Theoretical Study of the C-CI Bond Dissociation Enthalpy and Electronic Structure of Substituted Chlorobenzene Compounds

Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3PW91, B3P86） methods together with 6-31G^＊＊ and 6-311G^＊＊ basis sets. The results show that B3P86/6-311G^＊＊ method is the best method to compute the reliable BDEs for substituted chlorobenzene compounds which contain the C-C1 bond. It is found that the C-C1 BDE depends strongly on the computational method and the basis sets used. Substituent effect on the C-C1 BDE of substituted chlorobenzene compounds is further discussed. It is noted that the effects of substitution on the C-C1 BDE of substituted chlorobenzene compounds are very insignificant. The energy gaps between the HOMO and LUMO of studied compounds estimate the relative thermal stability ordering are also investigated and from this data we of substituted chlorobenzene compounds.

Structural Characterization and Acute Toxicity Prediction of Substituted Aromatic Compounds by Using Molecular Vertexes Correlative Index

A molecular structural characterization （MSC） method called molecular vertexes correlative index （MVCI） was used to describe the structures of 30 substituted aromatic compounds. Through multiple linear regression （MLR） and stepwise multiple regression （SMR）, a quantitative structure-toxicity relationship （QSTR） model with 4 variables was obtained. The correlation coefficient （R） of the model was 0.9467. Through partial least-squares regression （PLS）, another QSTR model with 5 principal components was obtained. The correlation coefficient （R） of the model was 0.9518. Both models were evaluated by performing the cross-validation with the leave-one-out （LOO） procedure and the Cross-Validation （CV） correlation coefficients （Rcv） were 0.9208 and 0.9214, respectively. The results suggested good stability and predictability of the models, and the molecular vertexes correlative index could successfully describe the structures of the substituted aromatic compounds.

Selective nitration of phenols using bismuth subnitrate/charcoal in the presence of trichloroisocyanuric acid under aprotic conditions

A mild,efficient and regioselective method for the mononitration of phenolic compounds is described using bismuth subnitrate/ charcoal in the presence of trichloroisocyanuric acid in CH2Cl2 at room temperature.

Correlation Study of Toxicity of Substituted Phenols to River Bacteria and Their Biodegradability in River Water

To study the correlation of toxicity with biodegradability （BODT） in order to promote QSBR development and understand the degradation mechanism. Methods Toxicity of substituted phenols to river bacteria was determined by the turbidities that were measured using a spectrophotometer （UV-190） at 530 nm against a blank control. The biodegradability of substituted phenols was expressed as BODT and the DO concentrations were determined by the iodometric titration method. Results The BODT and toxicity（log 1/IC50） of 12 substituted phenols to bacteria from the Songhua River were determined respectively. The correlation of biodegradability with toxicity was developed： BODT=8.21 （±2.22） pKa -32.44 （±8.28） log 1/IC50 ＋89.04 （±38.20）, n=12, R^2=0.791, R^2（adj）=0.745, SE=9.134, F=17.066, P=0.001. Conclusion The BODT of substituted phenols was influenced by their toxicity and the ionization constant pKa. The stronger the toxicity, the less readily the compound was degraded by river bacteria.

Study of Quantitative Structure-retention Relationship for Substituted Phenols

Quantum chemistry parameters of 20 substituted phenols were computed at the 6- 31G＊ level using DFT method. Based on theoretical linear solvation energy theory, the correlation equation that can predict the retention index （Ri） was developed using structural parameters of 15 substituted phenols with experimental data as theoretical descriptors, and the conventional correlation coefficient （R^2） is 0.9885. The correlation degree of each independent variable in the model was validated by variance inflation factors （VIF） and t-test. Cross-validation indicates that the model possesses high predicting ability. The correlation and predicting ability of the Ri equation are both more advantageous than those based on orientating group index, connectivity index, and topological index method. In addition, RI values of 5 compounds without experimental data were predicted with the model.

V(HSO_4)_3 catalyzed chemoselectivity acetylation of alcohols and phenols in solution and under solvent-free conditions

A variety of alcohols and phenols are efficiently acetylated with acetic anhydride in the presence of a catalytic amount of V（HSO4）3 in solution and under solvent free conditions. Mild reaction conditions, high yields of the products, easy procedure and selective acetylation of alcohols and phenols in the presence of amines and thiols are the main advantages of this procedure.

Quantitative Structure-activity Relationship(QSAR) Study of Toxicity of Substituted Aromatic Compounds to Photobacterium Phosphoreum

With the artificial neural network（ANN） method combined with the multiple linear regression（MLR）,based on a series of quantum chemical descriptors and molecular connectivity indexes,quantitative structure-activity relationship（QSAR） models to predict the acute toxicity（-lgEC50） of substituted aromatic compounds to Photobacterium phosphoreum were established.Four molecular descriptors that appear in the MLR model,namely,the second order valence molecular connectivity index（2XV）,the energy of the highest occupied molecular orbital（EHOMO）,the logarithm of n-octyl alcohol/water partition coefficient（logKow） and the Connolly molecular area（MA）,were inputs of the ANN model.The root-mean-square error（RMSE） of the training and validation sets of the ANN model are 0.1359 and 0.2523,and the correlation coefficient（R） is 0.9810 and 0.8681,respectively.The leave-one-out（LOO） cross validated correlation coefficient（Q L2OO） of the MLR and ANN models is 0.6954 and 0.6708,respectively.The result showed that the two methods are complementary in the calculations.The regression method gave support to the neural network with physical explanation,and the neural network method gave a more accurate model for QSAR.In addition,some insights into the structural factors affecting the acute toxicity and toxicity mechanism of substituted aromatic compounds were discussed.

Synthesis of Substituted u-Oxo-bis[tetra-phenyl porphyrinatoiron] Compounds from Free Base Porphyrins by a One-pot Method

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.

Montmorillonite K10 Clay Catalyzed One Pot Synthesis of 2,4,6-Tri Substituted Pyridine under Solvent Free Condition

Montmorillonite K10 catalyzed synthesis of 2,4,6 triaryl pyridine under solvent free condition is described. Montmorillonite effectively catalyzed the reaction in good to excellent yields. Using this solid catalyst, the reactions could be carried out in a short period of time with very good yield of triaryl pyridines, up to 97% under solvent free condition. This catalyst could be recycled very easily, which makes this methodology environmentally benign. The catalyst is active over three cycles.

Space Group Distribution in Substituted Phenols

Analysis on the space group distribution in 78 substituted phenols re-vealed its unusual high frequencies in groups with non-centrosymmetry or polar axis orhigher symmetry or Z' > 1. Based on the characteristics of intermolecular H-bondsformed by two OH groups,the space group distribution could be rationalized well.

Syntheses of N-substituted Dinaphtho Macrocyclic Compounds

The syntheses of 5 new 17-membered macrocycles containing naphthalene ring are reported. The macrocycle ring in each of these new ligands contains an O2N3-donor set. Structures of these new compounds were characterized by IR,1H NMR, MS and elemental analysis.

Reaction of Substituted Cyclopentadienyl-magnesium-Chloride with Carbonyl Compound ( Ⅰ )——Reaction of (1, 1-Dialkyl-3-Butenyl) Cyclopentadienyl-magnesium-chloride with Ketones

The substituted cyclopentadienyl-magnesium-chloride, obtained by exocyclic addition of 6,6-dialkylfulvene and allyl-magnesium-chloride, reacted with the ketone 3, the product was hydrolyzed and dehydrated to give the 2-(1 ,1-dialkyl-3-butenyl)-6,6-dialkyl-fulvene 5. The structure of 5 was determined by using the 1H NMR spectra of 5 and the adducts of 5 with tetracyanoethylene.

Comparison of Catalytical and Biological Activities for Substituted Polyoxotungstates Containing Ti and CpTi

The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave potential of the complexes indicated that the effect of the functionallization of POMs increased the oxidizing ability of the polyoxoanions. The inhibitory effects of the CpTi polyoxocomplexes on tumor cells are higher than those of the corresponding titanium polyoxocomplexes, and the toxicity of the former is lower than that of the latter. The oxygenation reactions of cyclohexene, styrene, trans stilbene and maleic acid with PhIO or hydrogen peroxide(30% aqueous solution) catalyzed respectively by Ti and CpTi polyoxocomplexes were compared.

Density Functional Investigations into the Adsorption of Methanol on Isomorphously Substituted ZSM-5

The adsorption of methanol in the acid sites of zeolites has attracted a great deal of attention because of its relevance to the industrial methanol to gasoline conversion process. In this work, the B3LYP hybrid density functional method was used to investigate the adsorption behavior of methanol on Bronsted acid sites in B, Al, Ga and Fe isomorphously substituted ZSM-5 zeolites. The optimized structures reveal a physisorbed methanol interacting with the zeolite framework through two hydrogen bonds. The order of the computed adsorption energy correlates with the acid strength of the isomorphously substituted ZSM-5: B-ZSM-5《Fe-ZSM-5<Ga-ZSM-5<Al-ZSM-5. The adsorption difference between methanol and ammonia is compared.

Quartz Crystal Microbalance Sensor Deposited with LB Films of Functional Polymers for the Detection of Phenols in Vapour Phase

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Studies on the Quantitative Structure-activity Relationship of Substituted Biphenyls by Density Function Theory (DFT)

Geometrical configurations of 16 substituted biphenyls were computed at the B3LYP/6-311G^＊＊ level with Gaussian 98 program. Based on linear solvation energy theory, lgKow as well as the structural and thermodynamic parameters obtained at this level was taken as theoretical descriptors, and corresponding equation predicting the toxicity of Daphnia magna （-lgEC5o） was thus obtained, in which three parameters were contained, i.e., n-octanol/water partition coefficients （lgKow）, dipole moment of the molecules（ μ） and entropy （S°）. For this equation, R^2 = 0.9582, q^2 = 0.8921 and SD = 0.102. The absolute t-scores of three variables are larger than the standard one in the confidence range of 95%, which confirms the creditability and stability of this model.

Organophosphonotungstic HPA of Keggin Type with Sulfo,Taurine and Glycine Substituted Ethylphosphonic Acids as the Coordinate Center

The title compounds 2ac were synthesized and characterized for the first time. Their proton numbers are around 3.2±0.15 and are not in proportion with the valid acidity-basicity of the central phosphonic acids. The entirety of phosphonic acids 1a-c is as the coordinate center of heteropoly anions of 2ac.

Synthesis of Glucoside Compounds of Ferrocenyl Phenols and Their Antianemic Activity

Six glucoside compounds have been synthesized by means of phase-transfer catalytic method and deacetylation from the starting material ferrocene. Their structures have been confirmed by elementary analysis, IR,1HNMR and MS. The antianemic activities of some compounds have also been tested. Results indicate that these glucoside compounds possess the antianemic activities and therefore, the further study is well worth making.