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,Ndimethylfor...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.展开更多
Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described. Mild reaction conditions, eas...Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described. Mild reaction conditions, easy workup, high yield, and easily available catalyst are important features of this method.展开更多
A two-step process was used to synthesize the high molecular weight poly (lactic acid) using thionyl chloride as an activator for the polycondensation of prepolymer of lactic acid. The products were characterized by G...A two-step process was used to synthesize the high molecular weight poly (lactic acid) using thionyl chloride as an activator for the polycondensation of prepolymer of lactic acid. The products were characterized by GPC, DSC, and 1H-NMR. Poly (L-lactic acid) (PLLA) with molecular weight Mw: 32875 was obtained when thionyl chloride was used, while low molecular weight PLLA Mw: 7350 was yielded without thionyl chloride. Effects of the concentration of thionyl chloride, polymerization time and bases on the molecular weight of poly (lactic acid) were investigated. In DSC scans the glass transition temperatures (Tg) of the resulting polymers varied from 25.3 to 57.6℃, and the Tg of poly(L-lactic acid) was higher than that of poly (D,L-lactic acid) (PDLLA). The melting points of poly (L-lactic acid) and poly (D, L-lactic acid) could not be found unless the polymers were obtained by thionyl chloride activator.展开更多
The ultrafast photodissociation dynamics of thionyl chloride after excitation with a 235 nm pump pulse has been studied using a femtosecond time-resolved mass spectroscopy.The observed parent transient suggests that t...The ultrafast photodissociation dynamics of thionyl chloride after excitation with a 235 nm pump pulse has been studied using a femtosecond time-resolved mass spectroscopy.The observed parent transient suggests that the excited states initiated by 235 nm are very shortlived,that is,approximately 166 fs.Not only a stepwise three-body dissociation pathway but also a concerted three-body dissociation pathway is observed.展开更多
Alkyl chlorides are robust precursors to carbon radicals;however,their relative inertness has hampered their practical use.Although modern photochemical strategies have greatly enhanced the utility of alkyl chlorides ...Alkyl chlorides are robust precursors to carbon radicals;however,their relative inertness has hampered their practical use.Although modern photochemical strategies have greatly enhanced the utility of alkyl chlorides as radical precursors,these methods often depend on strongly reducing conditions leading to unproductive side reactions.Here,we report a catalytic radical generation from 1°,2°,and 3°unactivated alkyl chlorides with zirconocene and photoredox catalysis,which enables both hydrogenation and borylation on a range of structurally complex molecules.This mild zirconocene-catalyzed protocol shows that zirconium can render the C−Cl bond cleavage more exergonic and can lower the activation energy of the transition state,amplifying the ability of metallocenes toward halogen atom transfer.展开更多
CuCl-based catalysts are the most commonly used catalysts for the“direct synthesis”of trimethoxysilane(M3).CuCl species are sensitive to air and water,and are prone to oxidation deactivation.When CuCl is directly us...CuCl-based catalysts are the most commonly used catalysts for the“direct synthesis”of trimethoxysilane(M3).CuCl species are sensitive to air and water,and are prone to oxidation deactivation.When CuCl is directly used as a catalyst,it needs to be purified before the utilization,and the operating conditions for the catalyst preparation are relatively harsh,requiring the inert gas environment.Considering a high-temperature activation step required for CuCl-based catalysts used for catalyzing synthesis of M3 to form active phase Cu–Si alloys(Cu_(x)Si)with Si powder,in this work,a series of catalysts for the“direct synthesis”of M3 were obtained by a one-step high-temperature activation of the mixture of stable CuCl_(2) precursors,activated carbon-reducing agent,and Si powder,simultaneously achieving the reduction of CuCl_(2) to CuCl and the formation of active phase Cu_(x)Si alloys of CuCl with Si powder.The prepared samples were characterized through various characterization techniques,and investigated for the catalytic performance for the“direct synthesis”of M3.Moreover,the operation conditions were optimized,including the activation temperature,catalyst dosage,Si powder particle size,and reaction temperature.The characterization results indicate that during the one-step activation process,the CuCl_(2) precursor is reduced to CuCl,and the resulting CuCl simultaneously reacts with Si powder to form active phases Cu3Si and Cu15Si4 alloys.The optimal catalyst Sacm(250,0.8:10)exhibits a good catalytic activity with selectivity of 95%and yield of 77%for M3,and shows a good universality for various alcohol substrates.Furthermore,the catalytic mechanism of the prepared catalyst for the“direct synthesis”of M3 was discussed.展开更多
A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light cata...A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C?C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.展开更多
In this review we discuss the history of research into the use of gold for the acetylene hydrochlorin‐ation reaction, and describe the recent developments which have led to its commercialisation. We discuss the use o...In this review we discuss the history of research into the use of gold for the acetylene hydrochlorin‐ation reaction, and describe the recent developments which have led to its commercialisation. We discuss the use of different precursors and the addition to gold of a secondary metal as methods which attempt to improve these catalysts, and consider the nature of the active gold species. The vast majority of poly vinyl chloride （PVC） produced globally still uses a mercuric chloride as a cata‐lyst, despite the environmental problems associated with it. Due to the agreement by the Chinese government to remove mercury usage in the PVC industry over the course of the next few years there is an obvious need to find a replacement catalyst;the potential use of gold for this process has been well known for several decades and to date gold seems to be the best candidate for this, pri‐marily due to its superior selectivity when compared to other metals.展开更多
Surface organometallic chemistry (SOMC) is a recently developing research field. It is of great significance for the quantitative modification, restoration of solid surface, identification of the physical and chemical...Surface organometallic chemistry (SOMC) is a recently developing research field. It is of great significance for the quantitative modification, restoration of solid surface, identification of the physical and chemical nature of surface and the preparation of new catalyst. The production of R 3 Sn-O-MCM-41 (R 3 SnM) was obtained by heating tributyltin chloride and Al-MCM-41 mixture at 170 °C for 5 h under stirring in nitrogen atmosphere. The composition, structure and surface physical and chemical properties of the samples were characterized by inductively coupled plasma mass spectrometry (ICP-MS), 13 C, 119 Sn, 29 Si and 27 Al solid state NMR (nuclear magnetic resonance) spectra, in-situ pyridine infrared spectroscopy (Py-IR), N 2 adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), etc. The results of ICP and organic elemental analysis shows that the grafting yield w Sn was 6.46% for R 3 SnM. H 0 (the negative logarithm of the acid concentration)and the number of acid sites for R 3 SnM respectively were 2.77-0.99 and 4.8 mmol·g-1 by the Hammett method. N 2 adsorption-desorption, XRD, TEM analysis showed that R 3 SnM with ordered hexagonal mesopore structure, resulted in the decease of surface areas and pore size as well as the increase of mesoporous volume and surface acidity, as compared to Al-MCM-41. R 3 SnM was used in the synthesis of isoamyl acetate. The yield of isoamyl acetate was 96% when n(isoamyl alcohol)︰n(acetic acid) 1.0︰1.0, 3 R SnM w 5%, 138 °C for 5 h. The catalyst can be reused and the yield of 86% can be attained when catalyst was reused five times at the same catalytic conditions.展开更多
文摘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.
文摘Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described. Mild reaction conditions, easy workup, high yield, and easily available catalyst are important features of this method.
基金National Science Foundation of China (2977 6035)
文摘A two-step process was used to synthesize the high molecular weight poly (lactic acid) using thionyl chloride as an activator for the polycondensation of prepolymer of lactic acid. The products were characterized by GPC, DSC, and 1H-NMR. Poly (L-lactic acid) (PLLA) with molecular weight Mw: 32875 was obtained when thionyl chloride was used, while low molecular weight PLLA Mw: 7350 was yielded without thionyl chloride. Effects of the concentration of thionyl chloride, polymerization time and bases on the molecular weight of poly (lactic acid) were investigated. In DSC scans the glass transition temperatures (Tg) of the resulting polymers varied from 25.3 to 57.6℃, and the Tg of poly(L-lactic acid) was higher than that of poly (D,L-lactic acid) (PDLLA). The melting points of poly (L-lactic acid) and poly (D, L-lactic acid) could not be found unless the polymers were obtained by thionyl chloride activator.
基金This work was supported by the National Natural Science Foundation of China(No.11564040,No.21763027,No.11204264,No.11464045),the Natural Science Foundation of Xinjiang(No.2017D01B36),“13th Five-Year”Plan for Key Discipline Physics Bidding Project(No.17SDKD0602),Xinjiang Normal University and Science Foundation for Doctorate Research of Xinjiang Normal University(XJNUBS1511,XJNUBS1408),Teaching research and reform program of Xinjiang Normal University(No:SDJG2016C8).
文摘The ultrafast photodissociation dynamics of thionyl chloride after excitation with a 235 nm pump pulse has been studied using a femtosecond time-resolved mass spectroscopy.The observed parent transient suggests that the excited states initiated by 235 nm are very shortlived,that is,approximately 166 fs.Not only a stepwise three-body dissociation pathway but also a concerted three-body dissociation pathway is observed.
文摘Alkyl chlorides are robust precursors to carbon radicals;however,their relative inertness has hampered their practical use.Although modern photochemical strategies have greatly enhanced the utility of alkyl chlorides as radical precursors,these methods often depend on strongly reducing conditions leading to unproductive side reactions.Here,we report a catalytic radical generation from 1°,2°,and 3°unactivated alkyl chlorides with zirconocene and photoredox catalysis,which enables both hydrogenation and borylation on a range of structurally complex molecules.This mild zirconocene-catalyzed protocol shows that zirconium can render the C−Cl bond cleavage more exergonic and can lower the activation energy of the transition state,amplifying the ability of metallocenes toward halogen atom transfer.
基金supported by the Key Research & Development Plan of Shandong Province (the Major Scientific and Technological Innovation Projects, 2021ZDSYS13)the Natural Science Foundation of Shandong Province (ZR2021MB135)
文摘CuCl-based catalysts are the most commonly used catalysts for the“direct synthesis”of trimethoxysilane(M3).CuCl species are sensitive to air and water,and are prone to oxidation deactivation.When CuCl is directly used as a catalyst,it needs to be purified before the utilization,and the operating conditions for the catalyst preparation are relatively harsh,requiring the inert gas environment.Considering a high-temperature activation step required for CuCl-based catalysts used for catalyzing synthesis of M3 to form active phase Cu–Si alloys(Cu_(x)Si)with Si powder,in this work,a series of catalysts for the“direct synthesis”of M3 were obtained by a one-step high-temperature activation of the mixture of stable CuCl_(2) precursors,activated carbon-reducing agent,and Si powder,simultaneously achieving the reduction of CuCl_(2) to CuCl and the formation of active phase Cu_(x)Si alloys of CuCl with Si powder.The prepared samples were characterized through various characterization techniques,and investigated for the catalytic performance for the“direct synthesis”of M3.Moreover,the operation conditions were optimized,including the activation temperature,catalyst dosage,Si powder particle size,and reaction temperature.The characterization results indicate that during the one-step activation process,the CuCl_(2) precursor is reduced to CuCl,and the resulting CuCl simultaneously reacts with Si powder to form active phases Cu3Si and Cu15Si4 alloys.The optimal catalyst Sacm(250,0.8:10)exhibits a good catalytic activity with selectivity of 95%and yield of 77%for M3,and shows a good universality for various alcohol substrates.Furthermore,the catalytic mechanism of the prepared catalyst for the“direct synthesis”of M3 was discussed.
基金supported by the National Natural Science Foundation of China(2140204621172060+1 种基金21472039)the Fundamental Research Funds for the Central Universities
文摘A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C?C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.
文摘In this review we discuss the history of research into the use of gold for the acetylene hydrochlorin‐ation reaction, and describe the recent developments which have led to its commercialisation. We discuss the use of different precursors and the addition to gold of a secondary metal as methods which attempt to improve these catalysts, and consider the nature of the active gold species. The vast majority of poly vinyl chloride （PVC） produced globally still uses a mercuric chloride as a cata‐lyst, despite the environmental problems associated with it. Due to the agreement by the Chinese government to remove mercury usage in the PVC industry over the course of the next few years there is an obvious need to find a replacement catalyst;the potential use of gold for this process has been well known for several decades and to date gold seems to be the best candidate for this, pri‐marily due to its superior selectivity when compared to other metals.
基金Supported by the National Science Foundation of Heilongjiang Province (B201010)the Education Department of Heilongjiang Province (12511595)
文摘Surface organometallic chemistry (SOMC) is a recently developing research field. It is of great significance for the quantitative modification, restoration of solid surface, identification of the physical and chemical nature of surface and the preparation of new catalyst. The production of R 3 Sn-O-MCM-41 (R 3 SnM) was obtained by heating tributyltin chloride and Al-MCM-41 mixture at 170 °C for 5 h under stirring in nitrogen atmosphere. The composition, structure and surface physical and chemical properties of the samples were characterized by inductively coupled plasma mass spectrometry (ICP-MS), 13 C, 119 Sn, 29 Si and 27 Al solid state NMR (nuclear magnetic resonance) spectra, in-situ pyridine infrared spectroscopy (Py-IR), N 2 adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), etc. The results of ICP and organic elemental analysis shows that the grafting yield w Sn was 6.46% for R 3 SnM. H 0 (the negative logarithm of the acid concentration)and the number of acid sites for R 3 SnM respectively were 2.77-0.99 and 4.8 mmol·g-1 by the Hammett method. N 2 adsorption-desorption, XRD, TEM analysis showed that R 3 SnM with ordered hexagonal mesopore structure, resulted in the decease of surface areas and pore size as well as the increase of mesoporous volume and surface acidity, as compared to Al-MCM-41. R 3 SnM was used in the synthesis of isoamyl acetate. The yield of isoamyl acetate was 96% when n(isoamyl alcohol)︰n(acetic acid) 1.0︰1.0, 3 R SnM w 5%, 138 °C for 5 h. The catalyst can be reused and the yield of 86% can be attained when catalyst was reused five times at the same catalytic conditions.
