无气味、实用的缩硫醛/酮化反应试剂：2-（1，3-二噻-2-亚基）-3-羰基丁酸甲酯

a-Oxo ketene dithioacetals, methyl 2-（1,3-dithian/dithiolan-2-ylidene）-3-oxobutanoate （2a/2b） prepared in nearly quantitative yields simply from methyl acetylacetate, carbon disulfide and 1,3-dibromopropane/1,2-dibromoethane in the presence of potassium carbonate, were investigated in the thioacetalization with various carbonyl compounds 3. It has been demonstrated that methyl 2-（1,3-dithian-2-ylidene）-3-oxobutanoate （2a） could act as a nonthiolic, odorless and practical thioacetalization reagent. A range of aldehydes and ketones 3 were converted into the corresponding dithioacetals 4 in high yields （up to 91%） in the presence of 2a. Moreover, 2a showed high chemoselectivity between aldehyde and ketone in thioacetalization.     

（E）-α-Bromovinylselenides as Convenient Precursors for Stereose-lective Synthesis of Trisubstituted Alkenes

Based on the different reactivity of selanyl and bromo groups,(E)-α-bromovinylselenides can undergo sequential cross coupling reactions with nucleophiles in the presence of transition metal complexes to form two carbon-carbon bonds in the same olefinic carbon leading to trisubstituted alkenes stereoselectively in good yields.     

Competition between C-C and C-H Activation in Reactions of Neutral Nickel Atom with Cycloalkanes （n = 3-7）

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）.     

SYNTHESIS AND APPLICATION AS POLYMER ELECTROLYTE OF HOMO- AND COPOLYMERS OF 3-(2-CYANO ETHOXY)METHYL- AND 3-(METHOXY(TRIETHYLENOXY))METHYL-3''''-METHYLOXETANE

Two oxetane-derived monomers, 3-(2-cyano-ethoxy)methyl- and 3-(methoxy-(triethylenoxy))methyl-3'-methyloxetane (COX and MTOX), were prepared from 3-hydroxymethyl-3'-methyloxetane. Their homo- and co-polymerization in solution were carried out by the cationic ring-opening polymerization with BF3·Et2O and 1,4-butanediol as co-initiator. The molecular weight and molecular weight distribution were determined using GPC so as to reveal the competition and interchange between active chain end (ACE) and activated monomer (AM) mechanism in the process. The reactivity ratios of the two monomers were calculated according to Kelen-Tudos using 1H-NMR analysis. The influence of functional side chains in the monomers on the copolymerization behaviors was discussed in virtue of the reactivity ratio data. When doped with lithium salt LiTFSI, the ion conductivity of the homopolymer of MTOX reached 10-3.58 S/cm at 30℃and 10-2.73 S/sm at 80℃, respectively, showing its potential to be used as polymer electrolyte for lithium ion battery.     

Study on the Deactivation Kinetics of Pd（PPh3）2Cl2 in the Monocarbonylation of Benzyl Chloride

The deactivation kinetics of Pd(PPh3)2Cl2 in the monocarbonylation of benzyl chloride to synthesize phenylacetic acid is studied in this paper. Solid 1-(2-pyridylazo)-2-naphthol (PAN) is used as the colouring agent, and the concentration of Pd(PPh3)2Cl2 in the system is measured through absorptiometry. The result shows that the optimum condition of the chromogenic reaction between Pd2+ and PAN is: 0.5 ml of 0.04% PAN added to 10 ml of Pd2+ solution (1.0×10-6-2.0×10-5 mol/L), and heated in a constant temperature water bath at 40℃ for about 30 min, with pH of the solution being about 3.0. The molar coefficient of absorption is 1.384×104 L/(mol·cm); the orders of the hydrolytic reaction to the concentration of Pd(PPh3)2Cl2, PPh3, phenylacetic acid and NaOH are 0.5, minus 0.8, 2 and 1.2, respectively. The activation energy (E) of the hydrolytic reaction is 75.59 kJ/mol, and the pre-exponential factor is 1.68×1012.     

Synthesis of Ethyl Oleate Catalyzed by Solid Superacid SO4^2-/TiO2/La3＋

Rare-earth compound solid superacid SO42-/TiO2/La3+ was prepared. Its catalytic activity was examined under different synthetic conditions for the esterification of propanoic acid and n-butyl alcohol as probing reaction. The optimum conditions were also found, which were the pH=8, the depositing time was 24 h, the mass fraction of La(NO3)3 used in solid superacid was 5%, the concentration of H2SO4 was 1.25 mol/L, the soaking time in H2SO4 was 16 h and the calcining temperature was 500 °C. The ethyl oleate was synthesized from oleic acid and ethanol in the presence of SO42-/TiO2/La3+. The optimum reaction conditions were obtained which were the reaction time was 6 h, molar ratio of oleic acid to ethanol was 1:4 and the mass fraction of catalyst was 4%.     

One Pot,Multi-component Synthesis of 3-[（4-Aryl-thiazol-2-yl）-hydrazono]-1,3-dihydro-indole-2-one

A series of 3-[（4-phenyl-thiazol-2-yl）-hydrazono]-1,3-dihydro-indole-2-one（4a-4g） and 3-{[4-（2-oxo2H-chromen-3-yl）-thiazol-2-yl]-hydrazono}-1,3-dihydro-indol-2-one（6a-6d） has been prepared in a one-step procedure from condensation reaction of isatin（1）,thiosemicarbazide（2） and bromoacetophenones（3）/or 3-（2-bromoacetyl）coumarins（4）.The method provides a simple and efficient route to prepare the compounds in good yields and in a short experimental time as compared to its stepwise procedure.     

Theoretical Studies on Reaction Mechanism of CH3SO with NO

The potential energy surface （PES） of CH3SO radical with NO reaction has been studied at MP2/6-311G（2df, p） and QCISD/6-311G（2df, p） levels. Geometries of the reactants, transition states （TS） and products were optimized at B3LYP/6-311G （d,p） level. The geometries of the transition states were found for the first time. The calculated results show that the reaction can proceed via singlet-state or triplet-state PES. Because of the high energy barrier of triplet surface, the singlet surface reactions are dominant. The topological analysis of electron density shows that there are two kinds of structaral transition states （the bifurcation-type ring structure transition state and the T-shaped conflict structure transition state） in the titled reaction. The total electronic density of the reactants, TS and products and the spin electronic density on the triplet surface were also discussed in this paper.     

Binding Model and 3D-QSAR of 3-（2-Chloropyrid-5- ylmethylamino）-2-cyanoacrylates as PSⅡ Electron Transport Inhibitor

The binding model of 3-（2-chloropyrid-5-ylmethylamino）-2-cyanoacrylate photosystem Ⅱ （PSⅡ） electron transport inhibitors with the D 1 protein of PSII was built. The high herbicidal activity of this kind of inhibitors was explained by docking studies： in addition to usual factors, the N atom on the pyridine ring could form an H-bond with the backbone amide of Phe265 on the D1 protein. 3D-QSAR analysis on sixteen 3-（2-chloropyrid-5-yl- methylamino）-2-cyanoacrylate compounds was performed using CoMFA method to explain the nature of interactions between the compounds and D1 protein. These studies may provide useful insights for designing new PSII electron transport inhibitors.     

全氟和多氟烷基磺酸的研究 X:在亲核取代反应中全氟烷基3-氧杂全氟烷基磺酸酯的唯一的硫-氧键断裂

Perfluoroalkyl 3-oxaperfluoralkanesulfonates XCF2OCF2CF2SO3CF2OCF2X (1) (X=CF2I (1a), CF2Cl (1b), HCF2 (1c), Cl2CF (1d)) reacted readily with various mucleophiles leading to S--O seission exclusively, thus 1 -- XCF2OCF2CF2SO2Y+XCF2OCF2COZ In the presence of a catalytic amount of halide (F-, Cl-, Br-, I-) and thiecyanate in diglyme 1 decomposed to give the corresponding sulfonly fluoride 2 (X=F) and acyl fluoride 3(Z=F). At room temperature 1 did not react with excess ethanol, but under refluxing for 12.5h, 1 was converted to 2 (Y=F) and 3 (Z=OEt). More powerful nucleophile ethoxide ion reacted readily with 1 at-60 - -50`C yielding Et2O and 3 (Z=OEt) but no 2 (Z=F). When the reaction was carried out at 80`C the yields of the products varied with the order of mixing of the reactants i.e. when 1 was added to excess ethoxide in ethanol, products are 3(Z=OEt), Et2O and 2(Y=F), but with ethoxide adding to 1 the yield of 2 (Y=F) was increased and that of ether decreased whereas the yield of 3 (Z=OEt) remained constant. Carboxylates (CF3CO2-, CH3CO2-) also caused S--O cleavage of 1 to give acetyl fluoride, 2 (y=F) and 3 (Z=F) as a result of decomposition of the intermediary mixed anhydride by the fluoride ion. In the same manner R2NH, C6H5NH2 reacted with 1 giving the products of S--O cleavage. In contrast to the nucleophilic reactions of α, α-di-H-perfluoroalkyl perfluoroalkanesulfonates (mainly C--O cleavage) it has been found that all nucleophies attack the sulfur atom of 1 exclusively. A possible interpretation is that the SN2 attack at sp3 carbon atom in highly fluorinated system is made impossible by the shielding effect of the two fluorine atoms in the alcoholic moiety and leaving the attack on the sulfur as the only alternative.     

Thermal Behavior and Decomposition Kinetics of the Complexes of CuX2 （X=NO3, Br, CI and CIO4） with 3,3＇-Dimethyl-1 -（1 H-1,2,4-triazol-1-yl）-2-butanone

The thermal behaviors of the complexes of Cu(DMTZB)4X2 (DMTZB=3,3‘-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, X=NO3 or ClO4) and Cu(DMTZB)2 X2 (X=Br or Cl) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC, EDS and elemental analysis techniques. The resuits showed that their decomposition proceeded in three different ways mainly depending on the anions in the molecules. The heat effect associated with the decomposition step of DMTZB molecules was also different. The decomposition mechanisms and the kinetic parameters of DMTZB were determined and calculated by jointly using four methods, which showed that its pyrolysis was controlled by D3 mechanism but with different activation energies and pre-exponential factors for different complexes.     

[12] ane N_3-based BODIPY as a selective and sensitive off–on sensor for the sequential recognition of Cu~(2+) ions and ADP

A novel [12]aneN3-based BODIPY sensor 1 can be applied in the sequential recognition of Cu2 and ADP in aqueous solution and living cells with high selectivity and sensitivity     

3-三氟-2-羟基/氨基-1-氟代丙基膦酸酯的合成

Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.     

PREPARATION AND STRUCTURE OF FIVE DERIVATIVES OF β-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM

A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β-(l→3)-D-glucan, sample PCS3-II, isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me2SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3-Ⅱ, C-PCS3-Ⅱ, M-PCS3-Ⅱ, HE-PCS3-Ⅱ and HP-PCS3-Ⅱ. Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), 1H-NMR, 13C-NMR, 2D-COSY, 2D-TOCSY and 2D-1H-detected 1H 13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β-(l→3)-D-glucan is in the order C-6 ＞ C-4 ＞ C-2 on the whole. The substitution of the samples S-PCS3-Ⅱ, C-PCS3-Ⅱ and M-PCS3-Ⅱoccurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3-II occurred at C-6 and C-4positions and of HP-PCS3-II almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from 13C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3-Ⅱ＞ C-PCS3-Ⅱ＞ M-PCS3-Ⅱ＞ HE-PCS3-Ⅱ＞ HP-PCS3-Ⅱ. This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation ofβ-(1→3)-D-glucan.     

Synthesis of Novel Benzoylphenylurea Chitin Inhibitors From Chlorothalonil （Ⅲ）

Six novel benzoylphenylurea chitin inhibitor derivatives were synthesized in the yields of 30%--50% from the readily available starting material chlorothalonil 1 via sequential fluorine exchange, aminolysis, hy-drolysis and acylation reactions.     

Synthesis and Bioactivity of Some New 2-(Alkoxy carbonyl alkyl)-6-bromo-3,4-dihydro-3-(α-methyl benzyl)-2-oxo- benzo[e] [2H-1,3,2-oxazaphosphinine] Derivatives

Synthesis of some new 2-(alkoxy carbonyl alkyl)-6-bromo-3,4-dihydro-3-(α-methyl benzyl)-2-oxo-3-benzo- [e][2H-1,3,2-oxazaphosphinine] derivatives was accomplished through a two step process, which involves the condensation of 2-[(α-methylbenzyl amino)methyl]-4-bromophenol (1) with phosphorus oxychloride in equimolar quantities in the presence of triethylamine in dry toluene in 50—55 ℃ producing the corresponding intermediate (2), and subsequent reaction with the amino acid alkyl ester in dry tetrahydrofuran in the presence of triethylamine at different temperatures. They exhibited significant antibacterial and fungal activity.     

PHOTOINDUCED ADDITION REACTIONS OF CHLORANIL WITH FURAN DERIVATIVES

Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to ~3TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.     

Synthesis,Structure and Photoluminescence of （CH_3-4,4＇-H_2bipy）-（HgCl_4） with CH_3-4,4＇-H_2bipy Generated in Situ

A novel viologen(4,4'bipyridinium)-based complex (CH3-4,4'-H2bipy)(HgCl4) (1),in which the CH3-4,4'-H2bipy (MQ2+) was generated in situ,has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group P21/c of monoclinic system with four formula units in a cell:a = 8.1848(6),b = 21.809(2),c = 9.0285(6) ,β = 107.377(1)°,V = 1538.0(2) 3,C11H11Cl4HgN2,Mr = 513.61,Dc = 2.218 g/cm3,S = 1.009,μ(MoKα) = 10.685 mm-1,F(000) = 956,R = 0.0360 and wR = 0.0812. The crystal structure analysis reveals that the title complex features an isolated structure based on a CH3-4,4'-H2bipy moiety and a mercury atom terminally bound by four chlorine atoms. Photoluminescence investigation reveals a strong emission in blue region,which may originate from π→π* charge-transfer interaction of the CH3-4,4'-H2bipy moiety.     

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction, Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox reaction decreased over La0.8Sr0.2Fe0.9Co0. 1O3 oxide, while LaFeO3 and La0.8Sr0.2FeO3 exhibited excellent structural stability and continuous oxygen supply.     

The Photocatalyzed Reduction of Aqueous Sodium Carbonate Using Nano SrFeO3

Heterogenous photocatalyzed reduction of aqueous Na2CO3 has been carried out by using nano SrFeO3 semiconductor powders.Formic acid,formaldehyde and methyl alcohol were identified as photoproducts,and were measured spectrophotometrically.The effect of the variation of different parameters such as sodium carbonate concentration,amount of photocatalyst and different light sources on the yield of photoproducts was also investigated.It shows that nano SrFeO3 has photocatalytic activity.Irradiation leads to the production of electrons in the conduction band of the SrFeO3 semiconductor.It is likely that the photoproduced electrons reduce CO3^2- initially to HCOO^-,and then to HCHO and CH3OH.