Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reac...Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reaction of imides with oxiranes. In this article the kinetics of the reaction of cyclic monoimides: succinimide, phtalimide, and glutarimide, with ethylene and propylene oxides in presence of triethylamine in aprotic solvent was studied. The rate laws for those processes were established based upon on dilatometric measurements. I was said that cyclic monoimides react with oxiranes in presence of triethylamine to give N-(2-hydroxyalkyl)imides as major product. This product react further with oxiranes in consecutive reaction. The kinetics of the reaction of cyclic mono-imides with oxiranes obey the following rate law: V = k1/2 c1/2cat c3/2imide c1/2oxirane. Based upon kinetic data the following orders of reactivity of imides and oxiranes were obtained: phtalimide ≥ succinimide > glutarimide and ethylene oxide > propylene oxide. The solvent (DMF, DMSO and dioxane) effect was also studied. From temperature dependences the thermodynamic parameters: activation energy, enthalpy and entropy from linear Eyring plots were obtained.展开更多
The kinetics of reaction between cyclic monoimides (succinimide, phtalimide, and glutarimide) with ethylene and propylene oxides in presence of sodium hydroxide was studied. The effect of substrate and catalyst concen...The kinetics of reaction between cyclic monoimides (succinimide, phtalimide, and glutarimide) with ethylene and propylene oxides in presence of sodium hydroxide was studied. The effect of substrate and catalyst concentrations on the course of the reaction was investigated. Kinetics of reaction was studied by dilatometry, i.e. by measuring volume contraction of reaction mixture. The kinetic law describing the reaction of imides with oxiranes is: . where ccat, cAH and cB are concentrations of catalyst, imide, and oxirane, respectively. The relative reactivity of imides and oxiranes was: GI > PI ≥ SI and EO > PO. The reaction mechanism was proposed based upon experimentally determined rate law for the reaction of cyclic monoimides and oxiranes as well as analytical and instrumental analysis of products. The elementary reaction between oxirane and imide anion is rate determining step. The imide anion is formed by hydrogen cation transfer into catalytic hydroxide anion from dissociated NaOH. In the consecutive elemental reaction an imidate anion attack on the oxirane molecule occurs. It is the slowest stage of the reaction, limiting the entire process. All the studied reactions obey the same mechanism as can be concluded from isokinetic relationship of studied systems)展开更多
Direct photolysis and quenching experiments with styrene oxide support the existence of an efficient triplet photochemical pathway to benzyl radical formation. Similar photolytic behavior for styrene glycol carbonate ...Direct photolysis and quenching experiments with styrene oxide support the existence of an efficient triplet photochemical pathway to benzyl radical formation. Similar photolytic behavior for styrene glycol carbonate strongly supports the 1,3-diradical, resulting from the scission of the benzylic C-O bond, as the geometric source of the triplet pathway. Primary photoproducts were determined by both NMR and HPLC analysis and we observed that toluene and bibenzyl were both primary photoproducts, not secondary photoproducts.展开更多
The mechanism of reaction of cyclic monoimides with oxiranes was established based upon kinetic studies and product analysis. It has been established that the reaction proceeds through initial formation of an adduct o...The mechanism of reaction of cyclic monoimides with oxiranes was established based upon kinetic studies and product analysis. It has been established that the reaction proceeds through initial formation of an adduct of imide and triethylamine. The crucial bond in adduct has ionic character;in non-aqueous solvents it is present as ion pair, while in water the adduct dissociate and free ions are present. The adduct enables the proton transfer from imide to oxirane. The rate determining step is reaction of imide and this adduct. Different values of entropy of transition states obtained from thermodynamic calculations suggest slightly different structure of transition state of rate determining step.展开更多
A diastereoselectivity-controllable formal[3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed,affording the corresponding tricyclic oxazolidine derivatives in moderate to e...A diastereoselectivity-controllable formal[3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed,affording the corresponding tricyclic oxazolidine derivatives in moderate to excellent yields with excellent diastereoselectivities in the presence of palladium(0)or scandium(III)triflate.This protocol allows selective synthesis of diastereomers of tricyclic oxazolidine derivatives under switchable and mild conditions.Further transformations of the obtained products were conducted by removing ester groups and arylvinyl moieties.展开更多
The aim of this research work was to evaluate the potential of using renewable natural feedstock,i.e.,Jatropha curcas oil(JCO)for the synthesis of non-isocyanate polyurethane(NIPU)resin for wood composite applications...The aim of this research work was to evaluate the potential of using renewable natural feedstock,i.e.,Jatropha curcas oil(JCO)for the synthesis of non-isocyanate polyurethane(NIPU)resin for wood composite applications.Commercial polyurethane(PU)is synthesized through a polycondensation reaction between isocyanate and poly-ol.However,utilizing toxic and unsustainable isocyanates for obtaining PU could contribute to negative impacts on the environment and human health.Therefore,the development of PU from eco-friendly and sustainable resources without the isocyanate route is required.In this work,tetra-n-butyl ammonium bromide was used as the activator to open the epoxy ring with 3-Aminopropyltriethoxisylane as a catalyst to yield urethane of JCO(UJCO).The UJCO were characterized by Fourier Transform Infra-Red spectroscopy(FTIR)and their oxirane,and hydroxyl values were measured.The result showed that a decrease in oxirane value was found while the hydroxyl value was increased during the time,confirming that the urethane group was formed.The presence of functional groups in FTIR spectra at wave numbers 1732.08,1562.34,and 3348.42 cm^(−1) indicates the functional groups of C=O(urethane carbonyl),–NH,and–OH,respectively confirmed this finding.The potential applications of NIPU in the wood composite were also outlined.展开更多
The reaction of singlet oxygen with ethylene has been studied at the ab initio level with both HF/3-21G and HF/6-31G basis sets, fully optimizing the geometries of the critical points. The transition state leading to ...The reaction of singlet oxygen with ethylene has been studied at the ab initio level with both HF/3-21G and HF/6-31G basis sets, fully optimizing the geometries of the critical points. The transition state leading to the intermediate peroxirane from the initial reactants is found,Iocated at 81.71 kJ/mol above the dissociation limit. The vibrational analysis is done with two basis sets. From the results it can be seen that the frequencies have not been made an improvement obviously with augmented 6-31G compared to 3-21G basis; it follows that main reason for too high HF/3-21G frequency could mainly be the vibrational anharmonicity. The eigenvector corresponding to the single imaginary vibrational frequency is dominated by the larger O-O distance. The finding of the transition state confirms that the peroxirane minimum can be reachable passing through a peroxirane-like saddle point. In addition , the mechanisms of the reaction forming oxirane are discussed as well.展开更多
The structures, energies, atomic chaiges and IR spectra of complexes (CH2)2O…XY (X, Y = H, F, Cl, Br, and I) have been examined by means of ab initio molecular orbital theory at the second-order level of Moller-Pless...The structures, energies, atomic chaiges and IR spectra of complexes (CH2)2O…XY (X, Y = H, F, Cl, Br, and I) have been examined by means of ab initio molecular orbital theory at the second-order level of Moller-Plesset perturbation correction. It is found that the hydrogen bond O…H-X is non-linear. The attraction between X and the H atoms in oxirane ring causes O…H-X bond bending. The hydrogen bond slighdy weakens the bond strength of C-O, and leads the bending and stretching mode of IR to shift to the red. The calculation results show that there is no evidence of a significant extent of proton transfer to give (CH2)2OH+ …X- in the isolated complexes.展开更多
文摘Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reaction of imides with oxiranes. In this article the kinetics of the reaction of cyclic monoimides: succinimide, phtalimide, and glutarimide, with ethylene and propylene oxides in presence of triethylamine in aprotic solvent was studied. The rate laws for those processes were established based upon on dilatometric measurements. I was said that cyclic monoimides react with oxiranes in presence of triethylamine to give N-(2-hydroxyalkyl)imides as major product. This product react further with oxiranes in consecutive reaction. The kinetics of the reaction of cyclic mono-imides with oxiranes obey the following rate law: V = k1/2 c1/2cat c3/2imide c1/2oxirane. Based upon kinetic data the following orders of reactivity of imides and oxiranes were obtained: phtalimide ≥ succinimide > glutarimide and ethylene oxide > propylene oxide. The solvent (DMF, DMSO and dioxane) effect was also studied. From temperature dependences the thermodynamic parameters: activation energy, enthalpy and entropy from linear Eyring plots were obtained.
文摘The kinetics of reaction between cyclic monoimides (succinimide, phtalimide, and glutarimide) with ethylene and propylene oxides in presence of sodium hydroxide was studied. The effect of substrate and catalyst concentrations on the course of the reaction was investigated. Kinetics of reaction was studied by dilatometry, i.e. by measuring volume contraction of reaction mixture. The kinetic law describing the reaction of imides with oxiranes is: . where ccat, cAH and cB are concentrations of catalyst, imide, and oxirane, respectively. The relative reactivity of imides and oxiranes was: GI > PI ≥ SI and EO > PO. The reaction mechanism was proposed based upon experimentally determined rate law for the reaction of cyclic monoimides and oxiranes as well as analytical and instrumental analysis of products. The elementary reaction between oxirane and imide anion is rate determining step. The imide anion is formed by hydrogen cation transfer into catalytic hydroxide anion from dissociated NaOH. In the consecutive elemental reaction an imidate anion attack on the oxirane molecule occurs. It is the slowest stage of the reaction, limiting the entire process. All the studied reactions obey the same mechanism as can be concluded from isokinetic relationship of studied systems)
文摘Direct photolysis and quenching experiments with styrene oxide support the existence of an efficient triplet photochemical pathway to benzyl radical formation. Similar photolytic behavior for styrene glycol carbonate strongly supports the 1,3-diradical, resulting from the scission of the benzylic C-O bond, as the geometric source of the triplet pathway. Primary photoproducts were determined by both NMR and HPLC analysis and we observed that toluene and bibenzyl were both primary photoproducts, not secondary photoproducts.
文摘The mechanism of reaction of cyclic monoimides with oxiranes was established based upon kinetic studies and product analysis. It has been established that the reaction proceeds through initial formation of an adduct of imide and triethylamine. The crucial bond in adduct has ionic character;in non-aqueous solvents it is present as ion pair, while in water the adduct dissociate and free ions are present. The adduct enables the proton transfer from imide to oxirane. The rate determining step is reaction of imide and this adduct. Different values of entropy of transition states obtained from thermodynamic calculations suggest slightly different structure of transition state of rate determining step.
基金supported by the National Natural Science Foundation of China(21861008,21761006)Guangxi Natural Science Foundation(2018GXNSFBA138037)+1 种基金Department of Science and Technology of Guangxi(AD19245049)“BAGUI Scholar”Program of Guangxi Province of China。
文摘A diastereoselectivity-controllable formal[3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed,affording the corresponding tricyclic oxazolidine derivatives in moderate to excellent yields with excellent diastereoselectivities in the presence of palladium(0)or scandium(III)triflate.This protocol allows selective synthesis of diastereomers of tricyclic oxazolidine derivatives under switchable and mild conditions.Further transformations of the obtained products were conducted by removing ester groups and arylvinyl moieties.
文摘The aim of this research work was to evaluate the potential of using renewable natural feedstock,i.e.,Jatropha curcas oil(JCO)for the synthesis of non-isocyanate polyurethane(NIPU)resin for wood composite applications.Commercial polyurethane(PU)is synthesized through a polycondensation reaction between isocyanate and poly-ol.However,utilizing toxic and unsustainable isocyanates for obtaining PU could contribute to negative impacts on the environment and human health.Therefore,the development of PU from eco-friendly and sustainable resources without the isocyanate route is required.In this work,tetra-n-butyl ammonium bromide was used as the activator to open the epoxy ring with 3-Aminopropyltriethoxisylane as a catalyst to yield urethane of JCO(UJCO).The UJCO were characterized by Fourier Transform Infra-Red spectroscopy(FTIR)and their oxirane,and hydroxyl values were measured.The result showed that a decrease in oxirane value was found while the hydroxyl value was increased during the time,confirming that the urethane group was formed.The presence of functional groups in FTIR spectra at wave numbers 1732.08,1562.34,and 3348.42 cm^(−1) indicates the functional groups of C=O(urethane carbonyl),–NH,and–OH,respectively confirmed this finding.The potential applications of NIPU in the wood composite were also outlined.
文摘The reaction of singlet oxygen with ethylene has been studied at the ab initio level with both HF/3-21G and HF/6-31G basis sets, fully optimizing the geometries of the critical points. The transition state leading to the intermediate peroxirane from the initial reactants is found,Iocated at 81.71 kJ/mol above the dissociation limit. The vibrational analysis is done with two basis sets. From the results it can be seen that the frequencies have not been made an improvement obviously with augmented 6-31G compared to 3-21G basis; it follows that main reason for too high HF/3-21G frequency could mainly be the vibrational anharmonicity. The eigenvector corresponding to the single imaginary vibrational frequency is dominated by the larger O-O distance. The finding of the transition state confirms that the peroxirane minimum can be reachable passing through a peroxirane-like saddle point. In addition , the mechanisms of the reaction forming oxirane are discussed as well.
基金Project supported jointly by the National Natural Science Foundation of Chinathe Foundation of State Key Laboratory of Structural Chemistry
文摘The structures, energies, atomic chaiges and IR spectra of complexes (CH2)2O…XY (X, Y = H, F, Cl, Br, and I) have been examined by means of ab initio molecular orbital theory at the second-order level of Moller-Plesset perturbation correction. It is found that the hydrogen bond O…H-X is non-linear. The attraction between X and the H atoms in oxirane ring causes O…H-X bond bending. The hydrogen bond slighdy weakens the bond strength of C-O, and leads the bending and stretching mode of IR to shift to the red. The calculation results show that there is no evidence of a significant extent of proton transfer to give (CH2)2OH+ …X- in the isolated complexes.
