The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro- carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ, pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substit...The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro- carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ, pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substituted-cyclopropanes Ⅺ and 2H-1,4-benzothiazin-2-ones Ⅻ.The structures of these products were confirmed by the analytical and spectral data.Compound Ⅷ and Ⅸ are two new ring systems.展开更多
A Nation-H catalyzed, single step and environmentally friendly process for synthesis of dihydropyrimidinones is described. This adopted protocol for Biginelli reaction has the advantages of reusability of the catalyst...A Nation-H catalyzed, single step and environmentally friendly process for synthesis of dihydropyrimidinones is described. This adopted protocol for Biginelli reaction has the advantages of reusability of the catalyst, high yields and ease of separation of pure products.展开更多
The ab initio method has been used to study the 1-3 H transfer reaction on formamidine substituted by halogen. The calculation results show that the substituted halogen has two effects on the 1-3 H transfer reaction...The ab initio method has been used to study the 1-3 H transfer reaction on formamidine substituted by halogen. The calculation results show that the substituted halogen has two effects on the 1-3 H transfer reaction: decreasing the activation energy and stabilizing the C=N double bond owing to the conjugative effect of p-π-p of products and transition states.展开更多
The stereodynamics and reaction mechanism of the H′（^2S） ＋ NH （X^3∑^-） → N（^4S） ＋ H2 reaction are thoroughly studied at collision energies in the 0.1 eV-1.0 eV range using the quasiclassical trajectory （QC...The stereodynamics and reaction mechanism of the H′（^2S） ＋ NH （X^3∑^-） → N（^4S） ＋ H2 reaction are thoroughly studied at collision energies in the 0.1 eV-1.0 eV range using the quasiclassical trajectory （QCT） on the ground 4A″ potential energy surface （PES）. The distributions of vector correlations between products and reagents P（φr）, P（φr） and P（φr,φr） are presented and discussed. The results indicate that product rotational angular momentum j′ is not only aligned, but also oriented along the direction perpendicular to the scattering plane; further, the product H2 presents different rotational polarization behaviors for different collision energies. Furthermore, four polarization-dependent differential cross sections （PDDCSs） of the product He are also calculated at different collision energies. The reaction mechanism is analyzed based on the stereodynamics properties. It is found that the abstraction mechanism is appropriate for the title reaction.展开更多
Quasi-classical trajectory （QCT） calculations are employed to study the dynamic properties for H（D）＋OF reactions on the adiabatic potential energy surface （PES） of the 1^3A″ triplet state. Obvious differences ...Quasi-classical trajectory （QCT） calculations are employed to study the dynamic properties for H（D）＋OF reactions on the adiabatic potential energy surface （PES） of the 1^3A″ triplet state. Obvious differences between the reaction probabilities for J=0, integral cross sections for J≠0, branch ratios of the product and internuclear distances as well as product rotational alignments between the title reactions axe found. These differences are attributed mainly to the different reduced masses of the reactants and the different zero-point energies （ZPEs） of the transition state.展开更多
Quasi-classical trajectory theory is used to study the reaction of O（3p） with H2 （D2） based on the ground 3A″ potential energy surface （PES）. The reaction cross section of the reaction O＋H2→＋OH＋H is in exce...Quasi-classical trajectory theory is used to study the reaction of O（3p） with H2 （D2） based on the ground 3A″ potential energy surface （PES）. The reaction cross section of the reaction O＋H2→＋OH＋H is in excellent agreement with the previous result. Vector correlations, product rotational alignment parameters （P2（j′. k）） and several polarizeddependent differential cross sections are further calculated for the reaction. The product polarization distribution exhibits different characteristics that can be ascribed to different motion paths on the PES, arising from various collision energies or mass factors.展开更多
The product rotational polarizations of reaction Li-SHF→LiF-kH at different collision energies, as well as at the different vibrational states and rotational states, are calculated by using the quasi-classical trajec...The product rotational polarizations of reaction Li-SHF→LiF-kH at different collision energies, as well as at the different vibrational states and rotational states, are calculated by using the quasi-classical trajectory method based on a new potential energy surface constructed by Aguado et al. [J. Chem. Phys. 119（2003） 10088]. We investigate the Mignment and the orientation of the product molecule by calculating the P（θr, φr） distribu- tions describing polar angle distribution, the P（θr） distributions describing the k-j＇ correlation and the P（φr） distributions describing the k-k＇-j＇ correlation. We also explore the dependence of reaction probabilities and cross sections on the rotational and vibrational quantum number of the title reaction. It is concluded that the vibrational state has more important impact on the angular distribution, reaction probability and cross section.展开更多
The reaction mechanism of 3 chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3 chlorophenol aqueous solutions have been saturated with air or N 2 previously. Under alkaline condi...The reaction mechanism of 3 chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3 chlorophenol aqueous solutions have been saturated with air or N 2 previously. Under alkaline condition, the reaction of OH radical with 3 chlorophenol produces 3 chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3 chlorophenol produces OH adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3 chlorophenol produces H adduct with the maximal absorption at about 320 nm. 3 chlorophenol is compared with 4 and 2 chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.展开更多
A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, t...A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.展开更多
We have investigated the H/D exchange reaction between heavy water and an ionic liquid, 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF4]), throughout the whole concentration region as a function of D2O mol%...We have investigated the H/D exchange reaction between heavy water and an ionic liquid, 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF4]), throughout the whole concentration region as a function of D2O mol% at room temperature. We expected that the extent of the H/D reaction would increase linearly with increasing content of D2O, but the results show an extended N-shaped behavior having a small maximum at around 40 mol% and the reaction becomes very slow at a specific concentration around 80 mol%. We found that this non-linear concentration dependence correlates with the pD dependence of the solutions.展开更多
Quasi-classical trajectory(QCT)calculations are reported for the H+LiH(v=0-2,j=0)→Li+H2 reaction on a new ground electronic state global potential energy surface(PES)of the LiH2 system.Reaction probability and integr...Quasi-classical trajectory(QCT)calculations are reported for the H+LiH(v=0-2,j=0)→Li+H2 reaction on a new ground electronic state global potential energy surface(PES)of the LiH2 system.Reaction probability and integral cross sections(ICSs)are calculated for collision energies in the range of 0 eV-0.5 eV.Reasonable agreement is found in the comparison between present results and previous available theoretical results.We carried out statistical analyses with all the trajectories and found two main distinct reaction mechanisms in the collision process,in which the stripping mechanism(i.e.,without roaming process)is dominated over the collision energy range.The polarization dependent differential cross sections(PDDCSs)indicate that forward scattering dominates the reaction due to the dominated mechanism.Furthermore,the reactant vibration leads to a reduction of the reactivity because of the barrierless and attractive features of PES and mass combination of the system.展开更多
In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor...In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor(HTO vapor) and 4-amino-2-methylbenzenesulfonic acid (and 5-amino-2-methylphenol) were dynamically observedat 50 (and 70 ) in a gas ℃ ℃ -solid system. Consequently, the fact that the specific activity of the acid increased withtime was obtained, and the T-for-H exchange reaction occurred. By applying the A"-McKay plot method to the dataobserved, the rate constant of each functional group for the reaction was obtained. After the additive property of theHammett’s rule was applied to this work, the new substituent constants were obtained. From the above-mentioned,the following four items have been confirmed: (1) the reactivity of the functional groups can be dynamically analyzed,and the A"-McKay plot method is useful to analyze the reactivity; (2) the additive property of the Hammett’s rule isapplicable to quantitative comparison of the reactivity of the functional groups; (3) the reactivity of the functionalgroups can be simultaneously analyzed by using the A"-McKay plot method in the T-H exchange reaction; and (4) themethod used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups.展开更多
文摘The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro- carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ, pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substituted-cyclopropanes Ⅺ and 2H-1,4-benzothiazin-2-ones Ⅻ.The structures of these products were confirmed by the analytical and spectral data.Compound Ⅷ and Ⅸ are two new ring systems.
文摘A Nation-H catalyzed, single step and environmentally friendly process for synthesis of dihydropyrimidinones is described. This adopted protocol for Biginelli reaction has the advantages of reusability of the catalyst, high yields and ease of separation of pure products.
基金Supported by the Yunnan Provincial Science and Technology Department (2003A0003M)
文摘The ab initio method has been used to study the 1-3 H transfer reaction on formamidine substituted by halogen. The calculation results show that the substituted halogen has two effects on the 1-3 H transfer reaction: decreasing the activation energy and stabilizing the C=N double bond owing to the conjugative effect of p-π-p of products and transition states.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11204392 and 11047125)
文摘The stereodynamics and reaction mechanism of the H′（^2S） ＋ NH （X^3∑^-） → N（^4S） ＋ H2 reaction are thoroughly studied at collision energies in the 0.1 eV-1.0 eV range using the quasiclassical trajectory （QCT） on the ground 4A″ potential energy surface （PES）. The distributions of vector correlations between products and reagents P（φr）, P（φr） and P（φr,φr） are presented and discussed. The results indicate that product rotational angular momentum j′ is not only aligned, but also oriented along the direction perpendicular to the scattering plane; further, the product H2 presents different rotational polarization behaviors for different collision energies. Furthermore, four polarization-dependent differential cross sections （PDDCSs） of the product He are also calculated at different collision energies. The reaction mechanism is analyzed based on the stereodynamics properties. It is found that the abstraction mechanism is appropriate for the title reaction.
基金Project supported by the National Natural Science Foundation of China (Grant No.10574083)the Natural Science Foundation of Shandong Province of China (Grant No.Y2006A23)+1 种基金the National Basic Research Program of China (Grant No.2006CB806000)the Open Fund of the State Key Laboratory of High Field Laser Physics (Shanghai Institute of Optics and Fine Mechanics)
文摘Quasi-classical trajectory （QCT） calculations are employed to study the dynamic properties for H（D）＋OF reactions on the adiabatic potential energy surface （PES） of the 1^3A″ triplet state. Obvious differences between the reaction probabilities for J=0, integral cross sections for J≠0, branch ratios of the product and internuclear distances as well as product rotational alignments between the title reactions axe found. These differences are attributed mainly to the different reduced masses of the reactants and the different zero-point energies （ZPEs） of the transition state.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.60977063 and 10574039)the Innovation Scientists and Technicians Troop Construction Projects of Henan Province of China (Grant No.084100510011)
文摘Quasi-classical trajectory theory is used to study the reaction of O（3p） with H2 （D2） based on the ground 3A″ potential energy surface （PES）. The reaction cross section of the reaction O＋H2→＋OH＋H is in excellent agreement with the previous result. Vector correlations, product rotational alignment parameters （P2（j′. k）） and several polarizeddependent differential cross sections are further calculated for the reaction. The product polarization distribution exhibits different characteristics that can be ascribed to different motion paths on the PES, arising from various collision energies or mass factors.
基金Supported by the National Natural Science Foundation of China under Grants No 11274205
文摘The product rotational polarizations of reaction Li-SHF→LiF-kH at different collision energies, as well as at the different vibrational states and rotational states, are calculated by using the quasi-classical trajectory method based on a new potential energy surface constructed by Aguado et al. [J. Chem. Phys. 119（2003） 10088]. We investigate the Mignment and the orientation of the product molecule by calculating the P（θr, φr） distribu- tions describing polar angle distribution, the P（θr） distributions describing the k-j＇ correlation and the P（φr） distributions describing the k-k＇-j＇ correlation. We also explore the dependence of reaction probabilities and cross sections on the rotational and vibrational quantum number of the title reaction. It is concluded that the vibrational state has more important impact on the angular distribution, reaction probability and cross section.
文摘The reaction mechanism of 3 chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3 chlorophenol aqueous solutions have been saturated with air or N 2 previously. Under alkaline condition, the reaction of OH radical with 3 chlorophenol produces 3 chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3 chlorophenol produces OH adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3 chlorophenol produces H adduct with the maximal absorption at about 320 nm. 3 chlorophenol is compared with 4 and 2 chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.
基金Supported by the National Natural Science Foundation of China(No.20773014 and 20933001)the Research Foundation of Education Bureau of Hebei Province(No.Z2011115)+3 种基金the 111 Project of China(No.B07012)the Natural Science Foundation of Hebei Province(No.B2012105002)the Research Foundation of Tangshan Administration of Science&Technology(121302011a)the Research Foundation of Tangshan normal college(2013A04)for their support of this work
文摘A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.
文摘We have investigated the H/D exchange reaction between heavy water and an ionic liquid, 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF4]), throughout the whole concentration region as a function of D2O mol% at room temperature. We expected that the extent of the H/D reaction would increase linearly with increasing content of D2O, but the results show an extended N-shaped behavior having a small maximum at around 40 mol% and the reaction becomes very slow at a specific concentration around 80 mol%. We found that this non-linear concentration dependence correlates with the pD dependence of the solutions.
文摘Quasi-classical trajectory(QCT)calculations are reported for the H+LiH(v=0-2,j=0)→Li+H2 reaction on a new ground electronic state global potential energy surface(PES)of the LiH2 system.Reaction probability and integral cross sections(ICSs)are calculated for collision energies in the range of 0 eV-0.5 eV.Reasonable agreement is found in the comparison between present results and previous available theoretical results.We carried out statistical analyses with all the trajectories and found two main distinct reaction mechanisms in the collision process,in which the stripping mechanism(i.e.,without roaming process)is dominated over the collision energy range.The polarization dependent differential cross sections(PDDCSs)indicate that forward scattering dominates the reaction due to the dominated mechanism.Furthermore,the reactant vibration leads to a reduction of the reactivity because of the barrierless and attractive features of PES and mass combination of the system.
文摘In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor(HTO vapor) and 4-amino-2-methylbenzenesulfonic acid (and 5-amino-2-methylphenol) were dynamically observedat 50 (and 70 ) in a gas ℃ ℃ -solid system. Consequently, the fact that the specific activity of the acid increased withtime was obtained, and the T-for-H exchange reaction occurred. By applying the A"-McKay plot method to the dataobserved, the rate constant of each functional group for the reaction was obtained. After the additive property of theHammett’s rule was applied to this work, the new substituent constants were obtained. From the above-mentioned,the following four items have been confirmed: (1) the reactivity of the functional groups can be dynamically analyzed,and the A"-McKay plot method is useful to analyze the reactivity; (2) the additive property of the Hammett’s rule isapplicable to quantitative comparison of the reactivity of the functional groups; (3) the reactivity of the functionalgroups can be simultaneously analyzed by using the A"-McKay plot method in the T-H exchange reaction; and (4) themethod used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups.
