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本文报道在冠醚和季铵盐等相转移催化剂存在下咪唑N-正丁基化反应的动力学研究结果。在一定的催化剂浓度下,反应速度与烷基卤的浓度呈一级反应动力学关系,同时与催化剂浓度亦呈一级反应比例关系在60±0.05℃,以四丁基溴化铵为催化剂,咪唑N-正丁基化反应速率常数κ=(1.90±0.02)×10~(-2),活化能E_a=11.7±0.5 kcal/mol,此外还研究了不同类型冠醚和季铵盐对反应的影响。反应机理可设想为:在相转移催化反应条件下,由催化剂中的阳离子R_4N_ 和亲核试剂Im-形成的离子对转移到有机相中与烷基卤发生反应,因此反应速率对烷基卤浓度变化极为敏感,也与催化剂在两相间的分配系数α值有关。一般以α值为1左右的季铵盐的催化效果最好,这可能是选择有效相转移催化剂的一个标志。 相似文献
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The intramolecular Wittig reaction has been applied to the syntheses of ethyl trifluoro-but-2-ynoate (2a) and ethyl heptafluoro-hex-2-ynoate (2b). Treatment of 2a and 2b withaqueous sodium hydroxide, followed by acidification, affords 3-ethoxy-4,4,4-trifluoro-2-bu-tenoic acid (3a) and 3-ethoxy-4,4,5,5,6,6,6-heptafluoro-2-hexenoic acid (3b) respectively. Anovel acetylenic ester to vinyl ether rearrangement takes place as thc corresponding methylestors. Their structures are ascertained by elemental analysis and IR and NMR spectra.The stereochemistry of this novel acetylenic ester to vinyl ether rearrangement has been studied.On the basis of ~1H NMR data, we find that the reaction is highly stereoseleetive and the Z-isomer predominated to the extent of above 94% in all cases. The results of the solventeffect of benzene and NOE enhancement in NMR spectroscopy further confirm the configura-tion of the Z- and E-isomer. 相似文献
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3, 4-Bis (trifluoromethyl)-perfluorohexene-(3) (1) reacted with diethylamine to give the 1-N, N-diethylamino-2-pentafluoroethyl -3-trifluoromethyl-perfluoropentene-(1)(2), which was easily hydrolyzed to the corresponding N, N-diethyl-2-penta-fluoroethyl- 3-trifluoromethyl-perfluoropenteno-(2)-amide (3). When compound 1 was allowed to react with n-butyl amine at 40-50`C, the 2,3,4-tris(trifluoromethyl)-4-pentafluoroethyl-1-n-butyl-aza- cyclobutene-(2) (5) was obtained as the main product and at-30-40`C, 3,4-bis(trifluoromethyl)-4-n-butylamino-perfluorohexene-(2) (4) as the main product. The isomers 3, 4-bis(trifluoromethyl)-4-allyloxy-perfluoro-hexen-(2) (6) and 2-pentafluoroethyl-3-trifluoromethyl-3-allyloxy-perfluoropentene-(1)(7) were formed when 1 was reacted with sodium allyl alcoholate. 相似文献
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