Benzyl chloride sulphide from

Further data from the polarography and cyclic voltammetry in dimethylformamide are given in Table 5.1 for a series of overall two-electron processes leading to cleavage of a benzyl-heteroatom bond. The first electron transfer step is of the dissociative electron transfer type leading to a benzyl radical. This radical is reduced firrther, at the working potential, to the benzyl carbanion. The carbanion fi om benzyl chlorides, esters, ethers, sulphides, sulphones and quaternary ammonium salts can be trapped by carbon dioxide to form phenylacetic acid [2]. Reac-... 

Dibenzyl diselenide, (C6H5.CH2)2Se2.—This compound may be obtained in a variety of ways (1) Sodium selenide is heated for several hours under reflux with benzyl chloride in alcoholic solution.2 (2) A good yield of the diselenide results when a solution of selenium in sodium sulphide or sodium hydroxide is shaken on a machine with benzyl chloride.3 (3) Potassium selenosulphate is shaken with the calculated quantity of benzyl chloride in the cold. (4) An alcohol solution of potassium benzyl selenosulphate is treated with an excess of iodine, and the diselenide remaining in solution is precipitated by the addition of water. The precipitate is collected immediately and recrystallised from alcohol, since the presence of iodine appears to aid decomposition, with deposition of selenium, and it is also necessary to wash the crystals with water to remove any traces of hydriodic acid before drying the product.4 (4) An aqueous solution of potassium benzyl selenosulphate is subjected to electrolysis, using a current of 0 25 to 0 5 ampere, the method of operation being similar to that used for di-p-nitrobenzyl diselenide. 

Benzyl phenyl sulphide, norbornene, cw-cyclooctene, and 4-vinyl-1-cyclohexene were obtained from Aldrich and (IS)-(-)-a-pinene from Fluka. Phenyl sulphide was prepared from benzene and sulphur chloride following the literature procedure[9]. Reference samples of sulphoxides and sulphones were prepared by oxidation of sulphides with sodium periodate[10] and hydrogen peroxide[ll] respectively. Reference samples of epoxides were made by following Kaneda et al.[ 2 procedure. Metal phthalocyanines[13] were prepared from appropriate metal salt, 1,2-dicyanobenzene with ammonium molybdate as catalyst and were characterized by elemental analysis. 

Recently copper(i) salts including thiolates have been studied as nucleophiles. Copper(i)butanethiolate and copper(i)cyanide in DMF did not react with t-butyl chloride or benzyl chloride, but halogenoaromatic compounds react under similar conditions. When the reactions were repeated in the presence of thiourea or quinoline, the expected products, di-t-butyl sulphide, valeronitrile and phenylacetonitrile, were obtained. The thiourea or quinoline probably act as ligands and bind strongly to the copper, forming the ion (CuL4)+, leaving the counterion (e.g. BuS from CuSBu) available for normal nucleophilic attack . 

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