新型丹皮酚肟酯的高效合成  

The Efficient Synthesis of New Paeonol Oxime Esters

作　　者：汪波 钟瑜红 罗年华 王勇 彭广萍 WANG Bo;ZHONG Yu-hong;LUO Nian-hua;WANG Yong;PENG Guang-ping(a.Educational Technology ＆ Expenimental Cente;b.School of Chemistry and Environmental Science.1.Shangrao Normal University,Shangrao 334001,China)

机构地区：[1]上饶师范学院教育技术与实验中心,江西上饶334001 [2]上饶师范学院化学与环境科学学院,江西上饶334001

出　　处：《合成化学》2018年第9期647-653,共7页Chinese Journal of Synthetic Chemistry

基　　金：江西省自然科学基金资助项目(20161BAB213059);江西省教育厅科技计划项目(GJJ151052);上饶师范学院大学生创新创业训练计划资助项目(2017-CX-17)

摘　　要：以丹皮酚为原料,与乙酸在N,N-二甲基乙酰胺(DMAc)和SOCl_2作用下反应制得乙酰丹皮酚酯(1); 1中酮羰基与盐酸羟胺反应生成相应的丹皮酚肟(2);在DMAc和CH_2Cl_2体系中,取代羧酸(3a^3l)与SOCl_2反应生成酰氯后随即与2反应合成了系列新型丹皮酚肟酯(4a^4l),产率80. 9%~95. 5%,其结构经~1H NMR、^(13)C NMR、IR和MS表征。以苯甲酰丹皮酚肟酯(4a)的合成为例,对反应条件进了优化。最优反应条件为:以DMAc(2 mL)为催化剂,酰氯化反应时间为20 min,酯化反应时间为3 h,产率95. 1%。并对DMAc促进丹皮酚肟酯合成反应的可能机理进行了探讨。Paeonol ester（ 1 ） was synthesized by chlorination of reaction of paeonol with acetic acid catalyzed by N,N -dimethylacetamide（DMAc） and thiony chloride. Then, paeonol oxime（ 2 ） was obtained by reaction of 1 with hydroxylamine hydrochloride. A series of new paeonol oxime esters（ 4a～4l ） with the yield of 80.9 %～95.5% were synthesized by chlorination of substituted carboxylic acids（ 3a～3l ） with thionyl chloride in DMAc and CH 2 Cl 2 , followed by esterification in situ with 2 . The structures were characterized by 1 H NMR, 13 C NMR, IR and MS. The reaction conditions were optimized using paeonol oxime ester（ 4a ） as an example. The results showed that the chlorination time of 20 min and the esterification time of 3 h were the optimal reaction conditions with DMAc（2 mL） as catalyst, and the yield of 4a was 95.1 %. The mechanism for the promotion of DMAc on the syntehsis of paeonol oxime esters was suggested.

关 键 词：丹皮酚 肟 酯 N N-二甲基乙酰胺 合成 

分 类 号：O625.42[理学—有机化学]