Gas-phase S-alkylation of benzenethiol with aliphatic alcohols, ethers, esters, alkyl halides and olefins over halide cluster catalysts of Groups 5 and 6 transition metals

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• 作者：Sayoko Nagashima^a ; Kentaro Kudo^a ; Hitomi Yamazaki^a ; Satoshi Kamiguchi^b ; Teiji Chihara^a ; ^{chihara@apc.saitama-u.ac.jp} ; ^{chiyara@cj9.so-net.ne.jp}
• 关键词：S-Alkylation ; Benzenethiol ; Sulfide ; Thioacetate ; Halide cluster
• 刊名：Applied Catalysis A: General
• 出版年：2013
• 出版时间：15 January, 2013
• 年：2013
• 卷：450
• 期：Complete
• 页码：50-56
• 全文大小：372 K

文摘

Benzenethiol was reacted with methanol under a hydrogen stream over [(Nb₆Cl₁₂)Cl₂(H₂O)₄]¡¤6H₂O supported on silica gel. Catalytic activity of the cluster commenced above 250 ¡ãC, yielding methyl phenyl sulfide. The selectivity was 98 % at 400 ¡ãC. Molybdenum, tantalum and tungsten halide clusters with the same octahedral metal framework also catalyzed the reaction. Primary alcohols with shorter alkyl chains were effective reagents for the S-alkylation. Aliphatic ethers, dialkyl carbonates, orthoesters and alkyl halides were effective reagents for the S-alkylation. When 1-hexene was applied to the reaction, spontaneous and catalytic S-alkylation proceeded simultaneously above 200 ¡ãC, yielding n-hexyl phenyl sulfide. When alkyl acetates were subjected to this reaction, the niobium cluster afforded S-phenyl thioacetate, and the other clusters afforded alkyl phenyl sulfides selectively. A Br?nsted acid site attributable to a hydroxo ligand, which is formed on the cluster complex by thermal activation, is proposed as the active site of the catalysts.