Enantioselective alternating copolymerization of carbon monoxide with 1 heptene was carried out using palladium catalyst modified by 1,4 3,6 dianhydro 2,5 dideoxy 2,5 bis(diphenylphosphino) L iditol (DDPPI). The chira...Enantioselective alternating copolymerization of carbon monoxide with 1 heptene was carried out using palladium catalyst modified by 1,4 3,6 dianhydro 2,5 dideoxy 2,5 bis(diphenylphosphino) L iditol (DDPPI). The chiral diphosphine was proved to be effective at enantioselective copolymerization. The pure poly(1,4 ketone) was obtained by dissolving the copolymer containing spiroketal and 1,4 ketone units in 1,1,1,3,3,3 hexafluoro 2 propanol and reprecipitating with methanol. Optical rotation, elemental analysis, spectra of 1H\|NMR, 13 C NMR and IR showed that our copolymer was optically active, isotatic, alternating poly(1,4 ketone) structure. The copolymerization was carried out at 45℃ for 48?h. Molecular weight: M n=4 02×10 3, M w/ M n=1 55 (GPC measurements with polystyrene standards). Optical rotation:[ α ] 20 589 =+63° (CH 2Cl 2, 5 0?mg/mL). T m=194℃, T g=11℃.展开更多
1,1,7-三氯-1-庚烯-3-酮是合成吡唑类除草剂的重要中间体。以5-氯戊腈为起始原料,经水解,酰氯化生成中间体5-氯戊酰氯,再与1,1-二氯乙烯加成,然后消除生成1,1,7-三氯-1-庚烯-3-酮,产品纯度≥99%,总收率为85.9%,产品经1 H NMR和红外光谱...1,1,7-三氯-1-庚烯-3-酮是合成吡唑类除草剂的重要中间体。以5-氯戊腈为起始原料,经水解,酰氯化生成中间体5-氯戊酰氯,再与1,1-二氯乙烯加成,然后消除生成1,1,7-三氯-1-庚烯-3-酮,产品纯度≥99%,总收率为85.9%,产品经1 H NMR和红外光谱验证。展开更多
The laminar flame propagation of 1-heptene/air mixtures covering equivalence ratios from 0.7 to 1.5 is investigated in a constant-volume cylindrical combustion vessel at 373K and elevated pressures (1, 2, 5, and 10 at...The laminar flame propagation of 1-heptene/air mixtures covering equivalence ratios from 0.7 to 1.5 is investigated in a constant-volume cylindrical combustion vessel at 373K and elevated pressures (1, 2, 5, and 10 atm). Laminar flame speed and Markstein length are derived from the recorded schlieren images. A kinetic model of 1-heptene combustion is developed based on our previous kinetic model of 1-hexene. The model is validated against the laminar flame speed data measured in this work and the ignition delay time data in literature. Modeling analyses, such as sensitivity analysis and rate of production analysis, are performed to help understand the high temperature chemistry of 1-heptene under various pressures and its influence on the laminar flame propagation. Furthermore, the laminar flame propagation of 1-heptene/air mixtures is compared with that of n-heptane/air mixtures reported in our previous work. The laminar flame speed values of 1-heptene/air mixtures are observed to be faster than those of n-heptane/air mixtures under most conditions due to the enhanced exothermicity and reactivity.展开更多
Eight metal cluster compounds have been synthesized from parent compound （μ3-CPh）Co3-（CO）9 and triphenylphosphine（arsine,stibine,bismuthine）. All the compounds were characterized by elemental analysis and IR sp...Eight metal cluster compounds have been synthesized from parent compound （μ3-CPh）Co3-（CO）9 and triphenylphosphine（arsine,stibine,bismuthine）. All the compounds were characterized by elemental analysis and IR spectrometry. They results showed that their catalytic activities for 1-butene hydroformylation and the yields of product both were higher than that of the parent compound in 97% and 20% more, respectively, at reaction conditions of 303.5 K, 0.392 MPa, and for 48 hours. The catalytic activities and the ratio of nor to iso by using PhCCo3（CO）7（APh3）m were increased with increase in the atomic numbers of element A（A=P,As,Sb,Bi）.展开更多
文摘Enantioselective alternating copolymerization of carbon monoxide with 1 heptene was carried out using palladium catalyst modified by 1,4 3,6 dianhydro 2,5 dideoxy 2,5 bis(diphenylphosphino) L iditol (DDPPI). The chiral diphosphine was proved to be effective at enantioselective copolymerization. The pure poly(1,4 ketone) was obtained by dissolving the copolymer containing spiroketal and 1,4 ketone units in 1,1,1,3,3,3 hexafluoro 2 propanol and reprecipitating with methanol. Optical rotation, elemental analysis, spectra of 1H\|NMR, 13 C NMR and IR showed that our copolymer was optically active, isotatic, alternating poly(1,4 ketone) structure. The copolymerization was carried out at 45℃ for 48?h. Molecular weight: M n=4 02×10 3, M w/ M n=1 55 (GPC measurements with polystyrene standards). Optical rotation:[ α ] 20 589 =+63° (CH 2Cl 2, 5 0?mg/mL). T m=194℃, T g=11℃.
基金supported by the National Key R&D Program of China (No.2017YFA0402800)National Natural Science Foundation of China (No.51622605 and No.91541201)Shanghai Science and Technology Committee (No.17XD1402000)
文摘The laminar flame propagation of 1-heptene/air mixtures covering equivalence ratios from 0.7 to 1.5 is investigated in a constant-volume cylindrical combustion vessel at 373K and elevated pressures (1, 2, 5, and 10 atm). Laminar flame speed and Markstein length are derived from the recorded schlieren images. A kinetic model of 1-heptene combustion is developed based on our previous kinetic model of 1-hexene. The model is validated against the laminar flame speed data measured in this work and the ignition delay time data in literature. Modeling analyses, such as sensitivity analysis and rate of production analysis, are performed to help understand the high temperature chemistry of 1-heptene under various pressures and its influence on the laminar flame propagation. Furthermore, the laminar flame propagation of 1-heptene/air mixtures is compared with that of n-heptane/air mixtures reported in our previous work. The laminar flame speed values of 1-heptene/air mixtures are observed to be faster than those of n-heptane/air mixtures under most conditions due to the enhanced exothermicity and reactivity.
文摘Eight metal cluster compounds have been synthesized from parent compound （μ3-CPh）Co3-（CO）9 and triphenylphosphine（arsine,stibine,bismuthine）. All the compounds were characterized by elemental analysis and IR spectrometry. They results showed that their catalytic activities for 1-butene hydroformylation and the yields of product both were higher than that of the parent compound in 97% and 20% more, respectively, at reaction conditions of 303.5 K, 0.392 MPa, and for 48 hours. The catalytic activities and the ratio of nor to iso by using PhCCo3（CO）7（APh3）m were increased with increase in the atomic numbers of element A（A=P,As,Sb,Bi）.
