A simple approach for the condensation of benzaldehyde with ethylene glycol was adopted without employing any catalyst. The study reveals that factors including temperature, molar ratio of reactants, and the water rem...A simple approach for the condensation of benzaldehyde with ethylene glycol was adopted without employing any catalyst. The study reveals that factors including temperature, molar ratio of reactants, and the water removal significantly influence the conversion ratio of benzaldehyde. The results indicate that the use of optimal reaction conditions such as temperature and water removing exhibits more pronounced effects on the conversion ratio of benzaldehyde compared with the use of catalysts. In a word, a green and simple method for the condensation of aldehyde and menthandiol has been devised and investigated.展开更多
A series of Mn/CeO2-Al2O3 and K/CeO2-Al2O3 catalysts for hydrogenation of benzoic acid to benzaldehyde were prepared to in- vestigate the effect of Mn, K addition on CeO2-Al2O3 catalyst. X-ray diffraction (XRD) and H2...A series of Mn/CeO2-Al2O3 and K/CeO2-Al2O3 catalysts for hydrogenation of benzoic acid to benzaldehyde were prepared to in- vestigate the effect of Mn, K addition on CeO2-Al2O3 catalyst. X-ray diffraction (XRD) and H2-temperature-programmed reduction (H2-TPR) results suggested that the interaction between CeO2 and MnOx enhanced the reducibility of catalysts and therefore benzoic acid conversion. The addition of K increased the number of basic number on the catalyst which leads to a high selectivity to benzaldehyde, but excessive addition imposed negative effects on the catalyst performance. A Mn-K/CeO2-Al2O3 catalyst was developed and investigated in the reaction. The simultaneous addition of Mn and K enhanced not only the catalytic activity but also the capacity to resist the coke formation over catalyst.展开更多
Effects of reaction parameter on yield of benzaldehyde produced from toluene oxidization using hydrogen peroxide in subcritical water are investigated. The experimental results show that if the molar ratio of hydrogen...Effects of reaction parameter on yield of benzaldehyde produced from toluene oxidization using hydrogen peroxide in subcritical water are investigated. The experimental results show that if the molar ratio of hydrogen peroxide to toluene is controlled within a reasonable range, the by-products may be neglected. The optimum technology of toluene oxidization to benzaldehyde is reaction time 60 min, reaction temperature 350℃, molar ratio of hydrogen peroxide to toluene 3.5. The yield of benzaldehyde can reach 17.2 % under the optimum condition. Research results of chemical reaction kinetics show that the consecutive reaction consists of two first-order reaction, and activation energy of these two reactions are 89 kJ·mol^-1 and 76 kJ·mol^-1 respectively,展开更多
Hydrogenation of benzaldehyde is a typical consecutive reaction, since the intermediate benzyl alcohol is apt to be further hydrogenated. Here we demonstrate that the selectivity of benzyl alcohol can be tuned via fun...Hydrogenation of benzaldehyde is a typical consecutive reaction, since the intermediate benzyl alcohol is apt to be further hydrogenated. Here we demonstrate that the selectivity of benzyl alcohol can be tuned via functionalization of carbon nanotubes (CNTs), which are used as the support of Pd. With the original CNTs, the selectivity of benzyl alcohol is 88% at a 100% conversion of benzaldehyde. With introduction of oxygen-containing groups onto CNTs, it drops to 27%. In contrast, doping CNTs with N atoms, the selectivity reaches 96% under the same reaction conditions. The kinetic study shows that hydrogenation of benzyl alcohol is significantly suppressed, which can be attributed to weakened adsorption of benzyl alcohol. This is most likely related to the modified electronic structure of Pd species via interaction with functionalized CNTs, as shown by XPS characterization.展开更多
Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic re...Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V+Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No. 4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzaldehyde were higher than those on the undoped catalyst. This was attributed to the disordered structure of V_2O_5 lattice of the K-doped catalyst and a better interracial contact between the particles.展开更多
The effect of different concentrations of benzaldehyde on the electrodeposition of Ni–W alloy coatings on a mild steel substrate from a citrate electrolyte was investigated in this study. The electrolytic alkaline ba...The effect of different concentrations of benzaldehyde on the electrodeposition of Ni–W alloy coatings on a mild steel substrate from a citrate electrolyte was investigated in this study. The electrolytic alkaline bath(p H 8.0) contained stoichiometric amounts of nickel sulfate, sodium tungstate, and trisodium citrate as precursors. The corrosion resistance of the Ni–W-alloy-coated specimens in 0.2 mol/L H2SO4 was studied using various electrochemical techniques. Tafel polarization studies reveal that the alloy coatings obtained from the bath containing 50 ppm benzaldehyde exhibit a protection efficiency of 95.33%. The corrosion rate also decreases by 21.5 times compared with that of the blank. A higher charge-transfer resistance of 1159.40 ?·cm2 and a lower double-layer capacitance of 29.4 μF·cm-2 further confirm the better corrosion resistance of the alloy coating. X-ray diffraction studies reveal that the deposits on the mild steel surface are consisted of nanocrystals. A lower surface roughness value(Rmax) of the deposits is confirmed by atomic force microscopy.展开更多
In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were...In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.展开更多
In this paper,the two effluents from PBA (3-phenoxy-benzaldehyde) production process were treated by polymeric adsorbent CHA-111.PBA or PBC (3-phenoxy-benzoic acid) was recovered from the wastewater in the process of ...In this paper,the two effluents from PBA (3-phenoxy-benzaldehyde) production process were treated by polymeric adsorbent CHA-111.PBA or PBC (3-phenoxy-benzoic acid) was recovered from the wastewater in the process of neutralization.As a secondary treatment method,adsorption with CHA-111 showed better efficiency than photocatolytic decomposition and solvent extraction.The optimal technological parameters were:adsorption:current velocity:2.0BV/hr(bed volume per hour),room temperature;desorption:current velocity:2.0BV/hr(bed volume per hour),room temperature;desorption:current velocity:1.0 BV/hr,80℃,8% sodium hydroxide aqueous solutions.In conclusion,99.9% COD in the neutralizing wastewater and 98.4% COD in the hydrolysis wastewater are removed successfully.展开更多
In this paper, a new catalysts system V-Cs-Cu-TI was studied in the gas phase selective oxidation for p-tert butyl toluene to p-tert benzaldehyde. The catalyst system was prepared by impregnation method. The results o...In this paper, a new catalysts system V-Cs-Cu-TI was studied in the gas phase selective oxidation for p-tert butyl toluene to p-tert benzaldehyde. The catalyst system was prepared by impregnation method. The results obtained are optimum value and have good advantages in environmental protection.展开更多
Functionalized benzylic zinc halides reacted with benzaldehydes in the presence of Lewis acid Me3SiCl giving high yields of trans-stilbenes under the catalysis of Co(PPh3)3Cl.
This paper has studied the recycling of the oxidation mediator Mn(Ⅲ)/Mn(Ⅱ) and sulfuric acid solution in process of indirect electrosynthesis of benzaldehyde. Experimental resalts show that mis recycling may be real...This paper has studied the recycling of the oxidation mediator Mn(Ⅲ)/Mn(Ⅱ) and sulfuric acid solution in process of indirect electrosynthesis of benzaldehyde. Experimental resalts show that mis recycling may be realized When electrolysis and synthetic reaction are carried out in the same concentration of 60% H2SO4 separately, then there will be no waste discharged, energy consumption will be decreased and almost no current efficiency will be lossed during recycling process. The optimun current efficiency is 76%, yield of benzaldehyde is 64%.展开更多
The hydrogenation of benzaldehyde over a series of nickel-containing mesoporous silicas with different nickel contents was studied at atmospheric pressure in the range temperature of 393 - 513 K under H2 ?ow. These ma...The hydrogenation of benzaldehyde over a series of nickel-containing mesoporous silicas with different nickel contents was studied at atmospheric pressure in the range temperature of 393 - 513 K under H2 ?ow. These materials (noted Nin-HMS with n = Si/Ni = 50, 25, 15) have been prepared at room temperature using a route based on hydrogen bonding and self-assembly between neutral primary amine micelles (S0) and neutral inorganic precursors (I0). They were characterized by their chemical analysis, BET surface area, XRD, FT-IR, and SEM microscopy. The obtained products were benzylalcohol, toluene, benzene with yields depending on the nickel content (Si/Ni ratio) and reaction temperature. The products of benzaldehyde hydrogenation (benzylalcohol, and toluene) and hydrogenolysis (benzene) were preferentially formed at low/middle and high reaction temperature respectively. The mesoporous Ni-containing materials were very active hydrogenation catalysts with almost 90% selectivity to benzylalcohol product and showed excellent stability. A mechanism in which the reaction could be initiated by a benzaldehyde reduction over Nin-HMS materials under hydrogen flow with formation of reaction products is proposed.展开更多
The dielectric constant e' and dielectric loss e' of several mixtures of propionaldehyde-polyethylene glycol (system 1) and benzaldehyde-polyethylene glycol (system II) have been measured within the frequency ...The dielectric constant e' and dielectric loss e' of several mixtures of propionaldehyde-polyethylene glycol (system 1) and benzaldehyde-polyethylene glycol (system II) have been measured within the frequency band 105-107 Hz and the temperature range 20-50℃. The dielectric behaviour is discussed. on the other hand, the dielectric relaxation time T. activation energy △He, and entorpy change △Se for the dielectric relaxation as well as activation energy of viscous flow △Hv are calculated for the same temperature range. It is suggested that the observed increase in T values with increas.ng glycol content is due to an increase in the hydrogen bonding in the aggregates or clusters which would be formed between the carbonyl group of the aldehyde and the hydrogen atoms from the glycot molecules. In addition, the higher values of T, △He, and △Se in case of system (II) than that in case of system (I) may be due to the greater volume of the aggregates and the stronger dipole-dipole forces in system (II) compared with those in system (I).展开更多
The quantum chemical method is employed to study the modified asymmetric allylation of benzaldehyde controlled by diisopropyl D-(-)-tartrate auxiliary. All the structures are optimized completely at the B3LYP/6-31G(d,...The quantum chemical method is employed to study the modified asymmetric allylation of benzaldehyde controlled by diisopropyl D-(-)-tartrate auxiliary. All the structures are optimized completely at the B3LYP/6-31G(d,p) level. The (R)-secondary alcohol can be achieved mainly through a six-membered ring chair-like transition state structure. From the relative reaction rates theory the main product configuration predicted is in agreement with the experiment result.展开更多
A chloromethylated styrene-divinylbenzene copolymer support system functionalized with 4-benzaldehyde and 2-benzaldehyde was prepared. The degree of functionalization with aldehyde groups is well suited for the subseq...A chloromethylated styrene-divinylbenzene copolymer support system functionalized with 4-benzaldehyde and 2-benzaldehyde was prepared. The degree of functionalization with aldehyde groups is well suited for the subsequent use of the products as Wittig reagents. The polymer bound aldehyde was reacted with Wittig reagents to give olefin groups grafted on styrene-divinylbenzene copolymers. The reactions were carded out in phase transfer catalysis conditions. A simple procedure for the calculation of the degree of functionalization and the statistical modeling of the structural repetitive unit of the copolymer are reported.展开更多
基金Supported by the National Natural Science Foundation of China(No.51073023)the Co-building Special Profect of Beijing Municipal Education Commission(China)
文摘A simple approach for the condensation of benzaldehyde with ethylene glycol was adopted without employing any catalyst. The study reveals that factors including temperature, molar ratio of reactants, and the water removal significantly influence the conversion ratio of benzaldehyde. The results indicate that the use of optimal reaction conditions such as temperature and water removing exhibits more pronounced effects on the conversion ratio of benzaldehyde compared with the use of catalysts. In a word, a green and simple method for the condensation of aldehyde and menthandiol has been devised and investigated.
基金Project supported by the Science and Technology Department of Zhejiang Province,China (2007C21103)
文摘A series of Mn/CeO2-Al2O3 and K/CeO2-Al2O3 catalysts for hydrogenation of benzoic acid to benzaldehyde were prepared to in- vestigate the effect of Mn, K addition on CeO2-Al2O3 catalyst. X-ray diffraction (XRD) and H2-temperature-programmed reduction (H2-TPR) results suggested that the interaction between CeO2 and MnOx enhanced the reducibility of catalysts and therefore benzoic acid conversion. The addition of K increased the number of basic number on the catalyst which leads to a high selectivity to benzaldehyde, but excessive addition imposed negative effects on the catalyst performance. A Mn-K/CeO2-Al2O3 catalyst was developed and investigated in the reaction. The simultaneous addition of Mn and K enhanced not only the catalytic activity but also the capacity to resist the coke formation over catalyst.
文摘Effects of reaction parameter on yield of benzaldehyde produced from toluene oxidization using hydrogen peroxide in subcritical water are investigated. The experimental results show that if the molar ratio of hydrogen peroxide to toluene is controlled within a reasonable range, the by-products may be neglected. The optimum technology of toluene oxidization to benzaldehyde is reaction time 60 min, reaction temperature 350℃, molar ratio of hydrogen peroxide to toluene 3.5. The yield of benzaldehyde can reach 17.2 % under the optimum condition. Research results of chemical reaction kinetics show that the consecutive reaction consists of two first-order reaction, and activation energy of these two reactions are 89 kJ·mol^-1 and 76 kJ·mol^-1 respectively,
基金supported by the National Science Foundation of China (No. 21006129,11079005 and 21033009)the Ministry of Science and Technology of China (No. 2011CBA00503)
文摘Hydrogenation of benzaldehyde is a typical consecutive reaction, since the intermediate benzyl alcohol is apt to be further hydrogenated. Here we demonstrate that the selectivity of benzyl alcohol can be tuned via functionalization of carbon nanotubes (CNTs), which are used as the support of Pd. With the original CNTs, the selectivity of benzyl alcohol is 88% at a 100% conversion of benzaldehyde. With introduction of oxygen-containing groups onto CNTs, it drops to 27%. In contrast, doping CNTs with N atoms, the selectivity reaches 96% under the same reaction conditions. The kinetic study shows that hydrogenation of benzyl alcohol is significantly suppressed, which can be attributed to weakened adsorption of benzyl alcohol. This is most likely related to the modified electronic structure of Pd species via interaction with functionalized CNTs, as shown by XPS characterization.
文摘Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V+Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No. 4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzaldehyde were higher than those on the undoped catalyst. This was attributed to the disordered structure of V_2O_5 lattice of the K-doped catalyst and a better interracial contact between the particles.
文摘The effect of different concentrations of benzaldehyde on the electrodeposition of Ni–W alloy coatings on a mild steel substrate from a citrate electrolyte was investigated in this study. The electrolytic alkaline bath(p H 8.0) contained stoichiometric amounts of nickel sulfate, sodium tungstate, and trisodium citrate as precursors. The corrosion resistance of the Ni–W-alloy-coated specimens in 0.2 mol/L H2SO4 was studied using various electrochemical techniques. Tafel polarization studies reveal that the alloy coatings obtained from the bath containing 50 ppm benzaldehyde exhibit a protection efficiency of 95.33%. The corrosion rate also decreases by 21.5 times compared with that of the blank. A higher charge-transfer resistance of 1159.40 ?·cm2 and a lower double-layer capacitance of 29.4 μF·cm-2 further confirm the better corrosion resistance of the alloy coating. X-ray diffraction studies reveal that the deposits on the mild steel surface are consisted of nanocrystals. A lower surface roughness value(Rmax) of the deposits is confirmed by atomic force microscopy.
基金supported by the National Natural Science Foundation of China (No. 21376163)
文摘In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.
基金Supported by the National'Natural Science Foundation of China (21036009, 21176268), the Higher-level Talent Project tor Guangdong Provincial Universities and the Fundamental.Research Funds for the Central Universities.
文摘In this paper,the two effluents from PBA (3-phenoxy-benzaldehyde) production process were treated by polymeric adsorbent CHA-111.PBA or PBC (3-phenoxy-benzoic acid) was recovered from the wastewater in the process of neutralization.As a secondary treatment method,adsorption with CHA-111 showed better efficiency than photocatolytic decomposition and solvent extraction.The optimal technological parameters were:adsorption:current velocity:2.0BV/hr(bed volume per hour),room temperature;desorption:current velocity:2.0BV/hr(bed volume per hour),room temperature;desorption:current velocity:1.0 BV/hr,80℃,8% sodium hydroxide aqueous solutions.In conclusion,99.9% COD in the neutralizing wastewater and 98.4% COD in the hydrolysis wastewater are removed successfully.
文摘In this paper, a new catalysts system V-Cs-Cu-TI was studied in the gas phase selective oxidation for p-tert butyl toluene to p-tert benzaldehyde. The catalyst system was prepared by impregnation method. The results obtained are optimum value and have good advantages in environmental protection.
基金This work was supported by the National Natural Science Foundation of China and the Northwest Normal University Science and Technology Devolopment Foundation of China.
文摘Functionalized benzylic zinc halides reacted with benzaldehydes in the presence of Lewis acid Me3SiCl giving high yields of trans-stilbenes under the catalysis of Co(PPh3)3Cl.
文摘This paper has studied the recycling of the oxidation mediator Mn(Ⅲ)/Mn(Ⅱ) and sulfuric acid solution in process of indirect electrosynthesis of benzaldehyde. Experimental resalts show that mis recycling may be realized When electrolysis and synthetic reaction are carried out in the same concentration of 60% H2SO4 separately, then there will be no waste discharged, energy consumption will be decreased and almost no current efficiency will be lossed during recycling process. The optimun current efficiency is 76%, yield of benzaldehyde is 64%.
文摘The hydrogenation of benzaldehyde over a series of nickel-containing mesoporous silicas with different nickel contents was studied at atmospheric pressure in the range temperature of 393 - 513 K under H2 ?ow. These materials (noted Nin-HMS with n = Si/Ni = 50, 25, 15) have been prepared at room temperature using a route based on hydrogen bonding and self-assembly between neutral primary amine micelles (S0) and neutral inorganic precursors (I0). They were characterized by their chemical analysis, BET surface area, XRD, FT-IR, and SEM microscopy. The obtained products were benzylalcohol, toluene, benzene with yields depending on the nickel content (Si/Ni ratio) and reaction temperature. The products of benzaldehyde hydrogenation (benzylalcohol, and toluene) and hydrogenolysis (benzene) were preferentially formed at low/middle and high reaction temperature respectively. The mesoporous Ni-containing materials were very active hydrogenation catalysts with almost 90% selectivity to benzylalcohol product and showed excellent stability. A mechanism in which the reaction could be initiated by a benzaldehyde reduction over Nin-HMS materials under hydrogen flow with formation of reaction products is proposed.
文摘The dielectric constant e' and dielectric loss e' of several mixtures of propionaldehyde-polyethylene glycol (system 1) and benzaldehyde-polyethylene glycol (system II) have been measured within the frequency band 105-107 Hz and the temperature range 20-50℃. The dielectric behaviour is discussed. on the other hand, the dielectric relaxation time T. activation energy △He, and entorpy change △Se for the dielectric relaxation as well as activation energy of viscous flow △Hv are calculated for the same temperature range. It is suggested that the observed increase in T values with increas.ng glycol content is due to an increase in the hydrogen bonding in the aggregates or clusters which would be formed between the carbonyl group of the aldehyde and the hydrogen atoms from the glycot molecules. In addition, the higher values of T, △He, and △Se in case of system (II) than that in case of system (I) may be due to the greater volume of the aggregates and the stronger dipole-dipole forces in system (II) compared with those in system (I).
文摘The quantum chemical method is employed to study the modified asymmetric allylation of benzaldehyde controlled by diisopropyl D-(-)-tartrate auxiliary. All the structures are optimized completely at the B3LYP/6-31G(d,p) level. The (R)-secondary alcohol can be achieved mainly through a six-membered ring chair-like transition state structure. From the relative reaction rates theory the main product configuration predicted is in agreement with the experiment result.
文摘A chloromethylated styrene-divinylbenzene copolymer support system functionalized with 4-benzaldehyde and 2-benzaldehyde was prepared. The degree of functionalization with aldehyde groups is well suited for the subsequent use of the products as Wittig reagents. The polymer bound aldehyde was reacted with Wittig reagents to give olefin groups grafted on styrene-divinylbenzene copolymers. The reactions were carded out in phase transfer catalysis conditions. A simple procedure for the calculation of the degree of functionalization and the statistical modeling of the structural repetitive unit of the copolymer are reported.