (Scheme 40). ° ... 

Trimethylsilyl alkenyl ethers (511), prepared by reaction of the corresponding ketones with trimethylsilyl chloride in DMF, react with polyhalo-geno-compounds in boiling DMF-chlorobenzene in the presence of cuprous chloride to give halogeno-ajJ-unsaturated ketones (512). The ethers (511) also react with phenylsulphenyl chloride to give / -keto-sulphides (513) and with di- and tri-chloroacetyl chlorides to give 1,3-diketones (514). ... 

Several syntheses of pyrans and benzopyrans have appeared supplementing the routes already available to these important ring systems. Fluoro-substituted pyrans have been prepared from 3,3,3-trifluoropropene, which was converted to the previously unknown adducts (116) with phenylsulphenyl chloride or... 

Compounds 181 react with alkylsulphenyl chlorides to form a mixture of 1,2-oxaphosphole derivatives and 1,2-adducts in 4 1 ratio. Decreasing the reaction temperature favored formation of oxaphosphole product. The same substrates reacted with phenylsulphenyl- and phenylselenenyl bromides to give only 1,2-oxaphosphole derivatives [133],... 

The enolate (143) of an a-phenylsulphenyl ester condenses with aldehydes to give the expected adduct (144), provided that anhydrous zinc chloride is... 

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