新型脱氢枞胺1,2,3-噻二唑衍生物的合成及表征

doi:10.3969/j.issn.0253-2417.2016.01.020

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (1): 141-146.doi: 10.3969/j.issn.0253-2417.2016.01.020

新型脱氢枞胺1,2,3-噻二唑衍生物的合成及表征

余星, 朱苗苗, 赵丽, 林中祥

南京林业大学大学化学工程学院, 江苏南京 210037

收稿日期:2014-11-20 出版日期:2016-02-25 发布日期:2016-03-18
通讯作者: 林中祥,教授,博士生导师,研究领域为有机合成及精细化工产品的开发;E-mail:linzhongxiang36@gmail.com。 E-mail:linzhongxiang36@gmail.com
作者简介:余星(1987-),男,安徽宁国人,硕士生,主要从事有机合成研究工作
基金资助:
国家自然科学基金资助项目(31170536);江苏高校优势学科建设工程资助项目(无编号)

Synthesis and Structural Characterization of Novel Dehydroabietylamine1, 2, 3-Thiadiazole Derivatives

YU Xing, ZHU Miao-miao, ZHAO Li, LIN Zhong-xiang

College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China

Received:2014-11-20 Online:2016-02-25 Published:2016-03-18

摘要/Abstract

摘要： 以脱氢枞胺为原料,在三氟乙酸酐和乙酸酐保护其氨基后,经B环铬酸氧化转化成为(酮)N-三氟乙酰基-7-氧代脱氢枞胺(2a)和N-乙酰基-7-氧代脱氢枞胺(2b),酮再与盐酸氨基脲缩合形成(缩氨基脲)N-三氟乙酰基脱氢枞胺-7-氨基脲酰腙(3a)和N-乙酰基脱氢枞胺-7-氨基脲酰腙(3b),然后在氯化亚砜的处理下发生Hurd-Mori反应,环合生成(B环并1,2,3-噻二唑衍生物)N-三氟乙酰基脱氢枞胺-6-烯[7,6-d]-并-1,2,3-噻二唑(4a)和N-乙酰基脱氢枞胺-6-烯[7,6-d]-并-1,2,3-噻二唑(4b),最后在碱性条件下水解脱去氨基保护基,合成了脱氢枞胺-6-烯[7,6-d]-并-1,2,3-噻二唑(5)。通过FT-IR、¹H NMR、¹³C NMR和ESI-MS等方法对2a、3a、4a、4b和5的结构进行了表征,进一步分析了4a、4b和5这3种新型脱氢枞胺1,2,3-噻二唑衍生物的谱图特征及结构差异。

关键词: 脱氢枞胺, Hurd-Mori反应, 1,2,3-噻二唑, 结构表征

Abstract: Dehydroabietylamine, the starting material, reacted with trifluoroacetic anhydride and acetic anhydride to protect amino group, then converted to ketones:N-trifluoroacetyldehydroabietylamine-7-one(2a) and N-acetyldehydroabietylamine-7-one(2b) by oxidation on ring-B with chromic, the obtained ketones were treated with semicarbazide hydrochloride to afford semicarbazones:N-trifluoroacetyldehydroabietylamine-7-one semicarbazone(3a) and N-acetyldehydroabietylamine-7-one semicarbazone (3b).Compounds 3a and 3b were transformed into ring-B fused 1, 2, 3-thiadiazole derivatives:N-trifluoroacetyldehydroabietylamine-6-ene[7, 6-d]-1, 2, 3-thiadiazole(4a) and N-acetyldehydroabietylamine-6-ene[7, 6-d]-1, 2, 3-thiadiazole(4b) by Hurd-Mori reaction with thionyl chloride.Finally, the amide were hydrolysised under alkaline condition to remove protecting groups, and gave dehydroabietylamine-6-ene[7, 6-d]-1, 2, 3-thiadiazole(5).The structures of three new synthesized dehydroabietylamine 1, 2, 3-thiadiazole derivatives 4a, 4b and 5 were characterized by FT-IR, ¹H NMR, ¹³C NMR and ESI-MS.Their spectrum feature and structure difference were also analyzed.

Key words: dehydroabietylamine, Hurd-Mori reaction, 1,2,3-thiadiazole, characterization

中图分类号:

TQ35

余星, 朱苗苗, 赵丽, 林中祥. 新型脱氢枞胺1,2,3-噻二唑衍生物的合成及表征[J]. 林产化学与工业, 2016, 36(1): 141-146.

YU Xing, ZHU Miao-miao, ZHAO Li, LIN Zhong-xiang. Synthesis and Structural Characterization of Novel Dehydroabietylamine1, 2, 3-Thiadiazole Derivatives[J]. Chemistry and Industry of Forest Products, 2016, 36(1): 141-146.

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新型脱氢枞胺1,2,3-噻二唑衍生物的合成及表征

Synthesis and Structural Characterization of Novel Dehydroabietylamine1, 2, 3-Thiadiazole Derivatives

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