Cyproconazole(5) is a good fungicide.In this paper,starting from p-chlorobenzonitrile and allylic bromide,the intermediate 1-(4-chlorophenyl)-2-cyclopropyl-1-ethanone(2) was obtained by Barbier-type reaction and Simmo...Cyproconazole(5) is a good fungicide.In this paper,starting from p-chlorobenzonitrile and allylic bromide,the intermediate 1-(4-chlorophenyl)-2-cyclopropyl-1-ethanone(2) was obtained by Barbier-type reaction and Simmons-Smith reaction.The product 5 was synthesized form 2 via α-methyl reaction,Corey-Chaykovsky reaction,and substitution reaction with 1,2,4-triazole.The total yield was 30.8%.5 and all intermediates were characterized and confirmed with 1H NMR and MS spectra.This procedure was cost-effective and applicable on a multigram scale.展开更多
完全交替的聚碳酸亚环己酯可用作微电子牺牲材料,文中用水杨醛,邻苯二胺和叔丁醇铝制备了SalenAlOC(CH3)3,以N,N-二甲胺基吡啶(DMAP)作为共催化剂催化二氧化碳和氧化环己烯共聚,用核磁共振(1H-NMR)对共聚产物进行了结构分析。结果表明,...完全交替的聚碳酸亚环己酯可用作微电子牺牲材料,文中用水杨醛,邻苯二胺和叔丁醇铝制备了SalenAlOC(CH3)3,以N,N-二甲胺基吡啶(DMAP)作为共催化剂催化二氧化碳和氧化环己烯共聚,用核磁共振(1H-NMR)对共聚产物进行了结构分析。结果表明,催化效率最高可达494 g Polym/g Cat,共聚产物中的碳酸酯键含量为99.9%,-Mn=30300 g/mol,分子量分布PDI=1.46;与SalenAl(OiPr)相比,SalenAlOC(CH3)3得到交替度大于99%的共聚产物的反应条件更宽,更加容易控制。展开更多
The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm wasstudied with synchrotron radiation source. The adiabatic ionization potentials of moleculeSi(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0....The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm wasstudied with synchrotron radiation source. The adiabatic ionization potentials of moleculeSi(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0.02 eV and 7.00±0.03 eV respectively. Inaddition, the appearance potentials of Si(CH3)2Cl+, Si(CH3)3+, SiCl+ and SiCH3+ weredetermined:AP(Si(CH3)2Cl+) ＝10.49±0.02eV, AP(Si(CH3)3+) ＝ 11.91 ±0.02eVAP(SiCl+) ＝ 18.64 ±0.06eV, AP(SiCH3+)＝ 18.62 ±0.02eVFrom these, some chemical bond energies of Si(CH3)3Cl+ were calculated:D(Si(CH3)2Cl+ - CH3) ＝0.43 ±0.02eV, D(Si(CH3)3+ - Cl) ＝ 1.85 ± 0.02eVD(SiCH3+ - (2CH3 ＋ Cl)) ＝ 8.56 ± 0．06eV, D(SiCH3+ - 2CH3) ＝6.71±0．06eVD(SiCl+ - 3CH3) ＝ 8.58 ± 0.06eV, D(SiCl＋- 2CH3) ＝ 8.15 ±0.06eVD(SiCH3+- (CH3 ＋ Cl)) ＝8.13 ±0.展开更多
The reaction mechanism of (CH3)3CO? radical with NO is theoretically investigated at the B3LYP/6-31G* level. The results show that the reaction is multi-channel in the single state and triplet state. The potential ene...The reaction mechanism of (CH3)3CO? radical with NO is theoretically investigated at the B3LYP/6-31G* level. The results show that the reaction is multi-channel in the single state and triplet state. The potential energy surfaces of reaction paths in the single state are lower than that in the triple state. The balance reaction: (CH3)3CONO(CH3)3CO?+NO, whose potential energy surface is the lowest in all the reaction paths, makes the probability of measuring (CH3)3CO? radical increase. So NO may be considered as a stabilizing reagent for the (CH3)3CO? radical.展开更多
The reaction mechanism of (CH3)3CO with CO has been theoretically investigated using density-functional theory (DFT) calculations at B3LYP/6-31G* level. In order to get more reliable energy values the single-point ene...The reaction mechanism of (CH3)3CO with CO has been theoretically investigated using density-functional theory (DFT) calculations at B3LYP/6-31G* level. In order to get more reliable energy values the single-point energy is evaluated at CCSD (T)/6-31++G** level. The results show that the reaction is multi-channel and the reaction of (CH3)3CO radical with CO mostly produces (CH3)3C + CO2. The reaction could play a role in eliminating air pollution.展开更多
文摘Cyproconazole(5) is a good fungicide.In this paper,starting from p-chlorobenzonitrile and allylic bromide,the intermediate 1-(4-chlorophenyl)-2-cyclopropyl-1-ethanone(2) was obtained by Barbier-type reaction and Simmons-Smith reaction.The product 5 was synthesized form 2 via α-methyl reaction,Corey-Chaykovsky reaction,and substitution reaction with 1,2,4-triazole.The total yield was 30.8%.5 and all intermediates were characterized and confirmed with 1H NMR and MS spectra.This procedure was cost-effective and applicable on a multigram scale.
文摘完全交替的聚碳酸亚环己酯可用作微电子牺牲材料,文中用水杨醛,邻苯二胺和叔丁醇铝制备了SalenAlOC(CH3)3,以N,N-二甲胺基吡啶(DMAP)作为共催化剂催化二氧化碳和氧化环己烯共聚,用核磁共振(1H-NMR)对共聚产物进行了结构分析。结果表明,催化效率最高可达494 g Polym/g Cat,共聚产物中的碳酸酯键含量为99.9%,-Mn=30300 g/mol,分子量分布PDI=1.46;与SalenAl(OiPr)相比,SalenAlOC(CH3)3得到交替度大于99%的共聚产物的反应条件更宽,更加容易控制。
文摘The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm wasstudied with synchrotron radiation source. The adiabatic ionization potentials of moleculeSi(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0.02 eV and 7.00±0.03 eV respectively. Inaddition, the appearance potentials of Si(CH3)2Cl+, Si(CH3)3+, SiCl+ and SiCH3+ weredetermined:AP(Si(CH3)2Cl+) ＝10.49±0.02eV, AP(Si(CH3)3+) ＝ 11.91 ±0.02eVAP(SiCl+) ＝ 18.64 ±0.06eV, AP(SiCH3+)＝ 18.62 ±0.02eVFrom these, some chemical bond energies of Si(CH3)3Cl+ were calculated:D(Si(CH3)2Cl+ - CH3) ＝0.43 ±0.02eV, D(Si(CH3)3+ - Cl) ＝ 1.85 ± 0.02eVD(SiCH3+ - (2CH3 ＋ Cl)) ＝ 8.56 ± 0．06eV, D(SiCH3+ - 2CH3) ＝6.71±0．06eVD(SiCl+ - 3CH3) ＝ 8.58 ± 0.06eV, D(SiCl＋- 2CH3) ＝ 8.15 ±0.06eVD(SiCH3+- (CH3 ＋ Cl)) ＝8.13 ±0.
文摘The reaction mechanism of (CH3)3CO? radical with NO is theoretically investigated at the B3LYP/6-31G* level. The results show that the reaction is multi-channel in the single state and triplet state. The potential energy surfaces of reaction paths in the single state are lower than that in the triple state. The balance reaction: (CH3)3CONO(CH3)3CO?+NO, whose potential energy surface is the lowest in all the reaction paths, makes the probability of measuring (CH3)3CO? radical increase. So NO may be considered as a stabilizing reagent for the (CH3)3CO? radical.
文摘The reaction mechanism of (CH3)3CO with CO has been theoretically investigated using density-functional theory (DFT) calculations at B3LYP/6-31G* level. In order to get more reliable energy values the single-point energy is evaluated at CCSD (T)/6-31++G** level. The results show that the reaction is multi-channel and the reaction of (CH3)3CO radical with CO mostly produces (CH3)3C + CO2. The reaction could play a role in eliminating air pollution.
