新型脱氢枞胺1,2,3-噻二唑衍生物的合成及表征

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、~(13) C 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。

Synthesis and Structural Characterization of Novel Dehydroabietylamine 1,2,3-Thiadiazole Derivatives

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.