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化学学报
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化学学报 ›› 1987, Vol. 45 ›› Issue (2): 166-171. 上一篇    下一篇

研究论文

2-甲基-1,5-苯并硫氮杂的基态和激发态反应的研究 I: 2-甲基-1,5-苯并硫氮杂-4(5H)-酮的卤化和亲核取代反应

WAMHOFF,H;马敬骥   

  1. 西德波恩大学有机和生物化学研究所
  • 发布日期:1987-02-15

Studies on ground and excited reactions of 2-methyl-1,5-benzothiazepines I: Chlorinations of 2-methyl-1,5-benzothiazepin-4(5H)-one and nucleophilic substitutions of 2-methyl-4-chloro-1,5-benzothiazepine

WAMHOFF,H;MA JINGJI   

  • Published:1987-02-15

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2-甲基-1,5-苯并硫氮杂-4(5H)-酮(1a)与不同的氯化试剂-五氯化磷、三氯氧磷和氯化砜在不同的条件下氯化,可分别生成:2-甲基-4-氯-1,5-苯并硫氮杂(2a)、2-氯-4-甲基-1,5-苯并硫氮杂(3a)、2-二氯甲基苯并噻唑(5)、2-三氯甲基苯并噻唑(6)和2-甲基-1,5-苯并硫氮杂-4(5H)-酮盐酸盐(4).2-甲基-4-氯-1,5-苯并硫氮杂与醇钠反应生成相应的2-甲基-4-烷氧基-1,5-苯并硫氮杂外,还可以分离到它的2,4-异构体,2-烷氧基-4-甲基-1,5-苯并硫氮杂.产物的结构均经元素分析、红外光谱、^1H和^1^3C核磁共振谱和质谱鉴定.

关键词: 氮杂环化合物, 氮杂环化合物, 取代反应, 重排反应, 激发态, 异构化反应, 卤化, 亲核反应, 酮, 硫杂环化合物

2-Methyl-4-chloro-1,5-benzothiazepine, 2-chloro-4-methyl-1,5-benzothiazepine, 2-(dichloromethyl)benzothiazole, 2-(trichloromethyl)benzothiazole, and 2-methyl-1,5-benzothiazepin-4(5H)-one hydrochloride are resp. separated from chlorinations of 2-methyl-1,5-benzothiazepin-4-(5H)-one (I) with different chlorination agents: phosphorus pentachloride, phosphorus oxychloride or sulfuryl chloride under different conditions. Nucleophilic substitutions of 2-methyl-4-chloro-1,5-benzothiazepine by alkoxides lead to 2-methyl-4-alkoxy-1,5-benzothiazepines and their 2,4-isomerization products, 2-alkoxy-4-methyl-1,5-benzothiazepines. From the reaction of 2-methyl-4-chloro-1,5-benzothiazepine with sodium thiocyanate only the corresponding 2-methyl-4-thiocyano-1,5-benzothiazepine is obtained.

Key words: NITROGEN HETEROCYCLICS, NITROGEN HETEROCYCLICS, SUBSTITUTION REACTION, REARRANGEMENT REACTION, EXCITED STATE, ISOMERIZATION REACTION, HALOGENATION, NUCLEOPHILIC REACTION, KETONE, SULFUR HETEROCYCLICS COMPOUNDS

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