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化学学报
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化学学报 ›› 1966, Vol. 32 ›› Issue (2): 174-185,189,190. 上一篇    下一篇

论文

1,2,4-三嗪类化合物的研究——Ⅳ.氯化N-[5’-(3’-甲硫基-6’-甲基)-1’,2’,4’-三嗪基]吡啶鎓盐的置换反应

李钧, 王序   

  1. 北京医学院药学系
  • 投稿日期:1965-03-12 发布日期:2013-06-03

THE CHEMISTRY OF 1,2,4-TRIAZINES Ⅳ.SUBSTITUTION REACTIONS OF N-[5’-(3’-METHYLMERCAPTO-6’-METHYL)-1’,2’,4’-TRIAZINYL] PYRIDINIUM CHLORIDE

LI CHUN, WANG HSIU   

  1. Peking Medical College
  • Received:1965-03-12 Published:2013-06-03

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氯化N-[5'-(3'-甲硫基-6'-甲基)-1',2',4'-三嗪基]吡啶鎓盐(Ⅱ)在吡啶中于室温通入硫化氢或与硫化氢饱和的硫氢化钠反应,均得到3-甲硫基-5-巯基-6-甲基-1,2,4-三嗪(Ⅲ);于较高温度与硫化氢反应,得3,5-二巯基-6-甲基-1,2,4-三嗪(Ⅳ).二者均可于氢氧化钠溶液中与碘甲烷反应,得到3,5-二甲硫基-6-甲基-1,2,4-三嗪(Ⅴ).Ⅱ在呲啶水溶液中与邻甲苯酚、闻甲苯酚、苯酚、间硝基苯酚、邻硝基苯酚或对硝基苯酚作用,得到相应的5-取代苯氧基化合物(Ⅶa-f);与硫酚作用,得5-苯硫基化合物(Ⅷ);在吡啶中与无水乙醇作用,得5-乙氧基化合物(Ⅸ).化合物Ⅱ在吡啶水溶液中与Ⅲ作用,得S-[5'-(3'-甲硫基-6'-甲基)-1',2',4'-三嗪基]-3-甲硫基-5-巯基-6-甲基-1,2,4-三嗪(Ⅻ);与3-甲硫基-5-氧代-6-甲基-4,5-二氢-1,2,4-三嗪(Ⅰ)作用,得N4[5'-(3'-甲硫基-6'-甲基)-1',2',4'-三嗪基]-3-甲硫基-5-氧代-6-甲基-4,5-二氢-1,2,4-三嗪(ⅩⅧ);与3-甲硫基-5-氧代-4,5-二氢-1,2,4-三嗪(ⅪⅩ)作用,得N4-[5'-(3'-甲硫基-6'-甲基)-1'2'4'-三嗪基]-3-甲硫基-5-氧代-4,5-二氢-1,2,4-三嗪(ⅩⅩ);与3-甲硫基-5-氧代-4,5-二氢-1,2,4-三嗪-6-羧酸乙酯(ⅩⅩⅢ)作用,得N4[5'-(3'-甲硫基-6'-甲基)-1',2',4'-三嗪基]-3-甲硫基-5-羰基-4,5-二氢-1,2,4-三嗪-6-羧酸乙酯(ⅩⅪⅤ);与喹唑酮-4(ⅩⅩⅦ)作用,得N3[5'-(3'-甲硫基-6'-甲基)-1',2',4'-三嗪基]-4-氧代-3,4-二氢喹唑啉(ⅩⅩⅧ).这些化合物的结构系通过其水解反应、胺解反应、红外吸收光谱、紫外吸收光谱或核磁共振谱等研究予以证明.3-甲硫基-5-对硝基苯氧基-6-甲基-1,2,4-三嗪(Ⅶf)与苯胺或对甲苯胺反应,得到3-甲硫基-5-取代苯胺基-6-甲基-1,2,4-三嗪对硝基苯酚复合物(Xa,b.后者用碱处理,得3-甲硫基-5-取代苯胺基-6-甲基-1,2,4-三嗪(Ⅺa,b及对硝基苯酚.

The synthesis of 5-substituted 3-methylmercapto-6-methyl-1,2,4-triazines by substitutiorF reactions of N-5'-(3'-methylmercapto-6'-methyl)-1',2',4'-triazinyl]pyridinium chloride (Ⅱ) was reported.On passing hydrogen sulfide into a suspension of compound (Ⅱ) in pyridine at room temperature, or on adding an aqueous solution of sodium hydrogen sulfide previously saturated with hydrogen sulfide to an aqueous solution of compound (Ⅱ), 3-methylmercapto5-mercapto-6-methyl-1,2,4-triazine (Ⅲ) resulted.When hydrogen sulfide was passed into a suspension of compound (Ⅱ) in pyridine at 90-95°, substitution reactions took place both at C3 and C5 positions with the formation of 3,5-dimercapto-6-methyl-1,2,4-triazine (IV).Both compounds Ⅲ and IV could be methylated with methyl iodide in aqueous sodium hydroxide solution to the same 3,5-dimethylmercapto-6-methyl-1,2,4-triazine (V).