以固体光气(BTC),丙烯酸(AA)和甲基丙烯酸(MAA)为主要原料,经酰化反应合成了丙烯酰氯(1,86%)和甲基丙烯酰氯(2,79%)。分别以1和2为原料,合成了两种丙烯酸酯类功能单体,其结构经1H NMR,13 C NMR,IR和元素分析表征。合成1的最佳条件为:BTC...以固体光气(BTC),丙烯酸(AA)和甲基丙烯酸(MAA)为主要原料,经酰化反应合成了丙烯酰氯(1,86%)和甲基丙烯酰氯(2,79%)。分别以1和2为原料,合成了两种丙烯酸酯类功能单体,其结构经1H NMR,13 C NMR,IR和元素分析表征。合成1的最佳条件为:BTC 0.3 mol,n(BTC)∶n(AA)=1∶1,三乙胺既作催化剂又作缚酸剂,于40℃～50℃反应8 h。展开更多
Several phenylselenyl esters were selected as precursors of acyl radicals and synthesised by our established method. Treatment of these phenylselenyl esters with tributyltinhydride and AIBN ge...Several phenylselenyl esters were selected as precursors of acyl radicals and synthesised by our established method. Treatment of these phenylselenyl esters with tributyltinhydride and AIBN generated the corresponding acyl radicals, which were found to proceed in 5 exo trig or 6 endo trig cyclisations to afford high yields of cyclopentanones and cyclohexanones, The substitution groups on the substrates have played an important role on the regioselectivity of cyclisations.展开更多
The potential energy surfaces for the C-C, C-Br and C-Cl dissociations of BrCH 2 COCl(S 1 ) are investigated at the CAS(8,7)/6 31G * and MR CI/cc pVDZ levels of theory, which provides some new insights into the mechan...The potential energy surfaces for the C-C, C-Br and C-Cl dissociations of BrCH 2 COCl(S 1 ) are investigated at the CAS(8,7)/6 31G * and MR CI/cc pVDZ levels of theory, which provides some new insights into the mechanism of the BrCH 2 COCl photodis sociation at 248nm. It is found that the relative strength of the C-C and C-Cl α bonds is one of the factors that influence the selectivity of the α bond fissions. However, the selectivity is mainly determined by the mechanism of dissociation upon n→π * excitation. The preference of the C-Cl α bond fission over the C-Br β bond cleavage is attributed to the nonadiabatic recrossing in previous studies. The present calculations predict that distance dependence of intramolecular energy relaxation is another important factor that influences the selectivity of the α and β bond cleavages.展开更多
文摘Several phenylselenyl esters were selected as precursors of acyl radicals and synthesised by our established method. Treatment of these phenylselenyl esters with tributyltinhydride and AIBN generated the corresponding acyl radicals, which were found to proceed in 5 exo trig or 6 endo trig cyclisations to afford high yields of cyclopentanones and cyclohexanones, The substitution groups on the substrates have played an important role on the regioselectivity of cyclisations.
文摘The potential energy surfaces for the C-C, C-Br and C-Cl dissociations of BrCH 2 COCl(S 1 ) are investigated at the CAS(8,7)/6 31G * and MR CI/cc pVDZ levels of theory, which provides some new insights into the mechanism of the BrCH 2 COCl photodis sociation at 248nm. It is found that the relative strength of the C-C and C-Cl α bonds is one of the factors that influence the selectivity of the α bond fissions. However, the selectivity is mainly determined by the mechanism of dissociation upon n→π * excitation. The preference of the C-Cl α bond fission over the C-Br β bond cleavage is attributed to the nonadiabatic recrossing in previous studies. The present calculations predict that distance dependence of intramolecular energy relaxation is another important factor that influences the selectivity of the α and β bond cleavages.
