We devoloped an efficient and simple method to synthesize fluorene derivatives via intramolecular Friedel-Crafts alkylation of chalcones.The transform is catalyzed by TfOH in CH_(3)NO_(2)at 80℃and the yield is up to ...We devoloped an efficient and simple method to synthesize fluorene derivatives via intramolecular Friedel-Crafts alkylation of chalcones.The transform is catalyzed by TfOH in CH_(3)NO_(2)at 80℃and the yield is up to 99%.展开更多
Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. ...Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of 1-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.展开更多
Solid superacid perfluorooctanesulfonic acid(POSA)catalyzed Friedel-Craftsalkylation of aromatic hydrocarbons with olefins in gas-liquid phase.The alkylationsgave good yields with simple operation and easy work up.The...Solid superacid perfluorooctanesulfonic acid(POSA)catalyzed Friedel-Craftsalkylation of aromatic hydrocarbons with olefins in gas-liquid phase.The alkylationsgave good yields with simple operation and easy work up.The amount of the catalystused in the reactions was small and could be reused.The optimum temperature of thereactions and the effect of the amount of the catalyst used in the reactions are alsodiscussed.展开更多
Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene.We have prepared ten new nickel(Ⅱ)dibromide complexes w...Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene.We have prepared ten new nickel(Ⅱ)dibromide complexes with various substituted bis(azolyl)methanes.They have been characterized using^(1)H NMR,IR,high resolution mass spectrometry and elemental analysis.The structures of three complexes have been unambiguously established using X-ray diffraction.It was found that these complexes in the presence of Et2AlCl or Et_(3)Al_(2)Cl_(3)are active both in ethylene oligomerization and Friedel-Crafts alkylation processes(activity up to 3720 kgoligomer·mol[Ni]^(−1)·h^(−1)).The use of Et_(3)Al_(2)Cl_(3)results in a higher share of alkylated products(up to 60%).Moreover,catalytic systems activated with Et_(3)Al_(2)Cl_(3)produced small amounts of odd carbon number olefins(up to 0.8%).The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins(C_(3)and C_(5)).展开更多
Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels usin...Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.展开更多
To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation ...To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation of anthracene and 2-alkylanthracene,oxidation of 2-alkylanthracene,and product purification.Optimal alkylation conditions yielded a 91.1%conversion of anthracene and a 71.73%selectivity for 2-alkylanthracene.To address the separation problem of anthracene and 2-alkylanthracene,solvent-assisted distillation technology was developed,resulting in a 98.9%purity of 2-alkylanthracene and a 91.82%separation yield.When the molar ratio of H2O_(2) to 2-alkylanthracene was 7:1,a 98.96%conversion of 2-alkylanthracene and a 99.94%selectivity for 2-alkylanthraquinone were achieved.A novel composition of 2-alkylanthraquinone,including 2-tert-butylanthraquinone,2-tert-amylanthraquinone,and 2-hexylanthraquinone,was developed.This composition could be effectively separated and purified through a combination of crystallization and washing processes.The elemental composition of the product met the existing standards,and its hydrogenation performance closely matched that of commercially available 2-tert-amylanthraquinone products.展开更多
Sulfamic acid was proved to be a cost-effective and recyclable catalyst for Friedel-Crafts type reaction of indole withα,β-unsaturated carbonyl compound and benzyl alcohol.Various indoles,α,β-unsaturated carbonyl ...Sulfamic acid was proved to be a cost-effective and recyclable catalyst for Friedel-Crafts type reaction of indole withα,β-unsaturated carbonyl compound and benzyl alcohol.Various indoles,α,β-unsaturated carbonyl compounds and a benzyl alcohol were successfully used in this type of reaction,and the corresponding products were obtained in good to excellent yields.展开更多
A series of new ligands L_1-L_7 were readily prepared in one step.Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by a novel Cu(Ⅱ)-L complex has been developed.The remarkable advantages of this react...A series of new ligands L_1-L_7 were readily prepared in one step.Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by a novel Cu(Ⅱ)-L complex has been developed.The remarkable advantages of this reaction are mild reaction conditions,simple workup procedure,high yields of products and the use of ethanol as a green solvent.展开更多
In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides her...In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.展开更多
To better understand the benzene alkylation with chloroaluminate ionic liquids(ILs) as catalyst, the interfacial properties between the benzene/butene binary reactants and chloroaluminate ILs with varying cation alkyl...To better understand the benzene alkylation with chloroaluminate ionic liquids(ILs) as catalyst, the interfacial properties between the benzene/butene binary reactants and chloroaluminate ILs with varying cation alkyl chain length and different anions were investigated using molecular dynamics(MD) simulations. The results indicate that ILs can obviously improve the interfacial width, solubility and diffusion of reactants compared to H_(2)SO_(4). The longer alkyl chains of cations present a density enrichment at the interface and protrude into the binary reactants phase. Furthermore, the ILs consisting of 1-octyl-3-methylimidazolium cations([Omim]^(+)) and the stronger acidity heptachlorodialuminate anions([Al_(2)Cl_(7)]^(-)) are more beneficial to promote the interfacial width and facilitate the dissolution and diffusion of benzene in both the IL bulk and the interfacial region in comparison to the ones with shorter alkyl chains cations and weaker acidity anions. The information gives us a better guideline for the design of ILs for benzene alkylation.展开更多
文摘We devoloped an efficient and simple method to synthesize fluorene derivatives via intramolecular Friedel-Crafts alkylation of chalcones.The transform is catalyzed by TfOH in CH_(3)NO_(2)at 80℃and the yield is up to 99%.
基金the grant from the National Natural Science Foundation of China （Key Program 20533010）.
文摘Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of 1-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.
文摘Solid superacid perfluorooctanesulfonic acid(POSA)catalyzed Friedel-Craftsalkylation of aromatic hydrocarbons with olefins in gas-liquid phase.The alkylationsgave good yields with simple operation and easy work up.The amount of the catalystused in the reactions was small and could be reused.The optimum temperature of thereactions and the effect of the amount of the catalyst used in the reactions are alsodiscussed.
基金This work was financially supported by the Russian Science Foundation-Russia(Project No.22-23-00578)NMR measurement was performed according to the Development Program of the Interdisciplinary Scientific and Educational School of Lomonosov Moscow State University"The future of the planet and global environmental change"'X-Ray analysis was supported by the RUDN University Strategic Academic Leadership Program.Elemental and GC analyses were performed with the financial support from the Ministry of Science and Higher Education of the Russian Federation using the equipment of the Centre for molecularcomposition studies of INEOS RAS.
文摘Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene.We have prepared ten new nickel(Ⅱ)dibromide complexes with various substituted bis(azolyl)methanes.They have been characterized using^(1)H NMR,IR,high resolution mass spectrometry and elemental analysis.The structures of three complexes have been unambiguously established using X-ray diffraction.It was found that these complexes in the presence of Et2AlCl or Et_(3)Al_(2)Cl_(3)are active both in ethylene oligomerization and Friedel-Crafts alkylation processes(activity up to 3720 kgoligomer·mol[Ni]^(−1)·h^(−1)).The use of Et_(3)Al_(2)Cl_(3)results in a higher share of alkylated products(up to 60%).Moreover,catalytic systems activated with Et_(3)Al_(2)Cl_(3)produced small amounts of odd carbon number olefins(up to 0.8%).The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins(C_(3)and C_(5)).
基金the support from National Key Research and Development Program of China(2021YFC2104400)the Tianjin Science and Technology Plan Project(21JCQNJC00340)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.
基金supported by a grant from the National Natural Science Foundation of China(NSFC 22378437)the SINOPEC Excellent Youth Funds(ST22174).
文摘To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation of anthracene and 2-alkylanthracene,oxidation of 2-alkylanthracene,and product purification.Optimal alkylation conditions yielded a 91.1%conversion of anthracene and a 71.73%selectivity for 2-alkylanthracene.To address the separation problem of anthracene and 2-alkylanthracene,solvent-assisted distillation technology was developed,resulting in a 98.9%purity of 2-alkylanthracene and a 91.82%separation yield.When the molar ratio of H2O_(2) to 2-alkylanthracene was 7:1,a 98.96%conversion of 2-alkylanthracene and a 99.94%selectivity for 2-alkylanthraquinone were achieved.A novel composition of 2-alkylanthraquinone,including 2-tert-butylanthraquinone,2-tert-amylanthraquinone,and 2-hexylanthraquinone,was developed.This composition could be effectively separated and purified through a combination of crystallization and washing processes.The elemental composition of the product met the existing standards,and its hydrogenation performance closely matched that of commercially available 2-tert-amylanthraquinone products.
基金the financial support from the Doctoral Research Fund of Henan University of Traditional Chinese Medicine
文摘Sulfamic acid was proved to be a cost-effective and recyclable catalyst for Friedel-Crafts type reaction of indole withα,β-unsaturated carbonyl compound and benzyl alcohol.Various indoles,α,β-unsaturated carbonyl compounds and a benzyl alcohol were successfully used in this type of reaction,and the corresponding products were obtained in good to excellent yields.
基金the financial support from the National Natural Science Foundation of China(Nos.20962018, 20862015,20762009 and 20562011)
文摘A series of new ligands L_1-L_7 were readily prepared in one step.Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by a novel Cu(Ⅱ)-L complex has been developed.The remarkable advantages of this reaction are mild reaction conditions,simple workup procedure,high yields of products and the use of ethanol as a green solvent.
文摘In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.
基金The financial support by State Key Laboratory of Heavy Oil Processing, China University of Petroleum。
文摘To better understand the benzene alkylation with chloroaluminate ionic liquids(ILs) as catalyst, the interfacial properties between the benzene/butene binary reactants and chloroaluminate ILs with varying cation alkyl chain length and different anions were investigated using molecular dynamics(MD) simulations. The results indicate that ILs can obviously improve the interfacial width, solubility and diffusion of reactants compared to H_(2)SO_(4). The longer alkyl chains of cations present a density enrichment at the interface and protrude into the binary reactants phase. Furthermore, the ILs consisting of 1-octyl-3-methylimidazolium cations([Omim]^(+)) and the stronger acidity heptachlorodialuminate anions([Al_(2)Cl_(7)]^(-)) are more beneficial to promote the interfacial width and facilitate the dissolution and diffusion of benzene in both the IL bulk and the interfacial region in comparison to the ones with shorter alkyl chains cations and weaker acidity anions. The information gives us a better guideline for the design of ILs for benzene alkylation.
