甲基柏木酮O-取代肟类化合物的合成与表征  

Synthesis and Characterization of Methyl Cedrone O-substituted Oximes

作　　者：张夏 罗一铭 黄静 刘辰婧 罗金岳[1] ZHANG Xia;LUO Yiming;HUANG Jing;LIU Chenjing;LUO Jinyue(College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,China;Zhejiang Zhenhai High School,Ningbo 315200,China)

机构地区：[1]南京林业大学化学工程学院,江苏南京210037 [2]浙江省镇海中学,浙江宁波315200

出　　处：《林产化学与工业》2019年第6期37-43,共7页Chemistry and Industry of Forest Products

基　　金：国家重点研发计划资助项目(2018YFD0600405);江苏高校品牌专业建设工程项目(PPZY2015C221“林产化工”)

摘　　要：以16-甲基-2,6,6,8-四甲基三环-8-烯酮肟(甲基柏木酮肟)和卤代物为原料,通过烷基化反应合成了6个甲基柏木酮O-取代肟类化合物:16-甲基-2,6,6,8-四甲基三环-8-烯酮O-苄基肟(2a)、16-甲基-2,6,6,8-四甲基三环-8-烯酮O-(4-氯苄基)肟(2b)、16-甲基-2,6,6,8-四甲基三环-8-烯酮O-(4-氰基苄基)肟(2c)、16-甲基-2,6,6,8-四甲基三环-8-烯酮O-(2,6-二氯苄基)肟(2d)、16-甲基-2,6,6,8-四甲基三环-8-烯酮O-(4-叔丁基苄基)肟(2e)和16-甲基-2,6,6,8-四甲基三环-8-烯酮O-(邻氟苄基)肟(2f)。采用FT-IR、GC-MS、1H NMR以及13C NMR等手段对产物进行结构表征,确认了产物结构。以苄基氯为例探讨了溶剂种类、催化剂四丁基溴化铵用量、苄基氯用量、反应温度以及反应时间对反应转化率和得率的影响,得到最佳的工艺条件为:以甲苯为溶剂,n(甲基柏木酮肟)∶n(四丁基溴化铵)∶n(苄基氯)=1.0∶0.12∶1.4,温度为70℃,反应时间24 h。在此条件下,产物2a的得率为78.10%,2b^2f的得率在58.91%~71.36%之间。Six novel methyl cedrone O-substituted oximes were synthesized by the alkylation reaction using methyl cedrone oxime(16-methyl-2,6,6,8-tetramethyl tricyclic-8-enone oxime) and halides as raw materials: 16-methyl-2,6,6,8-tetramethyltricyclo-8-enone O-benzyl oxime(2 a), 16-methyl-2,6,6,8-tetramethyltricyclo-8-enone O-(4-chlorobenzyl) oxime(2 b), 16-methyl-2,6,6,8-tetramethyltricyclo-8-enone O-(4-cyanobenzyl) oxime(2 c), 16-methyl-2,6,6,8-tetramethyltricyclo-8-enone O-(2,6-dichlorobenzyl) oxime(2 d), 16-methyl-2,6,6,8-tetramethyltricyclo-8-enone O-(4-tert-butylbenzyl) oxime(2 e), 16-methyl-2,6,6,8-tetramethyltricyclo-8-enone O-(o-fluorobenzyl) oxime(2 f). The structures of the products were identified by FT-IR, GC-MS, 1H NMR and 13C NMR. Taking benzyl chloride as an example, the effects of solvents, the amount of tetrabutyl ammonium bromide(TBAB) and benzyl chloride, the reaction temperature and reaction time on the conversion and yield of 2 a were discussed. The optimum condition was obtained as follows: toluene as solvent, n(methyl cedrone oxime) ∶n(TBAB) ∶n(benzyl chloride)=1.0 ∶0.12 ∶1.4, the reaction temperature was 70 ℃, the reaction time was 24 h. Under the optimal condition, the yield of product 2 a was 78.10%, the yield of 2 b-2 f ranged from 58.91% to 71.36%.

关 键 词：甲基柏木酮肟 烷基化反应 肟醚 结构表征 

分 类 号：TQ35[化学工程] O621[理学—有机化学]