Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supp...Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] for synthesis of epoxycyclohexane was prepared by phase transfer catalysis method. Effects of various factors in synthesis of epoxycyclohexane by reaction of cyclohexene and t-BuOOH in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2(acac)2 were also investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:l (based on 0.1 mol of t-BuOOH), volume of solvent -10ml, reaction temperature -80℃, reaction time -60min, and mass of molybdenum in the catalyst -2.30×0^(-3)g, the yield of epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and the purity of epoxycyclohexane is about 99.9% by gas chromatogram(GC) analysis.展开更多
By using the laser-monitoring technique,solid-liquid equilibrium data of glutaric acid in cyclohexanol,cyclohexanone,their five mixed solvents and acetic acid were measured within the temperature range from 292.15K to...By using the laser-monitoring technique,solid-liquid equilibrium data of glutaric acid in cyclohexanol,cyclohexanone,their five mixed solvents and acetic acid were measured within the temperature range from 292.15K to 354.60K by dynamic method.Empirical formula and λh equation were used to correlate the solubilities of glutaric acid in eight solvents.The maximal average relative deviations were 1.15% and 2.20% by using the em-pirical formula and λh equation to correlate the solubility data.The results showed that the empirical formula and λh model could correlate the solubility data of glutaric acid in eight solvents.In addition,the solubility data of glutaric acid in five mixtures(cyclohexanone+cyclohexanol)could be predicted with the NRTL equation utilizing the pa-rameters of the binary systems.The total average relative deviation was 3.60%.The results indicate that the NRTL equation could well predict the solubilities of glutaric acid in the mixed solvents of cyclohexanone and cyclohexanol.展开更多
The chemoselective C-and O-prenylation of cyclic 1,3-diketones was achieved by tuning the prenyl source and catalyst.In the presence of the solid acid Nafion,the coupling of 1,3-cyclohexanediones with isoprene gave C-...The chemoselective C-and O-prenylation of cyclic 1,3-diketones was achieved by tuning the prenyl source and catalyst.In the presence of the solid acid Nafion,the coupling of 1,3-cyclohexanediones with isoprene gave C-prenylated 5-chromenones.Alternatively,using prenol as the substrate with the Lewis acid Al Cl3 as the catalyst resulted in the exclusive O-prenylation of 1,3-cyclohexanediones.Notably,the resulting products could easily undergo aromatization to deliver prenylated resorcinols that are otherwise difficult to prepare.Our methodology is highly selective,atom-economical,operationally simple,easily scalable,and has potential applications throughout organic synthesis.展开更多
The heteroleptic dmit complex Et 4N 2 Ni 2(C 2S 4)(C 3S 5) 2 has been prepared by the reaction of NiCl 2·H 2O with Na 2dmit, NaSC 2H 4OH in the MeOH solution. The compound has been characteriz...The heteroleptic dmit complex Et 4N 2 Ni 2(C 2S 4)(C 3S 5) 2 has been prepared by the reaction of NiCl 2·H 2O with Na 2dmit, NaSC 2H 4OH in the MeOH solution. The compound has been characterized by X ray diffraction study, IR and UV Vis spectroscopy. Crystallographic data : space group: P2 1/n, a=11.843(2), b=11 079(1), c = 15.404(1) , β=110.33(1)°, V = 1895.1 3, Z=2, D c =1.62 g/cm 3 , μ =17.6 cm -1 , F (000)=956, R=0.052, R w =0.061. In the structure of the title complex, the tto (tto=tetrathioxalato) ligand in bridging form is chelated to two nickel atoms and dmit (dmit=1,3 dithiole 2 thione 4,5 dithiolate) ligands coordinated to nickel atoms.展开更多
The diester diacetylene macrocyclic cyclopentadienone 8 was prepared from the open chain diester acetylene cyclopentadienone 6 in high yield, using the classical Eglinton-Galbraith procedure [1]. Copper（lI） acetate ...The diester diacetylene macrocyclic cyclopentadienone 8 was prepared from the open chain diester acetylene cyclopentadienone 6 in high yield, using the classical Eglinton-Galbraith procedure [1]. Copper（lI） acetate in pyridine was used to effect intramolecular oxidative coupling of 6 under high dilution conditions. During the course of this work a few Diels-Alder reactions of cyclopentadienone 6 were also examined.展开更多
The title compound 4, 5-bis ( 2,-dinitrophenylthio )-1, 3-dithiole-2-thione [C3S5(C6H3N2O4)2] crystallizes in the orthogonal system, space group P212121,with a=10. 134(3) , b=20. 488(4), c=9. 656(3)A , V=2005. 1 A3, D...The title compound 4, 5-bis ( 2,-dinitrophenylthio )-1, 3-dithiole-2-thione [C3S5(C6H3N2O4)2] crystallizes in the orthogonal system, space group P212121,with a=10. 134(3) , b=20. 488(4), c=9. 656(3)A , V=2005. 1 A3, D_c=1. 76 g/cm￣3 , Z=4, M.=530. 56, λ=0. 71069 A, F(000)= 1072 , μ=6.1 cm￣(-1), T=296K.Final R= 0. 038, R.= 0. 045 for 1799 reflections with I≥3.5σ(I). In this nonplanar neutral molecule both nitrobenzol rings are approximately perpendicular to the dithiole ring with an asymmetric configuration.展开更多
基金Supported by the Outstanding Personality Innovation Funds of Henan Province(No.0121001900).
文摘Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] for synthesis of epoxycyclohexane was prepared by phase transfer catalysis method. Effects of various factors in synthesis of epoxycyclohexane by reaction of cyclohexene and t-BuOOH in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2(acac)2 were also investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:l (based on 0.1 mol of t-BuOOH), volume of solvent -10ml, reaction temperature -80℃, reaction time -60min, and mass of molybdenum in the catalyst -2.30×0^(-3)g, the yield of epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and the purity of epoxycyclohexane is about 99.9% by gas chromatogram(GC) analysis.
文摘By using the laser-monitoring technique,solid-liquid equilibrium data of glutaric acid in cyclohexanol,cyclohexanone,their five mixed solvents and acetic acid were measured within the temperature range from 292.15K to 354.60K by dynamic method.Empirical formula and λh equation were used to correlate the solubilities of glutaric acid in eight solvents.The maximal average relative deviations were 1.15% and 2.20% by using the em-pirical formula and λh equation to correlate the solubility data.The results showed that the empirical formula and λh model could correlate the solubility data of glutaric acid in eight solvents.In addition,the solubility data of glutaric acid in five mixtures(cyclohexanone+cyclohexanol)could be predicted with the NRTL equation utilizing the pa-rameters of the binary systems.The total average relative deviation was 3.60%.The results indicate that the NRTL equation could well predict the solubilities of glutaric acid in the mixed solvents of cyclohexanone and cyclohexanol.
文摘The chemoselective C-and O-prenylation of cyclic 1,3-diketones was achieved by tuning the prenyl source and catalyst.In the presence of the solid acid Nafion,the coupling of 1,3-cyclohexanediones with isoprene gave C-prenylated 5-chromenones.Alternatively,using prenol as the substrate with the Lewis acid Al Cl3 as the catalyst resulted in the exclusive O-prenylation of 1,3-cyclohexanediones.Notably,the resulting products could easily undergo aromatization to deliver prenylated resorcinols that are otherwise difficult to prepare.Our methodology is highly selective,atom-economical,operationally simple,easily scalable,and has potential applications throughout organic synthesis.
文摘The heteroleptic dmit complex Et 4N 2 Ni 2(C 2S 4)(C 3S 5) 2 has been prepared by the reaction of NiCl 2·H 2O with Na 2dmit, NaSC 2H 4OH in the MeOH solution. The compound has been characterized by X ray diffraction study, IR and UV Vis spectroscopy. Crystallographic data : space group: P2 1/n, a=11.843(2), b=11 079(1), c = 15.404(1) , β=110.33(1)°, V = 1895.1 3, Z=2, D c =1.62 g/cm 3 , μ =17.6 cm -1 , F (000)=956, R=0.052, R w =0.061. In the structure of the title complex, the tto (tto=tetrathioxalato) ligand in bridging form is chelated to two nickel atoms and dmit (dmit=1,3 dithiole 2 thione 4,5 dithiolate) ligands coordinated to nickel atoms.
文摘The diester diacetylene macrocyclic cyclopentadienone 8 was prepared from the open chain diester acetylene cyclopentadienone 6 in high yield, using the classical Eglinton-Galbraith procedure [1]. Copper（lI） acetate in pyridine was used to effect intramolecular oxidative coupling of 6 under high dilution conditions. During the course of this work a few Diels-Alder reactions of cyclopentadienone 6 were also examined.
文摘The title compound 4, 5-bis ( 2,-dinitrophenylthio )-1, 3-dithiole-2-thione [C3S5(C6H3N2O4)2] crystallizes in the orthogonal system, space group P212121,with a=10. 134(3) , b=20. 488(4), c=9. 656(3)A , V=2005. 1 A3, D_c=1. 76 g/cm￣3 , Z=4, M.=530. 56, λ=0. 71069 A, F(000)= 1072 , μ=6.1 cm￣(-1), T=296K.Final R= 0. 038, R.= 0. 045 for 1799 reflections with I≥3.5σ(I). In this nonplanar neutral molecule both nitrobenzol rings are approximately perpendicular to the dithiole ring with an asymmetric configuration.
