3-羟基-2-吡啶亚胺异构反应的机理

在RHF-6-31G,MP2/6-31G和MP2/6-31G水平上,对3-羟基-2-吡啶亚胺的气相、水分子作为催化剂的异构化反应进行了研究,结果表明,气象异构难于进行,水分子作为催化剂参与反应过程是目标反应所循的反应路径。     

Theoretical study of the gas-phase thermolysis reaction of alkyl (ethyl,isopropyl, and tert-butyl) N,N-dimethylcarbamates and N,N-diethylcarbamates

Theoretical studies on the thermolysis in the gas phase of alkyl N,N-dialkylcarbamates were carried out using ab initio theoretical methods, at the MP2/6-31G(d), MP2/6-31++G(d,p) and MP2/6-311++G(2d,p)//MP2/6-31G(d) levels. The reactions have two steps: the first one corresponds to the formation of an alkene and a neutral dialkylcarbamic acid intermediate via a six-membered cyclic transition state; the second one is the decarboxylation of this intermediate via a four-membered cyclic transition state, leading to carbon dioxide and the corresponding dialkylamine. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous. The bond-breaking processes are more advanced than the bond-forming ones, indicating a bond deficiency in the transition states. The rate constants calculated for all the reactions agree very well with the available experimental data.From the Proceedings of the 28th Congreso de Químicos Teóricos de Expresión Latina (QUITEL 2002)     

Gas-phase elimination reactions of 4-substituted-2-alkoxythiazoline-5-ones

Gas-phase eliminations of 4-substituted-2-alkoxythiazoline-5-ones have been studied. These compounds eliminate via a six-membered transition state to produce 4-substituted-thiazolidine-2,5-diones. These eliminations are unimolecular first-order reactions. Utilization of this thermolysis reaction in the synthesis of new 4-substituted-thiazolidine-2,5-diones is considered. Additional mechanistic information was obtained by comparing the kinetic data for thermal elimination reactions of these compounds with that of 1-ethoxythiazole. © 1996 John Wiley & Sons, Inc.     

Density functional theory study of mechanism of forming a spiro-Ge-heterocyclic ring compound from H2Ge=Ge: and ethene

The mechanism of the cycloaddition reaction between singlet H₂Ge=Ge: and ethene has been investigated by the B3LYP/6-311 ++G** method. From the potential energy profile and change of Gibbs free energy, it could be predict that the reaction has only one dominant reaction pathway at 298 K and 149.825 kPa. The reaction rule presented is that the two reactants first form a four-membered Ge-heterocyclic ring germylene through the [2 + 2] cycloaddition reaction; because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the π orbital of ethene forming a π → p donor–acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with ethene to form an intermediate; and because the Ge: atom in intermediate happens sp³ hybridization after transition state, then the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state.     

A density functional theory study of the gas-phase elimination reactions of 4-arylideneimino-1,2,4-triazol-3(2H )-ones and their 3(2H )-thione analogues

Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002)     

Ab initio method study on the isomerization of 3-amino-2-pyridone

Ab initio caculations with RHF/6-31G and MP2/6-31G have been used to study the isomerization of 3-amino-2-pyridone in gas-phase and in water. The results obtained show that 3-amino-2-pyridone is isomerized into 3-amino-2-hydroxy pyridine via a four-center cyclic transition state in the gas-phase, and via a six-center cyclic transition state in water. The activation energies of this reaction are 226.3336(RHF/6-31G) and 171.2269(MP2/6-31G) in gas-phase, and 81.6398(RHF/6-31G) and 59.8668(MP2/6-31G) kJ mol⁻¹ under the condition of a single water molecule as the catalyst, respectively.     

3-羟基-3-甲基-2-丁酮和苯甲酰甲酸甲酯热分解反应的 理论研究

用从头算的方法在6-31G水平上研究了3-羟基-3-甲基-2-丁酮(1)和苯甲酰甲酸甲酯(2)热分解反应的机理。结果是:前一反应是经历五元环过渡态到达氢键中间体,它接着直接分解成乙醛的异构体和丙酮,最后乙醛的异构体异构化成乙醛;后一反应经历六元环过渡态形成中间体1(INT1),中间体1(INT1)直接分解成中间体2(INT2)和甲醛,中间体2(INT2)经过第二个过渡态分解成苯甲醛的异构体和一氧化碳,最后苯甲醛异构体异构化成苯甲醛。其中氢迁过程是反应的速控步骤。在MP~2/6-31G//HF/6-31G+ZPE水平上,对应于这两个反应速控步骤的活化位垒分别是251.42kJ/moL和247.94kJ/mol。采用传统过渡态理论计算了两反应的热反应速率常数,理论的计算结果与实验值吻合较好。     

Computational study on the mechanism and thermodynamic of atmospheric oxidation of HCN with ozone

Oxidation of hydrogen cyanide with ozone on the singlet potential energy surface is carried out using the MP2 and CCSD(T)//MP2 theoretical approaches in connection with the 6-311++G(d,p) basis set. In this reaction, energy barrier of transition states are low, so the reaction of HCN with ozone can occur easily at atmospheric condition. With variety of pre-reactive complex, five types of products are obtained at the MP2 method which four types of them have enough thermodynamic stability at the standard condition. CO₂ + HNO are final adducts in a process that is computed to be exothermic by ?132.605 kcal/mol in standard enthalpy and spontaneous by ?144.166 kcal/mol in Gibbs free energy of reaction. In kinetic viewpoint, the production of OCN + HO₂ adducts path with one low level transition state is the most favored path.     

Theoretical studies on the reactions OH + CH3COCCl2 X (X = F, Cl, Br)

Theoretical investigations are carried out on the title reactions by means of the direct dynamics method. The optimized geometries, frequencies and minimum energy path are obtained at the MP2/6-31 + G(d,p) level, and energetic information is further refined at the MC-QCISD (single-point) level. The rate constants for both reactions are calculated by the improved canonical variational transition state theory with the small-curvature tunneling correction in a wide temperature range 200–3,000 K. The theoretical rate constant is in good agreement with the available experimental data. Furthermore, the effects of different halogen substitution on the rate constants are also discussed.     

Gas‐Phase Elimination Reaction of Ethyl (5‐cyanomethyl‐1,3,4‐thiadiazol‐2‐yl)carbamate: A Computational Study

The gas‐phase elimination reaction of ethyl (5‐cyanomethyl‐1,3,4‐thiadiazol‐2‐yl)carbamate has been studied computationally at the MP2/6–31++G(2d,p) level of theory. The values of the activation parameters and rate constants for the thermal decomposition were evaluated over a temperature range from 405.0 to 458.0 K. The temperature dependence of the rate constants was used to deduce the modified Arrhenius expression: log k_{405–458 K} = (9.01 ± 0.49) + (1.32 ± 0.16) log T – (6946 ± 30) 1/T, which is in good agreement with the expression obtained from experimental data. The results confirm that the mechanism is a cis‐concerted elimination that occurs in two steps: The first one corresponds to the formation of ethylene and an intermediate, 5‐(cyanomethyl)‐1,3,4‐thiadiazol‐2‐yl‐carbamic acid, via a six‐membered cyclic transition state, and the second one is the decarboxylation of this intermediate via a four‐membered cyclic transition step, leading to carbon dioxide and the corresponding 1,3,4‐thiadiazole derivative (5‐amino‐1,3,4‐thiadiazole‐2‐acetonitrile). The connectivity of transition states with their respective minima was verified through intrinsic reaction coordinate calculations, and the progress of the reaction was followed by means of Wiberg bond indices, resulting that both transition states have an “early” character, nearer to the reactants than to the products.     

Theoretical study for the CH3C(O)(CH2)2OH + OH reaction

The mechanisms and the kinetics of the OH radical reaction with 4-hydroxy-2-butanone (4H2B) are investigated theoretically. Five hydrogen-abstraction channels are identified for the title reaction. The first potential energy profile of the title reaction is presented. The rate constants for each reaction channel are evaluated using transition state theory method in the temperature range of 200–1,000 K. Branching ratio of the title reaction is calculated and plotted. It is shown that the “in-plane hydrogen abstraction” from the methoxy end is the dominant channel, and the other hydrogen-abstraction channels play the minor role. The comparison between theoretical and experimental results is discussed. The three-parameter Arrhenius expression for the rate constants is also provided.     

Mechanistic and dual-level direct dynamics studies on the reaction Cl + CH2FCl

Theoretical investigations are carried out on the reaction Cl + CH₂FCl by means of direct dynamics method. The minimum energy path (MEP) is obtained at the MP2/6-311G(d, p) level. The energetic information is further improved by single-point energy calculations using QCISD(T)/6-311++G(d, p) method. The kinetics of this reaction are calculated by canonical variational transition state theory incorporating with the small-curvature tunneling correction over a wide temperature range of 220–3,000 K, and rate constant expression are found to be k(T) = 1.48 × 10^?17 T ^2.04exp(?913.91/T). For the title reaction, H-abstraction reaction channel is the major channel at the lower temperatures. At higher temperatures, the contribution of Cl-abstraction reaction channel should be taken into account.     

Computational study of the thermal decomposition and the thermochemistry of allyl ethers and allyl sulfides

In spite of the several experimental and computational studies on the thermal decomposition of allyl ethers and allyl sulfides, there are still disagreements on aspects of the reaction mechanism, such as the true nature of the transition states and the grade of synchronicity of the reactions. This work presents a computational study of the gas-phase thermolysis reaction of allyl ethers and allyl sulfides substituted at α-carbon, at the M05-2X/6-31+G(d,p) level of theory and a temperature range from 586.15 to 673.15 K. The substituent groups were methyl, ethyl, n-propyl, i-propyl, allyl, benzyl and acetonyl. It was found that the sulfides react faster than the homologous ethers and that the substituent groups with the capacity of delocalize charge increase the reaction rate. Through natural bond orbital calculations, the transition states were characterized. The synchronicities and atomic charges of the studied reactions were determined. A computational study at the G3 level of theory on the thermochemistry of allyl ethers and sulfides was also carried out.     

Pyrolysis of aminonitriles,cyanohydrazones, and cyanoacetamides. Part I. Elimination reaction of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles and substituted benzaldehyde cyanoacetylhydrazones

Pyrolysis of the Schiff bases of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles (1–5) has been studied. These compounds eliminate via a six-membered transition state to produce substituted benzonitriles and 2-hydroxy-4,6-dimethylpyridine-3-carbonitrile. These eliminations are unimolecular first-order reactions. The kinetic data gave a good correlation with σ⁰ values of the substituents on the aryl group with ρ = 0.83 at 520 K. Utilization of the pyrolytic reaction in synthesis of various benzonitriles is considered, and mechanistic information has been obtained by comparing the kinetic data and product analysis of the Schiff bases with their open-chain substituted benzaldehyde cyanoacetylhydrazones (6–9) analogues. © 1996 John Wiley & Sons, Inc.     

Theoretical studies of decomposition kinetics of CF3CCl2O radical

The unimolecular decomposition reaction of CF₃CCl₂O radical has been investigated using theoretical methods. Two most important channels of decomposition occurring via C–C bond scission and Cl elimination have been considered during the present investigation. Ab initio quantum mechanical calculations are performed to get optimized structure and vibrational frequencies at DFT and MP2 levels of theory. Energetics are further refined by the application of a modified Gaussian-2 method, G2M(CC,MP2). The thermal rate constants for the decomposition reactions involved are evaluated using Canonical Transition State Theory (CTST) utilizing the ab initio data. Rate constants for C–C bond scission and Cl elimination are found to be 6.7 × 10⁶ and 1.1 × 10⁸ s^?1, respectively, at 298 K and 1 atm pressure with an energy barrier of 8.6 and 6.5 kcal/mol, respectively. These values suggest that Cl elimination is the dominant process during the decomposition of the CF₃CCl₂O radical. Transition states are searched on the potential energy surface of the decomposition reactions involved and are characterized by the existence of only one imaginary frequency (NIMAG = 1) during frequency calculation. The existence of transition states on the corresponding potential energy surface is further ascertained by performing intrinsic reaction coordinate (IRC) calculation.     

Theoretical study on the kinetics and branching ratios of the gas phase reactions of 1, 1-Dichlorodimethylether (DCDME) with Cl atom

Quantum mechanical calculations are carried out on the reactions of CH₃OCHCl₂ (DCDME) with Cl atom by means of DFT and couple cluster methods. The geometries of the reactants, products, and transition states involved in the reaction pathways are optimized at BHandHLYP level of theory using 6-311G(d,p) basis set. Transition states are searched on the potential energy surface involved during the reaction channels, and each of the transition states is characterized by the presence of only one imaginary frequency. The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate calculation. Single point energy calculations are performed at CCSD(T) level using the same basis set. The hydrogen abstraction rate constant for the title reaction is calculated at 298 K and atmospheric pressure using the canonical transition state theory including tunneling correction. The calculated value for rate constant as 1.204 × 10^?12 cm³ molecule^?1 s^?1 is found to be in very good agreement with the recent experimental data. The percentage contributions of both reaction channels are also reported at 298 K.     

SOM assembly of hydroxynaphthoquinone and its oxime: polymorphic X-ray structures and EPR studies

Investigation on solvent-induced polymorphism in X-ray structures of 2-hydroxy-1,4-naphthoquinone (Lawsone) 1, is carried out. In protic methanol, 1 crystallizes in monoclinic space group P2(1)/c (1a) comprising of 2D hydrogen bonded network via cyclic dimers. In aprotic solvent such as acetone on the other hand, 1 exhibits orthorhombic space group Pna 2(1) (1b) and emerges with 1D catemeric chain. Solvent-induced topological isomerism of cyclic dimers and helical catemeric chains arising from (i) bifurcated intra- and inter molecular hydrogen bondings viz. O-H...O=C interactions between C(2) hydroxyl and C(1), C(4) carbonyls, (ii) C-H...O interactions viz. C(3)-H...O(1)C(1) have been discussed. A signal for radical in 1 at g = 2.0058 is signatured by EPR spectrum and it's oxime derivative viz. 2-hydroxy-4-naphthoquinone-1-oxime 2, in solid state shows biradical and monoradical formation with aggregation of dimer and monomer due to non-covalent hydrogen bonds. Zero field split parameters for 2 are estimated to be D = 215 G, Ex = 13 G, Ey = 47 G at 298 K. A half field signal at 77 K indicates triplet ground state. Frozen glass EPR of 2 resolves as regioregular dimeric-monomeric species showing hyperfine interactions with 1-oximino nitrogen in dimer A (14N) = 15.5 G].     

Experimental and computational study of the thermal decomposition of 3-buten-1-ol in m-xylene solution

An experimental study of the thermal decomposition of a β-hydroxy alkene, 3-buten-1-ol, in m-xylene solution, has been carried out at three different temperatures: 553.15, 573.15, and 593.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (27.34 ± 1.24)–(19,328 ± 712) (kJ mol^?1) T ^?1. A computational study has been performed at the MP2/6-31+G(d) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. The Arrhenius equation obtained theoretically, ln k (s^?1) = (28.252 ± 0.025)–(19,738.0 ± 14.4) (kJ mol^?1) T ^?1, agrees very satisfactorily with the experimental one. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis which provides the natural atomic charges and the Wiberg bond indices used to follow the progress of the reaction. The enthalpy of the reaction has been calculated using experimental values taken from literature and theoretic calculations. The agreement between both values is satisfactory.     

Functional polymers. XIV. Grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto polymers with aliphatic groups

Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C? H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150–160°C with di-tertiary butylperoxide as the grafting initiator, grafts as high as 20–30% at grafting efficiencies of 50 and 80% have readily been obtained. It was very important to carry out the grafting reaction in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. Grafting reactions were carried out on a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate.     

Rate coefficient for the reaction SiO + Si2O2 at T = 10-1000 K

The reaction paths for the formation of Si3O3 molecules have been investigated at high level ab initio quantum chemical calculations by using the QCISD method with the 6-311++G(d,p) basis set. The cis-Si2O2 isomer does not participate in the chemical mechanism for the formation of Si3O3 molecules. Although the SiO + cis-Si2O2 reaction is exothermic and spontaneous, it is not expected to explain the growth mechanism of Si3O3 in the interstellar silicate grains of circumstellar envelopes surrounding M-type giants. The reaction of SiO with cyclic Si2O2 molecules is exothermic, is spontaneous, and has a nonplanar transition state. The Gibbs free energy for the transition state formation, (DeltaG0#), is around 5.5 kcal mol-1 at 298 K. The bimolecular rate coefficient for this reaction, kT, is about 1 x 10-12 cm3 molecule-1 s-1 at 298 K and in the collision limit, 1.5 x 10-10 cm3 molecule-1 s-1, at 500 K. The activation energy, Ea, is about 8 kcal mol-1. The enthalpy of Si3O3 fragmentation is 53.9 kcal mol-1 at 298 K. The SiO + cyclic Si2O2 reaction is expected to be the most prominent reaction path for the Si3O3 formation in interstellar environment and fabrication of silicon nanowires.