8-苯基-8-氮杂-5-氮杂鎓-螺旋环[4,5]癸烷卤化物盐的合成及其工艺优化  

SYNTHESIS AND TECHNOLOGICAL OPTIMIZATION OF 8-PHENYL-8-AZO-5-AZONIUMSPIROCYCLO-[4,5]DECANE HALIDE

作　　者：郑黄利[1] 徐崇福[1] 朱建华[1] 李艺林[1] 王颖[1] 

机构地区：[1]常州大学石油化工学院,江苏常州213164

出　　处：《精细石油化工》2014年第3期30-33,共4页Speciality Petrochemicals

摘　　要：以二乙醇胺和氯化亚砜为原料,经三步合成8-苯基-8-氮杂-5-氮杂鎓-螺旋环[4,5]癸烷卤化物盐。首先,二乙醇胺经SOCl2氯代得到双(2-氯乙基)胺盐酸盐,产率88.0%;接下来与苯胺亲核取代产生N-苯基哌嗪盐酸盐,产率78.0%;最后与1,4-二溴丁烷以十六烷基三甲基溴化铵为催化剂,合成目标产物,8-苯基-8-氮杂-5-氮杂鎓-螺旋环[4,5]癸烷卤化物盐。重点对第三步反应的工艺条件进行了优化。结果表明:在以K2CO3为缚酸剂,十六烷基三甲基溴化铵为相转移催化剂时,n(N-苯基哌嗪盐酸盐)∶n(1,4-二溴丁烷)=1∶1,反应温度为80℃,反应时间7h时,粗产物产率高达94.8%。经乙醇和乙腈混合液中重结晶得到浅黄色晶体,分离产率86.4%。所有合成产物的分子结构都经红外光谱,1 H和13 C核磁共振光谱进行了表征。8-Phenyl-8-azo-5-azoniumspirocyclo-[4,5] decane halide was synthesized with diethanolamine and thionyl chloride as raw materials in three steps.Diethanolamine was chlorinated with thionyl chloride to afford bis（2-chlorodiethyl）aminium chloride initially with the yield of 88.0 ％.Nucleophilic substitution with aniline was acted nest to generate N-phenyl piperazinium chloride with the yield of 78.0％.The target product,8-phenyl-8-aza-5-azoniumspiro-[4,5] decane halide,was got finally after reacted with 1,4-dibromobutane in presence of phase transfer reagent.Emphasis was placed on the optimization of the technological aspect for the third step.It was shown by the experimental results that the yield of the crude product was up to 94.8％ when potassium carbonate was used as acid-biding agent,hexadecyl trimethyl ammonium chloride was used as phase transfer agent,the molar ratio n （N-phenyl piperazinium chloride） ∶ n（1,4-dibromobutane） was 1 ∶ 1 and reacted at 80 ℃ for 7 h.A pale yellow crystalline fine product was obtained after re-crystallization in ethanolethyl nitrile mixt solvent with isolated yield of 86.4％.The molecular structures of all the products were characterized with IR spectroscopy,1H and 13C NMR spectroscopy.

关 键 词：双(2-氯乙基)胺盐酸盐 N-苯基哌嗪盐酸盐 8-苯基-8氮杂-5-氮杂鎓-螺旋环[4 5]癸烷卤化物盐 

分 类 号：O626.32[理学—有机化学]