关键词: 定量分析, 催化, 反应动力学, 氮杂环化合物, 溴化合物, 冠式化合物, 标记化合物, 相转移催化, 碳烯, 电子效应

The relative rate constants krel of the PTC reaction of p-substituted styrenes I (R = H, Me, Cl, MeO, NO2) with dibromocarbene were measured by radiocounting method and the krel values were analyzed by linear correlation method. The r+ value of the PTC reaction of a-arylstyrenes II (R1 = 3-Me, 4-Me, H, 3-Cl, 4-MeO, 3-CF3) with dibromocarbene system was smaller than the one obtained from substituted styrene reaction. It was suggested that the aryl group of a-arylstyrene might disperse the pos. charge from a carbon atom. A variety of the crown compounds were used as PTC catalysts for the reaction of 1,1-diphenylethylene and dibromocarbene and it was found that N,N'-disubstituted azacrown possessed the highest catalytic activity for this reaction. Six 1-14C-1, 1-dibromo-2-aryl-2-phenyl-cyclopropanes were prepared and identified by comparison with the unlabeled authentic samples III which were characterized by elemental anal., NMR, MS, and TLC anal.

Key words: QUANTITATIVE ANALYSIS, CATALYSIS, REACTION KINETICS, NITROGEN HETEROCYCLICS, BROMINE COMPOUNDS, CROWN ETHER COMPOUNDS, LABELLED COMPOUNDS, PHASE TRANSFER CATALYSIS, CARBENE, ELECTRONIC EFFECT