Study On The Synthesis And Solubility Of 1-Benzyl-4-Hydroxymethyl-1H-1,2,3-Triazole

1-Benzyl-4-hydroxymethyl-1H-1,2,3-triazole(BHMT) is an important organic intermediate, which can be applied to synthesize triazole ethers, polynuclear azoles, and ligands by replacing the hydroxyl group with halogens and other nucleophiles. BHMT was synthesized by click chemistry with atomic economically in this paper. The solid-liquid equilibrium of BHMT in different pure solvents and ethanol-aqueous solution were studied, which aims at providing some useful data to the purification process of BHMT.Firstly, benzyl azide was synthesized through azide substitution using benzyl chloride as the main raw material and its structure was characterized by FTIR, 1H NMR, and 13 C NMR. And more, the optimum reaction conditions were obtained through single factor experiments: n(Na N3): n(benzyl chloride)=1.25: 1, V(ethanol): V(H2O)=8: 1, at reflux temperature for 8h, the yield was 91.94%.Secondly, the yellowish needles crystal BHMT was obtained through 1,3-dipolar cycloaddition between propargyl alcohol and benzyl azide in the presence of copper(I). The structure of BHMT was confirmed by FTIR, 1H NMR and 13 C NMR. The influences of factors on the yield of BHMT were examined through single factor and orthogonal experiments: n(propargyl alcohol): n(benzyl azide)=1.15: 1, n(Cu SO4·5H2O): n(ascorbic acid): n(benzyl azide)=0.02: 0.20: 1.0,65℃ for 20 h, the yield was 92.64%.And then,solubility determination apparatus with a laser monitor using dynamic method was designed and assembled. The solubility of BHMT in toluene, tetrahydrofuran, acetone, ethyl acetate, chloroform, dichloromethane, water, several low-carbon aliphatic alcohols and ethanol-aqueous solution were measured within the temperature range from 281.15 K to 315.75 K under atmospheric pressure. The solubility of BHMT in solvents selected were found increasing with temperature rising, which was no report from the literature.Finally, the solid-liquid equilibrium data in different pure solvents were correlated with the van’t Hoff equation, λh equation and modified Apelblat equation, which the calculated values were in good consistent with the experimental data. The average relative deviation(ARD) were 2.41%, 2.14% and 1.82%, respectively. However, the ARD for ethanol-aqueous system were as high as 10.89% to 30.71%. And, the CNIBS/R-K model can be used for ethanol-aqueous system with a relatively satisfactory accuracy, and the ARD was 5.64%.The synthesis process proposed in this paper was full of application prospects due to the mild conditions, simple post-processing and environmental benign. The experimental solubility data meet the requirements for engineering design.