tert-Alkyl sulfides are conveniently prepared from a -( 1H-benzotriazol-I-y1)alkyl sulfides by displacement of the 1H-benzotriazol-I-yl group with Grignard reagents. The I-[a -(alkylthio)alkyl]-and I-[a -(arylthio)alkyl]-l Hbenzotriazole intermediates are easily available by several routes: i ) displacement of the halogen from appropriate halides by sodium salts of thiols, ii) condensation of IH-benzotriazole and thiols with carbonyl compounds, or iii) lithiation of N-substituted 1H-benzotriazoles and subsequent treatment with electrophiles.1. Introduction. -The most important classical methods for the preparation of alkylamines, alkyl ethers, and alkyl sulfides 2 (Z = NR, 0, and S, respectively) have involved formation of a C-N, C-0, or C-S bond by nucleophilic substitution at the central saturated C-atom in compounds of type 1 (X = halogen, sulfonate, or similar leaving group; Scheme 1 ). For amines, such methods are rarely high yielding because of the formation of mixtures [ 11. For ethers, this reaction (the Williamson synthesis) works well for the preparation of primary alkyl ethers 2a ( Z = 0), less well for see-alkyl ethers 2b (Z = 0), and not at all for tert-alkyl ethers 2c (Z = 0) [2]. For sulfides, satisfactory results are obtained for both 2a (Z = S ) and 2b (Z = S), but the method fails for tert-alkyl sulfides 2c ( Z = S) [3]. In fact, few methods are available for tert-alkyl sulfides, although they have been prepared in 20-76% yields from tertiary alcohols and thiols in glacial AcOH in the presence of HC10, [4]. tert-Butyl thiol was converted to tert-butyl sulfide by the Friedel-Crafts catalysts, AICI,, HF, BF, [5], or H,SO, [6]. It was also found that
