The unsaturated quaternary ammonium salt diethyldiallylammonium chloride(DEDAAC) was synthesized in a two-step synthetic method. The influences of the adding method of raw materials and temperature on the yields of di...The unsaturated quaternary ammonium salt diethyldiallylammonium chloride(DEDAAC) was synthesized in a two-step synthetic method. The influences of the adding method of raw materials and temperature on the yields of diethylallylamine (DEAA), and drying and temperature on the synthesis of DEDAAC were investigated. The content of in-process product DEAA was determined by non-aqueous titration. The structure of product DEDAAC was identified with IR, 1 H NMR and elemental analysis. The results show that adding allyl chloride and sodium hydroxide alternately can increase the yield of DEAA and decrease by-products. In further synthesizing of DEDAAC from DEAA, the step of drying DEAA is very necessary. When DEAA is dried by solid sodium hydroxide, good columnar crystals with a high purity(mp 199.5-201.0 ℃) are obtained; when DEAA is undried or the content of water in DEAA is above 20%, only platelets with bad quality are obtained even without crystals. The suitable synthesis conditions for DEAA and DEDAAC are 35 ℃, 6 h and 40 ℃, 36 h, respectively, and their yields are 69.7% and 67.3%, respectively.展开更多
A new six-membered cyclic carbonate monomer, 5-allyloxytrimethylene carbonate （ATMC）, was synthesized starting from glycerol, and the corresponding polycarbonates, poly（5-allyloxytrimethylene carbonate）（PATMC） w...A new six-membered cyclic carbonate monomer, 5-allyloxytrimethylene carbonate （ATMC）, was synthesized starting from glycerol, and the corresponding polycarbonates, poly（5-allyloxytrimethylene carbonate）（PATMC） were further synthesized by ring-opening polymerization in bulk at 150℃ using stannous octanoate as an initiator. The structures of the monomer and the polymers were confirmed by IR, IH-NMR, 13C-NMR, and GPC analysis.展开更多
A novel benzoxazine monomer 3-（4-allyloxy）phenyl-3,4-dihydro-2H-6-（N-maleimido）-l,3-benzoxazine （AMB） was synthesized and structure was confirmed by FT-IR, 1H NMR. Thermal analysis （DSC） of AMB showed the intr...A novel benzoxazine monomer 3-（4-allyloxy）phenyl-3,4-dihydro-2H-6-（N-maleimido）-l,3-benzoxazine （AMB） was synthesized and structure was confirmed by FT-IR, 1H NMR. Thermal analysis （DSC） of AMB showed the introduction of allyloxy group melting point and exhibited a narrow and symmetric curing exothermic window.展开更多
Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in soluti...Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.展开更多
In the presence of catalytic amount of In（OTf）3 （10 mol%）, a series of aldimines reacted with tetraallyltin in a 2：1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom effici...In the presence of catalytic amount of In（OTf）3 （10 mol%）, a series of aldimines reacted with tetraallyltin in a 2：1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol （allyl）4Sn/In（OTf）3 for simple imines was developed.展开更多
Allylsucrose has been prepared by reaction of sucrose with allyl chloride in the NaOH-DMSO system. DS^↑- （average degree of substitution） of allylsucrose calculated by elemental analysis was 6.7, and the efficiency...Allylsucrose has been prepared by reaction of sucrose with allyl chloride in the NaOH-DMSO system. DS^↑- （average degree of substitution） of allylsucrose calculated by elemental analysis was 6.7, and the efficiency of allyl chloride was 83.7%. The mechanism of the reaction was based on the acceleration of base-catalyzed reactions in dipolar aprotic solvents. The novel method is facile and suitable for large-scale preparation.展开更多
(R)- and (S)-2-Allyl-1,3,2-dinaphtho(α,β)\dioxaborepin ((R)-2 and (S)-2) have been first prepared by the reaction of (R)-(+)- or (S)-(-)-1,1′-bi-2-naphthol and triallylborane in THF at room temperature, respectivel...(R)- and (S)-2-Allyl-1,3,2-dinaphtho(α,β)\dioxaborepin ((R)-2 and (S)-2) have been first prepared by the reaction of (R)-(+)- or (S)-(-)-1,1′-bi-2-naphthol and triallylborane in THF at room temperature, respectively. (S)-2 and (R)-2 are sensitive to moisture and oxygen in air and disproportionate easily to triallylborane and 1,1′-bi-2-naphthyl bis(1,1′-bi-2-naphtholborate) at ambient temperature. However, THF is a stabilizer for them. The reactions of (R)-2 or (S)-2 and some aliphetic or aromatic aldehydes in CH_ 2 Cl_ 2 at -78℃ for several hours afforded β-alkylenyl alcohols in up to 84.8% ee. Among them, optically active 1\|(3,5-dichlorophenyl)-3-butenol and 1-(2-methoxyphenyl)-3-butenol were first prepared展开更多
BACKGROUND Allyl isothiocyanate(AITC),a classic anti-inflammatory and antitumorigenic agent,was recently identified as a potential treatment for obesity and insulin resistance.However,little is known about its direct ...BACKGROUND Allyl isothiocyanate(AITC),a classic anti-inflammatory and antitumorigenic agent,was recently identified as a potential treatment for obesity and insulin resistance.However,little is known about its direct impact on the liver.AIM To investigate the effect and underlying mechanism of AITC in nonalcoholic fatty liver disease(commonly referred to as NAFLD).METHODS To establish a mouse and cellular model of NAFLD,C57BL/6 mice were fed a high fat diet(HFD)for 8 wk,and AML-12 cells were treated with 200μM palmitate acid for 24 h.For AITC treatment,mice were administered AITC(100 mg/kg/d)orally and AML-12 cells were treated with AITC(20μmol/L).RESULTS AITC significantly ameliorated HFD-induced weight gain,hepatic lipid accumulation and inflammation in vivo.Furthermore,serum alanine aminotransferase and aspartate aminotransferase levels were markedly reduced in AITC-treated mice.Mechanistically,AITC significantly downregulated the protein levels of sterol regulatory elementbinding protein 1(SREBP1)and its lipogenesis target genes and upregulated the levels of proteins involved in fatty acidβ-oxidation,as well as the upstream mediators Sirtuin 1(Sirt1)and AMPactivated protein kinaseα(AMPKα),in the livers of HFD-fed mice.AITC also attenuated the nuclear factor kappa B(NF-κB)signaling pathway.Consistently,AITC relieved palmitate acid-induced lipid accumulation and inflammation in AML-12 cells in vitro through the Sirt1/AMPK and NF-κB signaling pathways.Importantly,further studies showed that the curative effect of AITC on lipid accumulation was abolished by siRNA-mediated knockdown of either Sirt1 or AMPKαin AML-12 cells.CONCLUSION AITC significantly ameliorates hepatic steatosis and inflammation by activating the Sirt1/AMPK pathway and inhibiting the NF-κB pathway.Therefore,AITC is a potential therapeutic agent for NAFLD.展开更多
A novel thermosetting resin system for superabrasives based on novolak and bismaleimide （BMI） was developed. The novolak resin was allylated and then copolymerized with BMI. The structure of allyl novolak and reacti...A novel thermosetting resin system for superabrasives based on novolak and bismaleimide （BMI） was developed. The novolak resin was allylated and then copolymerized with BMI. The structure of allyl novolak and reaction mechanism were analyzed by FFIR. Thermal and mechanical properties were characterized by using com- prehensive thermal analyzer （DSC-TG） and strength tester, respectively. The results showed that high molecular weight of novolak was advantageous for heat-resistance, but was unfavorable for the bending strength. High allyl content improved the heat-resistance but lowered the bending strength. When the molecular weight of novolak was 450 and allyl content was 50%, the best resin system with good heat-resistance and bending strength was obtained. It was suitable for the manufacturing of superabrasive tools.展开更多
Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacol-borate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfact...Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacol-borate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfactory to good yields. The carboxylative Suzuki coupling reaction proceeded smooth-ly under mild conditions in the presence of palladium nanoparticles generated in situ through the formation of a π-benzylpalladium chloride intermediate.展开更多
In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was f...In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was found that the contactangle of the copolymer films decreased from 68° to 30° with the increase of AG content in the copolymer. The adsorptionamount of bovine serum albumin (BSA) and the adhesive macrophage onto the film surface also decreased significantly withincreasing α-allyl glucoside content from 0 to 42 wt% in the copolymer. These preliminary results reveal that both thehydrophilicity and the biocompatibility of polyacrylonitrile-based membranes could be improved by copolymerizin gacrylonitrile with vinyl carbohydrates.展开更多
In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respective...In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respectively in moderate to good yields.展开更多
The combination of relatively low-cost ionic liquids, simple copper salt, and terminal oxidant tert-butyl hydroperoxide provided an efficient and environmentally friendly approach to the preparation of ionone-like die...The combination of relatively low-cost ionic liquids, simple copper salt, and terminal oxidant tert-butyl hydroperoxide provided an efficient and environmentally friendly approach to the preparation of ionone-like dienones. Six pyridinium ionic liquids were evaluated in allylic oxidation of α-ionone and β-ionone. The 60%-70% yields of 3-oxo-α-ionone were obtained with 0.02 0.20 mmol of CuCl2·2H2O as catalyst, 3-5 mmol of tert-butyl hydroperoxide as oxidant and 1 g of [Bpy]PF6 as solvent for 4-20 h at 60℃. The facile recovery and recycle of catalyst were also achieved. More significantly, peculiar phase behaviors of [Bpy]PF6 and [Epy]PF6 offered the catalytic system advantages of homogeneous reaction and heterogeneous separation. Scanning electron microscope （SEM） images of [Bpy]PF6 provided evidences for the behaviors. Transmission electron microscope （TEM） micrographs showed copper salt nanoparticles catalyst formed and stabilized in pyridinium ionic liquids.展开更多
A new kind of modified thermoset resins were synthesized by phase-transfer Williamson reaction from novolac resin and mixtures of allyl- and propargyl-chlorides. The compositions of the resins were defined by 1H NMR ...A new kind of modified thermoset resins were synthesized by phase-transfer Williamson reaction from novolac resin and mixtures of allyl- and propargyl-chlorides. The compositions of the resins were defined by 1H NMR （nuclear magnetic resonanse） spectroscopy and the dependence of the cured materials properties on the composition was established. Increase of a propargyl content resulted in char yield raise and the maximum value had been found for propargylated resin--58%. DSC （differential scanning calorimetry）-analysis of the resins has demonstrated that exothermic enthalpy of the curing process could be adjusted by varying the content of propargyl and allyl groups in the resin.展开更多
Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
A convenient method for the chlorination in allylic position was developed by using the aqueous solution of sodium hypochlorite(2%_5% active chlorine) and an acid as chlorination reagent in a diphase system. The metho...A convenient method for the chlorination in allylic position was developed by using the aqueous solution of sodium hypochlorite(2%_5% active chlorine) and an acid as chlorination reagent in a diphase system. The method has the advantage of cheap reagents, mild reaction conditions and good yields. The quantity and the feeding rate of the chlorination reagent can be controlled easily. The method is particularly suitable for the chlorination in laboratories.展开更多
文摘The unsaturated quaternary ammonium salt diethyldiallylammonium chloride(DEDAAC) was synthesized in a two-step synthetic method. The influences of the adding method of raw materials and temperature on the yields of diethylallylamine (DEAA), and drying and temperature on the synthesis of DEDAAC were investigated. The content of in-process product DEAA was determined by non-aqueous titration. The structure of product DEDAAC was identified with IR, 1 H NMR and elemental analysis. The results show that adding allyl chloride and sodium hydroxide alternately can increase the yield of DEAA and decrease by-products. In further synthesizing of DEDAAC from DEAA, the step of drying DEAA is very necessary. When DEAA is dried by solid sodium hydroxide, good columnar crystals with a high purity(mp 199.5-201.0 ℃) are obtained; when DEAA is undried or the content of water in DEAA is above 20%, only platelets with bad quality are obtained even without crystals. The suitable synthesis conditions for DEAA and DEDAAC are 35 ℃, 6 h and 40 ℃, 36 h, respectively, and their yields are 69.7% and 67.3%, respectively.
基金support of the National Natural Science Foundation of China(Grant No.20104005)
文摘A new six-membered cyclic carbonate monomer, 5-allyloxytrimethylene carbonate （ATMC）, was synthesized starting from glycerol, and the corresponding polycarbonates, poly（5-allyloxytrimethylene carbonate）（PATMC） were further synthesized by ring-opening polymerization in bulk at 150℃ using stannous octanoate as an initiator. The structures of the monomer and the polymers were confirmed by IR, IH-NMR, 13C-NMR, and GPC analysis.
文摘A novel benzoxazine monomer 3-（4-allyloxy）phenyl-3,4-dihydro-2H-6-（N-maleimido）-l,3-benzoxazine （AMB） was synthesized and structure was confirmed by FT-IR, 1H NMR. Thermal analysis （DSC） of AMB showed the introduction of allyloxy group melting point and exhibited a narrow and symmetric curing exothermic window.
基金This work was supported by the Fund for Young Scientist from the National Advanced Materials Committee of China
文摘Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.
基金the National Natural Science Foundation of China(Nos.20421202,20372033)for financialsupport.
文摘In the presence of catalytic amount of In（OTf）3 （10 mol%）, a series of aldimines reacted with tetraallyltin in a 2：1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol （allyl）4Sn/In（OTf）3 for simple imines was developed.
基金Supported by the National Natural Science Foundation of China (No. 20076006).
文摘Allylsucrose has been prepared by reaction of sucrose with allyl chloride in the NaOH-DMSO system. DS^↑- （average degree of substitution） of allylsucrose calculated by elemental analysis was 6.7, and the efficiency of allyl chloride was 83.7%. The mechanism of the reaction was based on the acceleration of base-catalyzed reactions in dipolar aprotic solvents. The novel method is facile and suitable for large-scale preparation.
文摘(R)- and (S)-2-Allyl-1,3,2-dinaphtho(α,β)\dioxaborepin ((R)-2 and (S)-2) have been first prepared by the reaction of (R)-(+)- or (S)-(-)-1,1′-bi-2-naphthol and triallylborane in THF at room temperature, respectively. (S)-2 and (R)-2 are sensitive to moisture and oxygen in air and disproportionate easily to triallylborane and 1,1′-bi-2-naphthyl bis(1,1′-bi-2-naphtholborate) at ambient temperature. However, THF is a stabilizer for them. The reactions of (R)-2 or (S)-2 and some aliphetic or aromatic aldehydes in CH_ 2 Cl_ 2 at -78℃ for several hours afforded β-alkylenyl alcohols in up to 84.8% ee. Among them, optically active 1\|(3,5-dichlorophenyl)-3-butenol and 1-(2-methoxyphenyl)-3-butenol were first prepared
基金Supported by Natural Science Foundation of China,No.81700504 and No.81700511Science Foundation of Health Bureau of Zhejiang Province,No.2017183691+1 种基金Natural Science Foundation of Zhejiang Province,No.LY17H030006 and No.LQ15H030002Zhejiang Medical Science and Technology Project,No.2017193668
文摘BACKGROUND Allyl isothiocyanate(AITC),a classic anti-inflammatory and antitumorigenic agent,was recently identified as a potential treatment for obesity and insulin resistance.However,little is known about its direct impact on the liver.AIM To investigate the effect and underlying mechanism of AITC in nonalcoholic fatty liver disease(commonly referred to as NAFLD).METHODS To establish a mouse and cellular model of NAFLD,C57BL/6 mice were fed a high fat diet(HFD)for 8 wk,and AML-12 cells were treated with 200μM palmitate acid for 24 h.For AITC treatment,mice were administered AITC(100 mg/kg/d)orally and AML-12 cells were treated with AITC(20μmol/L).RESULTS AITC significantly ameliorated HFD-induced weight gain,hepatic lipid accumulation and inflammation in vivo.Furthermore,serum alanine aminotransferase and aspartate aminotransferase levels were markedly reduced in AITC-treated mice.Mechanistically,AITC significantly downregulated the protein levels of sterol regulatory elementbinding protein 1(SREBP1)and its lipogenesis target genes and upregulated the levels of proteins involved in fatty acidβ-oxidation,as well as the upstream mediators Sirtuin 1(Sirt1)and AMPactivated protein kinaseα(AMPKα),in the livers of HFD-fed mice.AITC also attenuated the nuclear factor kappa B(NF-κB)signaling pathway.Consistently,AITC relieved palmitate acid-induced lipid accumulation and inflammation in AML-12 cells in vitro through the Sirt1/AMPK and NF-κB signaling pathways.Importantly,further studies showed that the curative effect of AITC on lipid accumulation was abolished by siRNA-mediated knockdown of either Sirt1 or AMPKαin AML-12 cells.CONCLUSION AITC significantly ameliorates hepatic steatosis and inflammation by activating the Sirt1/AMPK pathway and inhibiting the NF-κB pathway.Therefore,AITC is a potential therapeutic agent for NAFLD.
文摘A novel thermosetting resin system for superabrasives based on novolak and bismaleimide （BMI） was developed. The novolak resin was allylated and then copolymerized with BMI. The structure of allyl novolak and reaction mechanism were analyzed by FFIR. Thermal and mechanical properties were characterized by using com- prehensive thermal analyzer （DSC-TG） and strength tester, respectively. The results showed that high molecular weight of novolak was advantageous for heat-resistance, but was unfavorable for the bending strength. High allyl content improved the heat-resistance but lowered the bending strength. When the molecular weight of novolak was 450 and allyl content was 50%, the best resin system with good heat-resistance and bending strength was obtained. It was suitable for the manufacturing of superabrasive tools.
文摘Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacol-borate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfactory to good yields. The carboxylative Suzuki coupling reaction proceeded smooth-ly under mild conditions in the presence of palladium nanoparticles generated in situ through the formation of a π-benzylpalladium chloride intermediate.
基金The authors are grateful to the National Natural Science Foundation of China for financial support(Grant No.20074033).
文摘In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was found that the contactangle of the copolymer films decreased from 68° to 30° with the increase of AG content in the copolymer. The adsorptionamount of bovine serum albumin (BSA) and the adhesive macrophage onto the film surface also decreased significantly withincreasing α-allyl glucoside content from 0 to 42 wt% in the copolymer. These preliminary results reveal that both thehydrophilicity and the biocompatibility of polyacrylonitrile-based membranes could be improved by copolymerizin gacrylonitrile with vinyl carbohydrates.
基金the Natural Science Foundation of the Education Commission of Jiangsu Province
文摘In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respectively in moderate to good yields.
基金Supported by the National Natural Science Foundation of China （20472057）
文摘The combination of relatively low-cost ionic liquids, simple copper salt, and terminal oxidant tert-butyl hydroperoxide provided an efficient and environmentally friendly approach to the preparation of ionone-like dienones. Six pyridinium ionic liquids were evaluated in allylic oxidation of α-ionone and β-ionone. The 60%-70% yields of 3-oxo-α-ionone were obtained with 0.02 0.20 mmol of CuCl2·2H2O as catalyst, 3-5 mmol of tert-butyl hydroperoxide as oxidant and 1 g of [Bpy]PF6 as solvent for 4-20 h at 60℃. The facile recovery and recycle of catalyst were also achieved. More significantly, peculiar phase behaviors of [Bpy]PF6 and [Epy]PF6 offered the catalytic system advantages of homogeneous reaction and heterogeneous separation. Scanning electron microscope （SEM） images of [Bpy]PF6 provided evidences for the behaviors. Transmission electron microscope （TEM） micrographs showed copper salt nanoparticles catalyst formed and stabilized in pyridinium ionic liquids.
文摘A new kind of modified thermoset resins were synthesized by phase-transfer Williamson reaction from novolac resin and mixtures of allyl- and propargyl-chlorides. The compositions of the resins were defined by 1H NMR （nuclear magnetic resonanse） spectroscopy and the dependence of the cured materials properties on the composition was established. Increase of a propargyl content resulted in char yield raise and the maximum value had been found for propargylated resin--58%. DSC （differential scanning calorimetry）-analysis of the resins has demonstrated that exothermic enthalpy of the curing process could be adjusted by varying the content of propargyl and allyl groups in the resin.
基金supported by the National Natural Science Foundation of China(No.29772007)
文摘Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
文摘A convenient method for the chlorination in allylic position was developed by using the aqueous solution of sodium hypochlorite(2%_5% active chlorine) and an acid as chlorination reagent in a diphase system. The method has the advantage of cheap reagents, mild reaction conditions and good yields. The quantity and the feeding rate of the chlorination reagent can be controlled easily. The method is particularly suitable for the chlorination in laboratories.
