非重氮化法合成偶氮化合物1,2,3,4,5,6-三(4-偶氮苯基)苯

本实验通过基础原料苯肼和1,4-环己二酮合成了1,4-环己二酮单苯腙(1),(1)在乙醇和二氯亚砜作用下三聚芳构化得到了1,2,3,4,5,6-三(4-偶氮苯基)苯(2),从而通过重氮化法合成了一种新型的偶氮化合物.该法操作简单,对环境友好,为生产偶氮化合物提供了新的途径.

Synthesis of Chlorosulfonyl-containing Pyrazolone Azo Compounds with Thionyl Chloride-DMF System

Chlorosulfonyl-containing pyrazolone azo compounds (2a, 2b) have been prepared by reaction of the corresponding sodium sulfonate (1a, 1b) with thionyl chloride in the presence of a catalytic quantity of N,Ndimethylformamide in dry benzene. The effects of reaction temperature, time, catalyst and solvent amount on the yield of 2a and 2b were investigated. The results show that chlorination of 1a and 1b under optimal conditions gives 2a and 2b in 95.5% and 99.2% yield respectively. The given method is facile and suitable for large-scale synthesis.

Photo-induced Alignment Behavior of Azobenzene-containing Polymer Films with Different Cross-linking Degree

Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree （from 0 to 32%, which was monitored by FT-IR spectra measurement）. Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated ＂writing＂ and ＂erasing＂ cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.

Study on the reactions of azo compounds with acyl halides mediated by Sm/TiCl_4

Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides from very simple starting materials directly.

Study on the prediction of visible absorption maxima of azobenzene compounds

The geometries of azobenzene compounds are optimized with B3LYP/6-311G* method, and analyzed with nature bond orbital, then their visible absorption maxima are calculated with TD-DFT method and ZINDO/S method respectively. The results agree well with the observed values. It was found that for the calculation of visible absorption using ZINDO/S method could rapidly yield better results by adjusting OWFπ-π (the relationship between π-π overlap weighting factor) value than by the TD-DFT method. The method of regression showing the linear relationship between OWFπ-π and BLN-N (nitrogen-nitrogen bond lengths) as OWFπ-π=?8.1537+6.5638BLN-N, can be explained in terms of quantum theory, and also be used for prediction of visible absorption maxima of other azobenzne dyes in the same series. This study on molecules’ orbital geometry indicates that their visible ab- sorption maxima correspond to the electron transition from HOMO (the highest occupied molecular orbital) to LUMO (the lowest unoccupied molecular orbital).

Preparation, Characterization and Biological Activity Studies of New Azo Compounds

A new series of azo were derived from 2,5-di（p-amino phenyl）-3,6-diphenyl pyrazine in the presence of benzoic acid, salicylic acid, p-amino salicylic acid, p-methoxy phenol and pmethyl phenol. The structures of the synthesized compounds were determined on the basis of their FTIR, UV （ultraviolet）, elemental analysis and H-NMR （H-nuclear magnetic resonance） spectral date. The purity of synthesized compounds was checked by performing TLC （thin layer chromatography）. The antibacterial activity was evaluated in DMSO （dimethyl sulfoxide）.

Gold carbene chemistry from diazo compounds

Diazo compounds are generally used as carbene precursors. Traditionally, dirhodium, copper and iron catalysts were used to decompose diazo compounds to form the key metal carbene intermediates. Recently, the gold catalysts have been developed as a unique type of metal catalyst to decompose diazo compounds. The derived gold carbene showed much different characters comparing with other transition metal carbenes. They could go through a series of cycloaddition, insertion and coupling reactions. Here, the recent progress of the gold carbene chemistry from diazo compounds was reviewed, including the scope of reactions,mechanism and synthetic applications.

Supported noble metal nanoparticles as photo/sono-catalysts for synthesis of chemicals and degradation of pollutants

This review summarizes the utilization of supported noble metal nanoparticles (such as Au/TiO2, Au/ZrO2, Ag/AgCl) as efficient photo/sono-catalysts for the selective synthesis of chemicals and degradation of environmental pollutants. Supported noble metal nanoparticles could efficiently catalyze the conversion of solar energy into chemical energy. Under UV/visible light irradiation, important chemical transformations such as the oxidation of alcohols to carbonyl compounds, the oxidation of thiol to disulfide, the oxidation of benzene to phenol, and the reduction of nitroaromatic compounds to form aromatic azo compounds, are effectively achieved by supported noble metal nanoparticles. Under ultrasound irradiation, supported noble metal nanoparticles could efficiently catalyze the production of hydrogen from water. Moreover, various pollutants, including aldehydes, alcohols, acids, phenolic compounds, and dyes, can be effectively decomposed over supported noble metal nanoparticles under UV/visible light irradiation. Under ultrasound irradiation, pollutant molecules can also be completely degraded with supported noble metal nanoparticles as catalysts.

Synthesis of aziridines by visible-light induced decarboxylative cyclization of N-aryl glycines and diazo compounds

A visible-light induced decarboxylative aza-Darzens reaction between N-aryl glycines and diazo compounds was developed, which affords various mono-substituted aziridines in good yields.

Physio-and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester

Combining the stability of chemical crosslinking and the processability of physical crosslinking is a well-established strategy to design new materials with desirable stimuli–responsive properties. Herein, a series of azobenzenebased thermotropic liquid crystalline polyesters were synthesized by introducing mesogenic dial named 4,4＇-bis（6-hydroxyhexyloxy）azobenzene（BHHAB）, 2-phenylsuccinic acid（PSA）, and different contents of 1,2,3-propanetricarboxylic acid（PTA） as the chemical crosslinker. All these polyesters showed good thermal stability and smectic liquid crystalline phase. Wide-angel X-ray diffraction（WAXD） and the fluorescence emission spectra confirmed the existence of π–πstacking interactions as the physical crosslinking in the polymer chains, particularly at the lower content of PTA. However, when the PTA content increased, the chemical crosslinking changed the chain conformation, and thus the intensity of physical crosslinking slackened gradually. Combining the physical and chemical crosslinking, these polyesters showed the thermoplastic processability, thermal shape memory, heat-assisted healing and photoresponsive behaviors. Taking advantages of these features, these multiple stimuli–responsive polymers can bring more chances for smart materials such as soft actuator.