引用本文:
赵晓锋, 刘祖亮. 氨基硝基吡啶及其氮氧化物的亲核取代胺化反应[J]. 应用化学,
2011, 28(4): 376-381.
doi:
10.3724/SP.J.1095.2011.00381
Citation: ZHAO Xiaofeng, LIU Zuliang. Amination of Aminonitropyridine and Its N-Oxide via Vicarious Nucleophilic Substitution of Hydrogen[J]. Chinese Journal of Applied Chemistry, 2011, 28(4): 376-381. doi: 10.3724/SP.J.1095.2011.00381
Citation: ZHAO Xiaofeng, LIU Zuliang. Amination of Aminonitropyridine and Its N-Oxide via Vicarious Nucleophilic Substitution of Hydrogen[J]. Chinese Journal of Applied Chemistry, 2011, 28(4): 376-381. doi: 10.3724/SP.J.1095.2011.00381
氨基硝基吡啶及其氮氧化物的亲核取代胺化反应
摘要:
以盐酸羟胺、1,1,1-三甲基肼碘化物(TMHI)和4-氨基-1,2,4-三唑(ATA)为胺化剂,研究了2-氨基-3,5-二硝基吡啶(1)和2-氨基-3,5-二硝基吡啶-1-氧化物(3)的亲核取代(VNS)胺化反应。结合VNS胺化反应机理讨论了胺化剂活性、胺化剂和胺化底物的立体、电子效应对产物的组成和收率的影响。以羟胺为胺化剂时,氨基可被引入到底物的6-位和4-位,胺化产物的收率在64%~89%之间;以TMHI和ATA为胺化剂时,氨基只能被引入到底物的6-位,胺化产物的收率在90%以上;在相同条件下,胺化产物的收率随胺化剂活性的提高而提高;受N+→O-的影响,化合物3的胺化产物收率稍高于化合物1的胺化产物收率。
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关键词:
- 氨基二硝基吡啶
- / 氨基二硝基吡啶氧化物
- / 亲核取代胺化
- / 胺化剂
English
Amination of Aminonitropyridine and Its N-Oxide via Vicarious Nucleophilic Substitution of Hydrogen
Abstract:
2-Amino-3,5-dinitropyridine(1) and 2-amino-3,5-dinitropyridine-1-oxide(3) have been aminated by various nucleophilic substitution reaction,using hydroxylamine hydrochloride,4-amino-1,2,4-triazole and 1,1,1-trimethylhydrazinium iodide as aminating agents.Based on amination via vicarious nucleophilic substitution(VNS) of hydrogen,the stereo-electronic effects of aminating agents and reactants on the composition and yield of target compounds were discussed.Reactants 1 and 3 were aminated at the 6-position and 4-position using hydroxylamine with a yield in the range of 64%~89%.Reactions of 1 and 3 respectively with 4-amino-1,2,4-triazole or 1,1,1-trimethylhydrazinium generated compounds which were aminated at the 6-position,with a yield over 90%.Under the same conditions,the yields for the target compounds were improved with the increase of the activities of aminating agents.
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Key words:
- amino-dinitropyridine
- / amino-dinitropyridine-oxide
- / VNS amination
- / amination reagent
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