4-Bromo-3-methylphenol(BMP)is an important chemical intermediate with wide applications in the fields of medicine and pesticides.The synthesis of BMP from m-cresol via bromination is easy to carry out on an industrial...4-Bromo-3-methylphenol(BMP)is an important chemical intermediate with wide applications in the fields of medicine and pesticides.The synthesis of BMP from m-cresol via bromination is easy to carry out on an industrial scale.However,due to the formation of regioisomeric impurities during bromination and the low melting point of BMP,the separation process is prone to the formation of oily substances,resulting in low yield and purity.In this work,a new cocrystallization engineering approach was proposed to separate and purify BMP.Through design of experiments,the cocrystallization process of BMP and triethylenediamine(DABCO)was optimized using a minimum-run resolution IV screening design combined with response surface methodology.In addition,the obtained 2BMP-DABCO powder was characterized by thermal analysis,powder X-ray diffraction,infrared spectroscopy,and scanning electron microscopy.Single crystals of 2BMP-DABCO were grown from acetone by slow evaporation,and detailed structural information was obtained through single-crystal X-ray diffraction.The self-assembly mechanism was further clarified by density functional theory calculations.This study provides a simple,robust,and scalable method for the production of BMP and offers a reference for the separation and purification of phenolic substances.展开更多
Dimethylphenols serve as important intermediates in synthesizing pharmaceuticals and agrochemicals,yet traditional distillation struggles to separate their isomers due to minimal boiling point differences,and the deve...Dimethylphenols serve as important intermediates in synthesizing pharmaceuticals and agrochemicals,yet traditional distillation struggles to separate their isomers due to minimal boiling point differences,and the development of melt crystallization is hampered by lacking solid–liquid equilibrium (SLE) data for some isomers.Therefore,the SLE data of both binary and ternary mixtures of 2,3-dimethylphenol (2,3-DMP),3,5-dimethylphenol (3,5-DMP),and 3,4-dimethylphenol (3,4-DMP) were determined by using differential scanning calorimetry in this work.Additionally,crystallographic analysis was conducted to investigate the thermodynamic characteristics of these mixtures.The experimental results indicated that all the systems investigated in this research exhibited eutectic behavior.The experimentally obtained SLE data were well correlated with the Wilson and non-random two-liquid models.The excess thermodynamic functions were calculated to analyze the types and intensities of the molecular interactions occurring in the mixtures.Furthermore,this study developed a model for the correlation between the theoretical crystallization yield and the actual cooling yield and final yield in melt crystallization.This study has furnished reliable data essential for developing and optimizing the melt crystallization process of mixtures of 2,3-DMP,3,5-DMP,and 3,4-DMP.展开更多
A new green technology of producing chromic anhydride with an electrochemical synthesis method was studied to solve the pollution problems in the traditional production process of chromic anhydride.A self-made electro...A new green technology of producing chromic anhydride with an electrochemical synthesis method was studied to solve the pollution problems in the traditional production process of chromic anhydride.A self-made electrosynthesis reactor of pure titanium and stainless steel, with a multiple-unit metal oxides combination anode, a cathode of stainless steel, and a reinforced combination cation exchange membrane with perfluorosulfonic and perfluorocarboxylic polymers was used to carry out, the direct electrochemical synthesis experiment of chromic anhydride from sodium dichromate.From the experimental results and the principle of electrochemical reaction, it was found that the process of electrochemical synthesis reaction of chromic anhydride might be quantitatively followed by the variation of operating voltage measured macroscopically with reaction time. Operating voltages were experimentally measured at the different initial sodium dichromate concentrations of the anolyte in the electrosynthesis process of chromic anhydride, and the variation of operating voltage with reaction time was discussed. The mathematical model of the variation of operating voltages with reaction time and the rate of change equations of operating voltage were established.The model characterizes the change of operating voltages in the electrosynthesis process of chromic anhydride, and provideds the foundations for the further study and process monitoring of the electrochemical synthesis of chromic anhydride.展开更多
A new green technology of producing chromic anhydride with an electrochemical synthesis method was studied to solve the pollution problems in the traditional production process of chromic anhydride.The anolyte used wa...A new green technology of producing chromic anhydride with an electrochemical synthesis method was studied to solve the pollution problems in the traditional production process of chromic anhydride.The anolyte used was sodium dichromate solution, and the anode used was a self-made combination electrode of titanium matrix with a multiple-unit metal oxides active coating.The electrochemical behavior of sodium dichromate solution on a combination electrode of titanium matrix was studied with cyclic voltammetry as a part of the fundamental researches of this technique.The electrooxidation reaction of 160 cycles indicated that the electrode possessed a very stable electrochemical behavior.The peak currents ip and peak potentials Ep of the oxidation peaks for sodium dichromate solution of different concentrations, i.e., water under the existence of sodium dichromate, were experimentally measured at different temperatures and sweep rates v on the electrode.The equations of peak current ip versus v1/2 and peak potential Ep versus lnv were established, indicating that the electrode reaction was an irreversible diffusion-controlled reaction.The kinetic parameters and activation energy of electrode reaction was calculated, and the effects of temperature on the kinetic parameters and activation energy were preliminarily discussed.展开更多
基金supported by the National Natural Science Foundation of China(22177011(R.Z.Qiao),21977012(R.Z.Qiao),and 21572018(C.Li))the National High-Level Hospital Clinical Research Funding(2023-NHLHCRF-YXHZ-ZRMS-02)the Joint Project of BRCBC(Biomedical Translational Engineering Research Center of BUCT-CJFH)(XK2020-06).
文摘4-Bromo-3-methylphenol(BMP)is an important chemical intermediate with wide applications in the fields of medicine and pesticides.The synthesis of BMP from m-cresol via bromination is easy to carry out on an industrial scale.However,due to the formation of regioisomeric impurities during bromination and the low melting point of BMP,the separation process is prone to the formation of oily substances,resulting in low yield and purity.In this work,a new cocrystallization engineering approach was proposed to separate and purify BMP.Through design of experiments,the cocrystallization process of BMP and triethylenediamine(DABCO)was optimized using a minimum-run resolution IV screening design combined with response surface methodology.In addition,the obtained 2BMP-DABCO powder was characterized by thermal analysis,powder X-ray diffraction,infrared spectroscopy,and scanning electron microscopy.Single crystals of 2BMP-DABCO were grown from acetone by slow evaporation,and detailed structural information was obtained through single-crystal X-ray diffraction.The self-assembly mechanism was further clarified by density functional theory calculations.This study provides a simple,robust,and scalable method for the production of BMP and offers a reference for the separation and purification of phenolic substances.
基金funded by the National Natural Science Foundation of China(22308358,22208346,22421003)IPE Project for Frontier Basic Research(QYJC-2023-05)CAS Project for Young Scientists in Basic Research(YSBR-038).
文摘Dimethylphenols serve as important intermediates in synthesizing pharmaceuticals and agrochemicals,yet traditional distillation struggles to separate their isomers due to minimal boiling point differences,and the development of melt crystallization is hampered by lacking solid–liquid equilibrium (SLE) data for some isomers.Therefore,the SLE data of both binary and ternary mixtures of 2,3-dimethylphenol (2,3-DMP),3,5-dimethylphenol (3,5-DMP),and 3,4-dimethylphenol (3,4-DMP) were determined by using differential scanning calorimetry in this work.Additionally,crystallographic analysis was conducted to investigate the thermodynamic characteristics of these mixtures.The experimental results indicated that all the systems investigated in this research exhibited eutectic behavior.The experimentally obtained SLE data were well correlated with the Wilson and non-random two-liquid models.The excess thermodynamic functions were calculated to analyze the types and intensities of the molecular interactions occurring in the mixtures.Furthermore,this study developed a model for the correlation between the theoretical crystallization yield and the actual cooling yield and final yield in melt crystallization.This study has furnished reliable data essential for developing and optimizing the melt crystallization process of mixtures of 2,3-DMP,3,5-DMP,and 3,4-DMP.
文摘A new green technology of producing chromic anhydride with an electrochemical synthesis method was studied to solve the pollution problems in the traditional production process of chromic anhydride.A self-made electrosynthesis reactor of pure titanium and stainless steel, with a multiple-unit metal oxides combination anode, a cathode of stainless steel, and a reinforced combination cation exchange membrane with perfluorosulfonic and perfluorocarboxylic polymers was used to carry out, the direct electrochemical synthesis experiment of chromic anhydride from sodium dichromate.From the experimental results and the principle of electrochemical reaction, it was found that the process of electrochemical synthesis reaction of chromic anhydride might be quantitatively followed by the variation of operating voltage measured macroscopically with reaction time. Operating voltages were experimentally measured at the different initial sodium dichromate concentrations of the anolyte in the electrosynthesis process of chromic anhydride, and the variation of operating voltage with reaction time was discussed. The mathematical model of the variation of operating voltages with reaction time and the rate of change equations of operating voltage were established.The model characterizes the change of operating voltages in the electrosynthesis process of chromic anhydride, and provideds the foundations for the further study and process monitoring of the electrochemical synthesis of chromic anhydride.
文摘A new green technology of producing chromic anhydride with an electrochemical synthesis method was studied to solve the pollution problems in the traditional production process of chromic anhydride.The anolyte used was sodium dichromate solution, and the anode used was a self-made combination electrode of titanium matrix with a multiple-unit metal oxides active coating.The electrochemical behavior of sodium dichromate solution on a combination electrode of titanium matrix was studied with cyclic voltammetry as a part of the fundamental researches of this technique.The electrooxidation reaction of 160 cycles indicated that the electrode possessed a very stable electrochemical behavior.The peak currents ip and peak potentials Ep of the oxidation peaks for sodium dichromate solution of different concentrations, i.e., water under the existence of sodium dichromate, were experimentally measured at different temperatures and sweep rates v on the electrode.The equations of peak current ip versus v1/2 and peak potential Ep versus lnv were established, indicating that the electrode reaction was an irreversible diffusion-controlled reaction.The kinetic parameters and activation energy of electrode reaction was calculated, and the effects of temperature on the kinetic parameters and activation energy were preliminarily discussed.
