A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA...A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.展开更多
The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-（2-bromo-4-fluoro-phenyl）-l- cyclohexen-1-yl trifluoromethane-sulfonate was studied with the density functional theory （DFT）. The g...The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-（2-bromo-4-fluoro-phenyl）-l- cyclohexen-1-yl trifluoromethane-sulfonate was studied with the density functional theory （DFT）. The geometries of the reactants, transition states, intermediates and products were optimized at the B3LYP/6-31 ＋G＊ level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-31 I＋G＊ level was individually investigated. Polarizable continuum models （PCM） were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3, does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the rate- limiting step is reduced by 56.53 kJ mo1-1 in gas and 44.84 kJ mol-l in solvent, demonstrating a high catalytic efficiency of CuI.展开更多
A two-hydroxyphenyl adamantane-type epoxy resin oligomer,namely 1,3-bis（4-（2,3-epoxpropyloxy）phenyl） adamantine （BEPAD）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The...A two-hydroxyphenyl adamantane-type epoxy resin oligomer,namely 1,3-bis（4-（2,3-epoxpropyloxy）phenyl） adamantine （BEPAD）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The unit cell of C28H32O4：Mr =432.5,monoclinic,space group P21/n,with a =10.510（6）,b =16.972（9）,c =13.374（7） （A）,β =109.356（6）°,V=2251（2） （A）3,Z =4,Dc =1.277 Mg·m^-3 and μ（MoKa） =0.084 mm^-1.In BEPAD,the methylene and epoxide rings on two ends are statistically disordered.The intermolecular interactions are also discussed,suggesting that the intermolecular interactions in BEPAD are stronger than that in the crystals of similar compounds due to the large adamantine group between the two benzene rings.展开更多
基金This work is sponsored by the National Natural Science Foundation of China (No. 59473901).
文摘A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.
文摘The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-（2-bromo-4-fluoro-phenyl）-l- cyclohexen-1-yl trifluoromethane-sulfonate was studied with the density functional theory （DFT）. The geometries of the reactants, transition states, intermediates and products were optimized at the B3LYP/6-31 ＋G＊ level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-31 I＋G＊ level was individually investigated. Polarizable continuum models （PCM） were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3, does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the rate- limiting step is reduced by 56.53 kJ mo1-1 in gas and 44.84 kJ mol-l in solvent, demonstrating a high catalytic efficiency of CuI.
基金supported by the National Natural Science Foundation of China(No.51273160 and 51473134)
文摘A two-hydroxyphenyl adamantane-type epoxy resin oligomer,namely 1,3-bis（4-（2,3-epoxpropyloxy）phenyl） adamantine （BEPAD）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The unit cell of C28H32O4：Mr =432.5,monoclinic,space group P21/n,with a =10.510（6）,b =16.972（9）,c =13.374（7） （A）,β =109.356（6）°,V=2251（2） （A）3,Z =4,Dc =1.277 Mg·m^-3 and μ（MoKa） =0.084 mm^-1.In BEPAD,the methylene and epoxide rings on two ends are statistically disordered.The intermolecular interactions are also discussed,suggesting that the intermolecular interactions in BEPAD are stronger than that in the crystals of similar compounds due to the large adamantine group between the two benzene rings.
