bluuebunny/crossref_metadata_2025_split huggingface dataset:
Linear dependence of the degree of aggregation on the solvent aggregating power (SAgP)
Authors: Jiang Xi‐Kui , Ji Guo‐Zhen , Luo Guang‐Lin 
Published: September 2010

AbstractWith k8/k16, the ratio of the hydrolytic rate‐constants of p‐nitrophenyl octanoate (C8) to hexadecanoate (C16), as the indicator of the degree of aggregation, the linear dependence of the degree of aggregation on solvent aggregating power (SAgP) has been established in five aquiorgano solvents, each within a certain range of volume fraction (ϕ values) of the organic cosolvent. The meaning of this linearity has been discussed.
Nitriles in heterocyclic synthesis: Studies on ethyl 3‐amino‐4,4‐dicyano‐3‐butenoate
Authors: Soliman A.Y. , Bakeer H.M. 
Published: September 2010

AbstractNew polyfunctionally substituted heterocyclic compounds were synthesized from ethyl 3‐amino‐4,4‐dicyano‐3‐butenoate (1) as a starting material.
A comparison of the determination of stability constants of complexes of Pb(II) with amino acids using micro‐pH‐metric titrations and cyclic voltammetry
Authors: Lu Ai‐Ru , Pettit D. Leslie , Bernard Gareth , Gregor E. Jan 
Published: September 2010

AbstractThis paper reports the determination of stability constants for complexes of Pb(II) with Gly, Ala, Asp and Gly‐Gly using both micro‐pH‐metric titrations and the application of convolution‐de‐convolution cyclic voltammetry at 25°C and I = 0.10 mol·dm−3 (KNO3). Stability constants were calculated from pH‐metric data using the SUPERQUAD computer program and cyclic voltammograms were collected, stored and manipulated using the E G and G CONDECON 300 software. A′ considerably larger ligand: metal ratio (e.g. 50:1) was possible using voltammetry. Under these conditions, hydroxy complex formation was minimised and the formation of bis‐complexes optimised. Computer based calculations were carried out on PC‐compatible microcomputers fitted with mathematics coprocessors. Evaluation of results from the two techniques suggests that stability constants for the species [PbL2] are reliable when calculated from voltammetry while those for [PbL] are more reliable when determined by pH‐metric titration.
Determination of trace silver in waste water by 9,10‐dimethylacridinium fluorosulfonate‐K2S2O8 chemiluminescence system
Authors: Lin Jin‐Ming , Zhang Fan 
Published: September 2010

AbstractA new highly sensitive method for determination of trace silver in waste water with 9,10‐dimethylacridinium fluorosulfonate (DAFA)‐K2S2O8 system was suggested. In the basic aqueous solution, trace of silver (I) showed strongly catalytic effect on the chemiluminescence system with the presence of 2,2′‐bipyridine. The range of the linear relationship between light intensity and concentration of silver (I) is 1.0 × 103 mol / L to 6.0 × 103 mol / L. The detection limit is 8.0 × 103 mol / L, and the RSD for 5.0 × 103 mol / L Ag (I) is 6.5% (n=13). In the existence of potassium fluoride, the selectivity is higher. Combining the treatment with nitric acid, the method is applied to determine some environmental waste water and the results are similar to atomic absorption spectroscopy.
Sensitized photooxygenation VI. Kinetic studies on the singlet oxygenation of 6‐ethyl‐3, 4‐dihydro‐2H‐pyran‐5‐carboxylic acid ethyl ester and 6‐isopropyl‐3,4‐dihydro‐2H‐pyran‐5‐carboxylic acid ethyl ester
Authors: Huang Ze‐En , Liang Xiao‐Guang , Leung Hiu‐Kwong , Chan Yuk‐Yee 
Published: September 2010

AbstractKinetic studies of the singlet oxygenation of the title compounds were performed according to Monroe's method. The reaction rate increases with temperature decreasing, leading to a negative activation enthalpy and a large negative activation entropy. These data are interpreted as the evidence for the intermediacy of an exciplex. The solvent effect on the reaction rate suggests that the “dioxetane” path involves a transition state or an intermediate with significant zwitterionic character. The electronic effect of the substituent is obvious, with electron‐withdrawing substituent retarding the reaction and electron‐donating substituent increasing the reaction rate. However, steric bulkiness at the 6‐position does not play an important role in the reaction rate.
Interaction of cyclodextrins with 1,3‐di(1‐naphthyl)propane and the additive effects of ionic surfactants
Authors: Xie Rui‐Qiang , Lei Xue‐Gong , Liu You‐Cheng 
Published: September 2010

AbstractThe interaction between cyclodextrins (CDs) and 1,3‐di(1‐naphthyl)propane (1) in aqueous methanol (V:V=1:1) has been investigated by means of fluorescence emission and UV absorption. Fluorescence enhancement and absorption spectra reveal that β‐ or γ‐CD can form inclusion complexes with 1, but a‐CD cannot. One of these complexes is identified as ground state complex (2:1), i.e. the eclipsed conformer of 1 is included. Molecule 1 can be driven out of the CD cavity by sodium dodecylsulfate (SDS) molecule, but cannot by cetyltrimethylammonium bromide (CTAB) or sodium cetylsulfate (SCS) molecules due to their alkyl chain coiling.
Geometry optimization and electronic structures of molecules H3AXAH3
Authors: Wang Zhi‐Zhong , Shen Er‐Zhong 
Published: September 2010

AbstractThe geometries of molecules H3AXAH3 (X=O, S, Se and A=C, Si) have been optimized using STO‐3G ab initio calculations and gradient method and the results are in good agreement with reported experimental values. From the STO‐3G optimized geometries, we have also calculated the electronic structures of these molecules using 4–31G and 6–31G basis sets to obtain the MO energies, atomic net charges and dipole moments. The ionization potentials calculated by 6–31G basis set are in good agreement with experimental values.
Crystal structure of K6CrNb15O42
Authors: Wu Bo‐Lin , Zha Cong‐Ji , Yuan Run‐Zhang 
Published: September 2010

AbstractK6CrNb15O42 crystallizes in the hexagonal system with a =9.126 (3) Å, c =12.068(3) Å, V =870.4(5) Å2, and space group P62 / mcm, Z =1. The structure was solved using direct method and Fourier Techniques. Of the 829 unique reflections measured by counter techniques, 448 with 1 ≥ 3σ(I) were used in the least‐squares refinement of the model to R =0.034 (Rw =0.044). The structure of K6CrNb15O42 may be described as consisting of corner‐shared and edge‐shared octahedra, the ring units composed of six octahedra of Nb(1) are corner‐shared one another along the c‐axis to form hexagonal column octahedra chains which are connected by K+ and octahedra of Nb(2).
Kinetic study on the ligand exchange reactions between bis(alkylxanthato)palladium(II) and bis(N, N‐dialkyldithiocarbamato)palladium(II) by high‐performance liquid chromatography
Authors: Shen Shi‐Gang , Ding Tian‐Hui , Wang An‐Zhou 
Published: September 2010

AbstractThe rate constants and equilibrium constants of ligand exchange reactions between bis (alkylxanthato)palladium(II), Pd (S2COR)2 (R =Am, n‐Hex, Bz), and bis(N, N‐dialkyldithiocarbamato) palladium(II), Pd(S2CNR2)2 (R =Et, n‐Pr, n‐Bu), in chloroform solution have been determined in a temperature range of 20–50°C by means of high‐performance liquid chromatography. It was found that both the forward and reverse reactions are of second order. All of the equilibrium constants K determined are 10.3±1.0, much greater than the value (K=4) calculated statistically which indicates that the ternary complexes are more stable than the binary complexes. The experimental results revealed that the reaction rate decreases with the increase in the size of R and R1 groups and the latter are more remarkable, consistent with the deduction of steric effect. The activation parameters of the reactions have been calculated. In reaction series (11) and (12) (in the text) the isokinetic temperatures β =390±8 K and β =346 ± 15 K have been observed respectively. A plausible mechanism involving an eight‐membered ring intermediate has been proposed on the basis of experimental results.
Synthesis and structure of the cluster μ3‐sulfido‐μ‐–(diethylphosphorodithioato‐S, S'‐)‐allylthioureocyclo‐tris‐[ (μ‐sulfido)‐χ‐(diethylphosphorodithioato‐S, S')‐molybdenum(IV)], Mo3S4(C4H10O2S2P)4(C4H8N2S)
Authors: Lin Xian‐Ti , Lu Jia‐Xi , Huang Jian‐Quan , Huang Jin‐Ling 
Published: September 2010

AbstractTitle compound, Mr =1273.16, was synthesized by a substitution reaction and its crystal is triclinic belonging to space group P1 with cell parameters: a =13.944(2), b =14.143(7), c =14.233(3) Å, α =77.35(3)°, β =69.94(2)°, γ =63.50(3)°, V=2351(1) Å3, Z=2, Dc =1.799g cm−2. Room temperature, graphite‐filtered Mo Kα radiation (λ =0.71073Å) was used for data collection. μ =14.988 cm−1, F(000) =1280, R=0.051 for 7025 observed reflections. The crystal consists of decrete cluster molecules containing a cluster core [Mo2(μ3‐S)]10+ with three μ‐S, one μ‐dtp(dtp =[S2P(OC2H5)]2‐), three χ‐dtp and one allylthioureo to form a local six‐coordinated sphere around each Mo atom. The bonds of cluster skeleton [Mo3(μ3‐S)(μ‐S)3]4+, MoMo 2.744∼2.766, Mo—(μ2‐S) 2.340∼2.342 and Mo—(μ‐S)2.272∼2.296 Å, are comparable with those found in the related analogues.
Synthesis and structure of an open‐type trinuclear molybdenum cluster compound [Mo3(μ3‐S)(μ‐S)2‐(μ‐OAc)(S2CNC4H8)3(O)2] · 0.5CH2Cl2 · 2H2O
Authors: Lu Shao‐Fang , Huang Zi‐Xiang , Huang Jian‐Quan , Zhang Bin , Huang Jin‐Ling 
Published: September 2010

AbstractThe title compound was prepared by the reaction of Mo3S4(dtp)4(H2O) [dtp =S2P(OEt)2] with NaOAc·3H2O and C4H2NCS2NH4. Crystallographic data: [Mo3(μ‐S)(μ‐S)2(μ‐OAc)‐(S2CNC4H2)3(O)2] · 0.5CH2Cl2 · 2H2O,Mr=980.18, triclinic, space group P1, a =12.360(3), b =16.653(6), c =9.206(2) Å, α =101.97(2), β =108.32 (2), γ =86.14(3)°. V=1759.6(9)Å2, Z =2, Dc =1.85 g/cm2, F(000) =962, μ(Mo Kα) =16.53 cm−1. Final R =0.044 for 4301 reflections with I>3σ (I). This compound may be regarded as a mixed‐valent trinuclear molybdenum cluster {Mo3(V) Mo(V) (μ2‐S) (μ‐S)2‐(μ‐OAc) (S2CNC4H8)3 (O)2}. The Mo—Mo distances are 2.783(1), 2.833(1) and 3.374(2)Å in the Mo3 non‐equilateral triangle and there exist only two Mo—Mo bonds. The cluster was obtained by oxidation and ligand substitution of {Mo2(μ2‐S) (μ‐S)2[μ‐S2P(OEt)2)] [S2P(OEt)2]3 (H2O)}.
Studies on condensed heterocyclic compounds II. Synthesis and antibacterial activity of 3‐(4′‐pyridyl)‐6‐aroylamino/arylamino‐S‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles
Authors: Zhang Zi‐Yi , Chen Xin 
Published: September 2010

Abstract3‐(4′‐Pyridyl)‐4‐amino‐5‐mercapto‐1,2,4‐triazole (1) reacted with aroyl isothiocyanates 2a‐1 to yield twelve novel 3‐(4′‐pyridyl)‐6‐aroylamino‐S‐triazolo [3,4‐b]‐1,3,4‐thiadiazoles, 4a‐1. Triethylamine was necessary for the condensation of 1 with phenyl isothiocyanate (3) to give 3‐(4′‐ pyridyl)‐6‐phenylamino‐S‐triazolo [3,4‐b]‐1,3,4‐thiadiazole (6). The structures were confirmed by the elemental and spectral analyses. Their antibacterial activity against B. Subtilis, E. Coli, E. aerogenes and S. aureus was observed preliminary.
Studies on the synthesis of amino acids XII. Solid‐liquid phase transfer catalytic dicondensation of 1,4‐diacetyl‐2,5‐piperazinedione with aldehydes
Authors: Du Zheng‐Ming , Zhou Xiao‐Ming , Shi Yao‐Zeng , Hu Hong‐Wen 
Published: September 2010

Abstract3,6‐Diarylidene‐2,5‐piperazinediones (2) and 3‐alkylidene‐6‐arylidene‐2,5‐piperazinediones (6) were synthesized from diacetyl‐2,5‐piperazinedione (1) under solid‐liquid phase transfer catalytic conditions. 2 could be easily convered to α‐amino acid by reducing with zinc powder and hydrolyzing with concentrated hydrochloric acid. The effect of different phase transfer catalysts and reaction conditions were studied.
The role of 3d orbitals in the bonding of phosphorus compounds
Authors: Li Le‐Min , Xiao Li , Liang Zhen‐Xuan 
Published: September 2010

AbstractAb initio LCAO‐MO‐SCF calculations for several typical molecules containing phosphorus have been undertaken to study the role of phosphorus 3d orbitals in the bonding. It is emphasized that the discussion about the 3d orbital participation in bonding should be based on a reasonable choice of basis sets and it seems suitable to choose the atomic orbitals in proper molecular environment as the basis set. As an approximation, the optimized minimal STO‐NG basis sets have been adopted in the present paper. The results obtained well exhibit the model of 3d orbital participation in bonding. It is shown that under the influence of highly electronegative ligands the phosphorus 3d orbitals contract greatly, their energy levels drop considerably, and thus they can effectively participate in bonding. The presence of highly electronegative ligands seems necessary. The contribution of 3d orbitals to bonding is achieved mainly through the concerted formation of σ bonds and p‐d backbonds, though the contribution to σ bonding is minor. The three‐center, four‐electron bond model is only approximately correct. The results of the present paper demonstrate that the model of 3d orbital participation in bonding favoured by experimental chemists is reasonable and possesses sound ground.
Photoelectrochemical behavior, XPS and Auger of n‐In2S3
Authors: Gong Sun‐Quan , Tan Zheng 
Published: September 2010

Abstractn‐In2S3 has been prepared by CVT method. The photoelectrochemical behavior of n‐In2S3 in a polysulfide redox solution was investigated. It was found that photoetching remarkably increased the fill factor. The maximum quantum efficiency of carrier collection reached 95% after 12h irradiation at 100 mW/cm2 at an applied potential of + 1.2 V. XPS and Auger analysis were carried out for examining surface and bulk concentration. The photoetching effect could be satisfactorily explained.
Ab initio studies on the thermolysis of azetidine
Authors: Chen Guang‐Ju , Fu Xiao‐Yuan , Tang Ao‐Qing 
Published: September 2010

AbstractThe reaction mechanism of the thermolysis of azetidine to form ethylene and methylenimine has been studied by ab initio SCF MO method at STO–3G and 3–21G levels. Two possible stepwise pathways are explored. One is the breaking of C—C bond as the first step, while the other is the breaking of C—N bond. All the stationary points on the potential energy surface (PES) are fully optimized. MP2/3–21G single point calculations on all stationary points and MCSCF/STO‐3G computations for some stationary points are also carried out. The calculations indicate that azetidine decomposes via biradicaloid intermediates and the cleavage of C—N bond is preferable to that of C—C bond.
Determination of the thermodynamic dissociation constant of p‐nitrophenol in {NaCl+EtOH+H2O} mixture by ultra‐violet spectrophotometry
Authors: Yang Jia‐Zhen , Men Dian‐Yuan , Guan Xiu‐Dan 
Published: September 2010

AbstractThe thermodynamic ionization constant K° of p‐nitrophenol in {10 mass% ethanol‐water} mixed solvent is derived from measurements of its absorption spectrum and pH by the two methods: Debye‐Hückel extrapolation and polynomial approximation proposed by us in suitable buffer solution at constant ionic strength from 0.1 to 2.0 mol · kg−1 at 298.2 ± 0.2 K. The results from both methods are pK° = 7.406 and 7.415, respectively. The effect of medium on the ultraviolet spectra of p‐nitrophenol has been discussed.
Synthesis of perfluoroalkyl‐containing steroidal glycosides
Authors: Huang Wei‐Yuan , Lü Long 
Published: September 2010

AbstractA new kind of fluorine‐containing amphiphiles — perfluoroalkyl‐containing steroidal glycosides were synthesized in good yield through perfluoroalkylation by means of sodium dithionite‐initiated addition of RFI to olefinic system. Preliminary study showed that these glycosides could form vesicles in aqueous medium as observed by electron microscopy.
The reaction of perfluoroalkanesulfonyl halides VII. Preparation and reactions of trifluoromethanesulfonyl bromide
Authors: Huang Wei‐Yuan , Lü Long 
Published: September 2010

AbstractThe reaction between sodium trifluoromethanesulfinate, which was prepared from trifluoromethyl bromide, with bromine in aqueous solution resulted in the formation of trifluoromethanesulfonyl bromide (CF2SO2Br). CF3SO1Br reacted with alkenes and alkyne to give the corresponding adducts with the loss of SO2 in good yields, and with compounds containing active hydrogen to give brominated derivatives. A radical reaction mechanism was proposed and confirmed by EPR study.
ESR study on some copper(II) complexes of bis(4′‐benzo‐15‐crown‐5)
Authors: Li Yong , Wang Gui‐Jun 
Published: September 2010

AbstractESR measurements have been carried out for some copper(II) complexes of bis(4′‐benzo‐15‐crown‐5) at 77 K. The results of ESR spectrometric titration indicated that the binuclear complexes were prepared in the present system. The binuclear complexes revealed characteristic ESR g‐anisotropies (gZ<gX, gY) which are typical of the copper(II) complexes with a 3d ground state doublet. However, in this case, the innermolecular copper(II)‐copper(II) spin interaction was not observed. ESR measurements also showed that a small amount of the sandwich type copper(II) complexes were formed in the presence of excess bis (4′‐benzo‐15‐crown‐5). A reasonable explanation was given for the ESR results.
Dehydrodimers of arylaldoxime—‐a convenient source of iminoxy radicals
Authors: Wei Xu‐Dong , Hu Hong‐Wen , Hu Yue‐Fei , Jin Yong‐Shu , Jin Tong‐Zheng , Han Shi‐Ying , Xu Yun‐Xia 
Published: September 2010

AbstractArylaldoxime dehydrodimers 3a—1 have been prepared from the corresponding oximes 1a—1 by using (HCrO4)2(Py)4Co as oxidant. Their structures were assigned to be bisnitrone by XPS studies. ESR studies of 3a—1 in hot chloroform show that iminoxy radicals 2a—1 are formed. Therefore the dehydrodimers can provide a convenient source of these radicals.
The reaction of perfluoroalkanesulfinates VII. Fenton reagent‐initiated addition of sodium perfluoroalkanesulfinates to alkenes
Authors: Huang Wei‐Yuan , Lü Long 
Published: September 2010

AbstractThe addition of sodium perfluoroalkanesulfinates (RFSO3Na) to various olefins (CH2=CHR) initiated by Fenton reagent (Fe2+‐H2O3) in the presence of sodium azide gave the adducts RFCH3‐CHN3R in good yield. A radical mechanism was proposed based on the EPR and other evidences. The adducts were readily reduced through catalytic hydrogenation to give the corresponding amines RFCH2CH(NH3)R in high yield. The reaction represents a convenient and effective route to these useful organofluorine compounds.
Studies on the reactions of silyl enol ether with perfluoroorganic compounds1 III. Synthesis of perfluoroalkylated α, β‐unsaturated aldehydes and their derivatives
Authors: Huang Wei‐Yuan , Wu Yong‐Ming 
Published: September 2010

AbstractPer‐ and poly‐fluoroalkylated α, β‐unsaturated alkenals were synthesized by the reaction of silyl enol ether of alkanals with per‐ and poly‐fluoroalkyl iodide initiated by Na2S2O4 conveniently in high yield. Their corresponding alkenol and 2,4‐dinitrophenylhydrazone were also synthesized.
Syntheses and bioactivities of mixed butyl/cyclohexyl tin carboxylates
Authors: Xie Qing‐Lan , Yang Zhi‐Qiang , Zhang Zu‐Xin , Zhang Dian‐Kun 
Published: September 2010

AbstractEight novel compounds have been synthesized and they are two series of mixed tri(butyl/cyclohexyl) tin carboxylates: BunCy3‐n SnO2CR (n = 1, 2; R = n‐C3H7, C6H5, 4‐ClC6H4, 4‐NO2C4H4). In addition to the studies of their structures with IR, 119Sn and 13C NMR, we tested their fungicidal, insecticidal and acaricidal activities. The percentage of inhibition to the aforementioned phytopathogen is about 80—100% at 50 ppm in glasshouse and 100% for T. Uriticae at 500 ppm. Those findings indicate that this kind of compounds have both fungicidal and acaricidal activities and may have a good prospect for applications.
Complexo‐titrimetric determination of mercury using hexahydropyrimidine‐2‐thione as a selective masking agent
Authors: Narayana B. , Kuchinad T. Girish , Gajendragad M. R. 
Published: September 2010

AbstractA simple, rapid, accurate and selective complexometric method is proposed for the determination of mercury(II). Mercury(II) is first complexed with a known excess of EDTA and the surplus EDTA is back‐titrated at pH 5.0–6.0 with lead nitrate, xylenol orange being used as indicator. Hexa hydropyrimidine‐2‐thione (HPT) is then added to displace EDTA from the Hg‐EDTA complex quantitatively and the EDTA released is titrated with lead nitrate. Reproducible and accurate results are obtained for 2–55 mg of mercury, with a relative error of less than 0.5% and standard deviation of less than 0.04.
Determination of chloride ion by electrochemiluminescence and investigation of the mechanism
Authors: Lin Jin‐Ming , An Jing‐Ru 
Published: September 2010

AbstractThe electrochemiluminescence (ECL) of luminol in aqueous alkaline solution was studied. Trace amounts of chloride showed significant effect on the efficiency of light emission of luminol as a positive trigonometrical wave pulse was exerted on the solution. The detection limit for the chloride is 5.0 × 10−5 mol / L and the linear calibration range extends up to 1.0×10−2 mol /L; the relative standard deviation for 1.0×10−5 mol / L chloride is 5%. The influencing factors for chloride determination are also discussed. The possible mechanism for the electrochemiluminescence reaction may be due to the oxidation of chloride ion in the solution to ClO−, and the latter acts on luminol and then gives out luminescence. The method has been applied to determine the total chloride in tap water with satisfactory results.
Synthesis of 4‐substituted 3‐oxabicyclo[3.1.0]hexan‐2‐one
Authors: Xue Jie‐You , Tang Shi‐Xiong , Sun Ai‐Bin , Wu Fan , Qiao Li‐Xin , Cao Yu‐Rong , Wang Xiao‐Lan 
Published: September 2010

AbstractCyclopropanedicarboxylic acid anhydride can be converted to 4‐substituted 3‐oxabicyclo‐[3.1.0]hexan‐2‐one by reaction with Grignard reagents in ether or tetrahydrofuran solution.
Stereoselective synthesis of (5R,6S)‐6‐acetoxy hexadecanolide—The major component of the oviposition attractant pheromone of the mosquito Culex pipens fatigans and its enantiomer from L‐glutamic acid
Authors: Ding Yu , Li Jia‐Yao , Wang Zhi‐Qin 
Published: September 2010

AbstractA concise synthesis of the mosquito oviposition attractant pheromone, (‐)(5R, 6S)‐and (+)‐(5S, 6R)‐6‐acetoxy hexadecanolide from L‐glutamic acid is described. The key steps are the inversion of the configuration at C‐4 of 7, and the formation of δ‐lactone from the γ‐lactone through ring enlargement.
Phenyl iodonium bis(perfluoroalkanesulphonyl)‐methide‐dimethyl sulphoxide complex—Its formation and X‐ray structure analysis
Authors: Zhu Shi‐Zheng , Chen Qing‐Yun , Zhu Yu‐Hua , Wu Kuang 
Published: September 2010

AbstractIrradiation of phenyl iodonium bis(perfluoroalkanesulphonyl)methide in DMSO yields an 1:1 adduct, DMSO·PhIC(SO2RF)2 (2) which was confirmed by X‐ray crystal structure analysis.
Competitive coupling of amide anion over menthyl propionate anion with aryl radical
Authors: Wu Bi‐Qi , Zeng Fan‐Wen , Li Wei , Wu Guo‐Sheng 
Published: September 2010

AbstractA competitive coupling of amide anion over menthyl propionate anion with aryl radical in photo‐SRN 1 mechanism was encountered. The reaction afforded N‐aryl propionic amide in excellent yield. In contrast, the expected nucleophilic photo‐SRN 1 substitution originating from the carbanion was observed in the case of t‐butyl propionate. According to the proposed mechanisms and MO correlation diagrams of the coupling step of nucleophiles with aryl radical, the interesting contrast is reasonably attributed to the variation in energy gap between x*C‐O and x*Ar of (ArNu)+. Usually, the odd electron of (ArNu)+ is weightly populated at x*C‐O, however, the diminished privilege of x*C‐O in menthyl propionate promotes a dominant population of the odd electron at x*Ar, which leads to the fragmentation of (ArNu)+ into the starting carbanion and aryl radical.
Quantum chemical study on the mechanism of the consecutive addition of HCN to aminoacetonitrile
Authors: Hong San‐Guo , Liu Ruo‐Zhuang 
Published: September 2010

AbstractMINDO/3 method has been used to study the mechanism of the consecutive addition of HCN to aminoacetonitrile. The results obtained for the first three steps show that the reaction is exothermic, and step I is the rate determining step.