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2018 Volume 38 Issue 8
2018, 38(8): 1859-1871
doi: 10.6023/cjoc201804033
Abstract:
Transition metal-catalyzed direct C-H bond functionalization strategy has aroused wide concerns due to its high atom-economy and step-economy. Imine synthons exhibit diverse reactivities and are commonly employed to assemble nitrogen-containing complex molecules through direct C-H functionalization strategies, their reaction types and mechanisms are summarized in this paper.
Transition metal-catalyzed direct C-H bond functionalization strategy has aroused wide concerns due to its high atom-economy and step-economy. Imine synthons exhibit diverse reactivities and are commonly employed to assemble nitrogen-containing complex molecules through direct C-H functionalization strategies, their reaction types and mechanisms are summarized in this paper.
2018, 38(8): 1872-1884
doi: 10.6023/cjoc201803053
Abstract:
2(5H)-Furanone contains several reaction points, and its structure unit exists in a number of nature products, which makes the researches on the derivatizations of 2(5H)-furanone important. Some 2(5H)-furanone compounds, such as 3-(or 4-) halo-2(5H)-furanone, 5-nonsubstitued 2(5H)-furanone, 4-hydroxy-2(5H)-furanone and their derivatives, can react with organometallic reagents, alkyl halides, organoboron compounds, unsaturated hydrocarbons and unsaturated C=X (X=O, N) compounds, forming C-C bond at 3-, or 4-, or 5-position of 2(5H)-furanone, respectively. According to the different types of reagents, the C-C bond formation reactions based on 2(5H)-furanone synthons are reviewed, and their recent progress in organic synthesis methodology and application of bioactive compounds is summarized. In the future, it is important to make the 2(5H)-furanone C-C bond formation reaction more greener and efficiently used in polycyclization reaction.
2(5H)-Furanone contains several reaction points, and its structure unit exists in a number of nature products, which makes the researches on the derivatizations of 2(5H)-furanone important. Some 2(5H)-furanone compounds, such as 3-(or 4-) halo-2(5H)-furanone, 5-nonsubstitued 2(5H)-furanone, 4-hydroxy-2(5H)-furanone and their derivatives, can react with organometallic reagents, alkyl halides, organoboron compounds, unsaturated hydrocarbons and unsaturated C=X (X=O, N) compounds, forming C-C bond at 3-, or 4-, or 5-position of 2(5H)-furanone, respectively. According to the different types of reagents, the C-C bond formation reactions based on 2(5H)-furanone synthons are reviewed, and their recent progress in organic synthesis methodology and application of bioactive compounds is summarized. In the future, it is important to make the 2(5H)-furanone C-C bond formation reaction more greener and efficiently used in polycyclization reaction.
2018, 38(8): 1885-1896
doi: 10.6023/cjoc201804031
Abstract:
Alkaline-earth-metal compounds have been widely concerned due to its abundant reserve and the low-cost. In recent years, alkaline-earth-metal catalysis has achieved great progress in dehydrocoupling, hydroboration, hydrophosphination, hydroamination, hydrosilylation reactions experimentally and therotically. These types of reaction and catalytic mechanism, leading to indentify the role of alkaline-earth-metal in hydrogenation and dehydrogenation reaction are summarized. These reactions, in which the metal-hydride act as active species, generally undergo the reaction pathway involving the cleavage and formation of the metal-hydride covalent bond. The reaction features and mechanisms are generally recognized accrossing to the classification and discussion of these reactions, which would provide guidance for further development of alkaline-earth-metal catalysis.
Alkaline-earth-metal compounds have been widely concerned due to its abundant reserve and the low-cost. In recent years, alkaline-earth-metal catalysis has achieved great progress in dehydrocoupling, hydroboration, hydrophosphination, hydroamination, hydrosilylation reactions experimentally and therotically. These types of reaction and catalytic mechanism, leading to indentify the role of alkaline-earth-metal in hydrogenation and dehydrogenation reaction are summarized. These reactions, in which the metal-hydride act as active species, generally undergo the reaction pathway involving the cleavage and formation of the metal-hydride covalent bond. The reaction features and mechanisms are generally recognized accrossing to the classification and discussion of these reactions, which would provide guidance for further development of alkaline-earth-metal catalysis.
2018, 38(8): 1897-1906
doi: 10.6023/cjoc201804035
Abstract:
The synthesis of carbohydrates through photoredox catalysis has achieved a great process in the past decade. This review highlights the latest advances in this research area, including the photo-induced O-glycosylation and C-glycosylation, and the functional group modification and thiol-ene coupling reactions of carbohydrates.
The synthesis of carbohydrates through photoredox catalysis has achieved a great process in the past decade. This review highlights the latest advances in this research area, including the photo-induced O-glycosylation and C-glycosylation, and the functional group modification and thiol-ene coupling reactions of carbohydrates.
2018, 38(8): 1907-1916
doi: 10.6023/cjoc201801013
Abstract:
Traditional liquid acid catalysts have environmental problems during their application. Perfluoroalkylsulfonylimide complexes show a wide application in catalysis due to their special anionic structures and super acid properties. The structures and properties of bis(perfluoroalkylsulfonyl)imide complexes are introduced. The synthesis and immobilization methods of bis(perfluoroalkylsulfonyl)imide complexes are summarized. The use of immobilized bis(perfluoroalkylsulfonyl)imide complexes in catalytic reactions is also reviewed. The development trends of perfluoroalkylsulfonylimide complexes in the catalytic application are prospected.
Traditional liquid acid catalysts have environmental problems during their application. Perfluoroalkylsulfonylimide complexes show a wide application in catalysis due to their special anionic structures and super acid properties. The structures and properties of bis(perfluoroalkylsulfonyl)imide complexes are introduced. The synthesis and immobilization methods of bis(perfluoroalkylsulfonyl)imide complexes are summarized. The use of immobilized bis(perfluoroalkylsulfonyl)imide complexes in catalytic reactions is also reviewed. The development trends of perfluoroalkylsulfonylimide complexes in the catalytic application are prospected.
2018, 38(8): 1917-1929
doi: 10.6023/cjoc201803021
Abstract:
The N-doped carbon materials supported Pd nanocatalysts have attracted extensive attention in the catalysis field due to its unique advantages such as high efficiency, easy separation, purification and recyclability. The recent progress in the synthesis and application of supported Pd nanocatalysts based on different types of carbon materials supports including N-doped porous/mesoporous carbon, N-doped graphene, N-doped carbon nanotube and N-doped carbon nanosheet is reviewed. And the research trends of N-doped carbon materials supported Pd nanocatalysts are also prospected.
The N-doped carbon materials supported Pd nanocatalysts have attracted extensive attention in the catalysis field due to its unique advantages such as high efficiency, easy separation, purification and recyclability. The recent progress in the synthesis and application of supported Pd nanocatalysts based on different types of carbon materials supports including N-doped porous/mesoporous carbon, N-doped graphene, N-doped carbon nanotube and N-doped carbon nanosheet is reviewed. And the research trends of N-doped carbon materials supported Pd nanocatalysts are also prospected.
2018, 38(8): 1930-1939
doi: 10.6023/cjoc201803022
Abstract:
Phenols are important central motifs that are abundant in many natural products, pharmaceuticals and agrochemicals.Moreover, the high reactivity of phenol derivatives makes them versatile building blocks for organic synthesis.Over the past decade, the synthesis of phenol derivatives via C-H hydroxylation of aromatics has received much attention due to its potential as an atom efficient methodology.Herein, the research advances on the C-H hydroxylation of aromatics are reviewed categorized by the types of hydroxylation source used.Detailed substrate scopes and reaction mechanisms will be discussed, as well as the limitations of current procedures and the prospects for the future.
Phenols are important central motifs that are abundant in many natural products, pharmaceuticals and agrochemicals.Moreover, the high reactivity of phenol derivatives makes them versatile building blocks for organic synthesis.Over the past decade, the synthesis of phenol derivatives via C-H hydroxylation of aromatics has received much attention due to its potential as an atom efficient methodology.Herein, the research advances on the C-H hydroxylation of aromatics are reviewed categorized by the types of hydroxylation source used.Detailed substrate scopes and reaction mechanisms will be discussed, as well as the limitations of current procedures and the prospects for the future.
2018, 38(8): 1940-1948
doi: 10.6023/cjoc201804004
Abstract:
Primary anilines are widely used in pharmaceutical, agrochemicals and material chemistry. In recent years, the green and efficient methods for constructing carbon-nitrogen (C-N) bonds to introduce primary amines has been one of the hottest topics in chemical synthesis. The direct C-H primary amination of aromatic compounds have received considerable attention due to its high efficiency and practicality. The recent progress in the C-H primary amination of aromatic compounds reactions is reviewed. Furthermore, the synthetic challenge and prospect in the future development for the synthesis of primary anilines through direct C-H amination are summarized.
Primary anilines are widely used in pharmaceutical, agrochemicals and material chemistry. In recent years, the green and efficient methods for constructing carbon-nitrogen (C-N) bonds to introduce primary amines has been one of the hottest topics in chemical synthesis. The direct C-H primary amination of aromatic compounds have received considerable attention due to its high efficiency and practicality. The recent progress in the C-H primary amination of aromatic compounds reactions is reviewed. Furthermore, the synthetic challenge and prospect in the future development for the synthesis of primary anilines through direct C-H amination are summarized.
2018, 38(8): 1949-1962
doi: 10.6023/cjoc201803013
Abstract:
Amines containing carbon-nitrogen (C-N) bonds are widely distributed in natural products, drug molecules and functional materials.C-N bonds are one of the most abundant and inert bonds in organic molecules.Selective cleavage of C-N bonds to construct carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds represents a new synthetic method in organic synthesis.It is difficult for the direct cleavage of C-N bond.Ammonium salts are a series of stable compounds easily obtained from amines.The recent progress of transition-metal-catalyzed cross-coupling reactions via C-N bond cleavage using ammonium salts as starting materials is summerized.
Amines containing carbon-nitrogen (C-N) bonds are widely distributed in natural products, drug molecules and functional materials.C-N bonds are one of the most abundant and inert bonds in organic molecules.Selective cleavage of C-N bonds to construct carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds represents a new synthetic method in organic synthesis.It is difficult for the direct cleavage of C-N bond.Ammonium salts are a series of stable compounds easily obtained from amines.The recent progress of transition-metal-catalyzed cross-coupling reactions via C-N bond cleavage using ammonium salts as starting materials is summerized.
2018, 38(8): 1963-1971
doi: 10.6023/cjoc201804032
Abstract:
A new class of mild sodium-dependent glucose cotransporter 2 (SGLT2) inhibitors with glucosyl isoflavone structure were prepared from puerarin. The in vitro biological activity was performed on Chinese hamster ovary (CHO) cells stably expressing human SGLT2 while taking[14C]-methyl-D-glucopyranoside ([14C]-AMG) as the substrate. Some derivatives exhibited potent activity against SGLT2 with IC50 among 20~30 nmol/L. The inhibitory activities of derivatives with more lipophilic substitutents were more potent. The compounds whose 4'-OH and 7-OH were both protected with alkyl or benzyl are more active than those with only the 4'-OH being protected. The inhibitory activity of some homologues has no great difference. 4'-O-n-Hexylpuerarin (1i), 4'-O-n-octylpuerarin (1j), 4'-O-(4-methylbenzyl)puerarin (1l), 4'-O-(4-methoxylbenzyl)-puerarin (1m) with moderate inhibitory activity against SGLT2 may have anti-oxidant and anti-atherosclerotic properties due to the presence of Ar-OH in the molecule structure, which will be very useful to treat diabetic disease and cardiovascular complications.
A new class of mild sodium-dependent glucose cotransporter 2 (SGLT2) inhibitors with glucosyl isoflavone structure were prepared from puerarin. The in vitro biological activity was performed on Chinese hamster ovary (CHO) cells stably expressing human SGLT2 while taking[14C]-methyl-D-glucopyranoside ([14C]-AMG) as the substrate. Some derivatives exhibited potent activity against SGLT2 with IC50 among 20~30 nmol/L. The inhibitory activities of derivatives with more lipophilic substitutents were more potent. The compounds whose 4'-OH and 7-OH were both protected with alkyl or benzyl are more active than those with only the 4'-OH being protected. The inhibitory activity of some homologues has no great difference. 4'-O-n-Hexylpuerarin (1i), 4'-O-n-octylpuerarin (1j), 4'-O-(4-methylbenzyl)puerarin (1l), 4'-O-(4-methoxylbenzyl)-puerarin (1m) with moderate inhibitory activity against SGLT2 may have anti-oxidant and anti-atherosclerotic properties due to the presence of Ar-OH in the molecule structure, which will be very useful to treat diabetic disease and cardiovascular complications.
2018, 38(8): 1985-1992
doi: 10.6023/cjoc201803019
Abstract:
A series of pyrazole-fused isocoumarins were synthesized by the reaction of ninhydrin hydrate and arylhydrazones in the presence of bromodimethylsulfonium bromide (BDMS) at room temperature. The reaction has the advantages of mild conditions, simple operation, the ready accessibility of the catalyst, and short reaction times.
A series of pyrazole-fused isocoumarins were synthesized by the reaction of ninhydrin hydrate and arylhydrazones in the presence of bromodimethylsulfonium bromide (BDMS) at room temperature. The reaction has the advantages of mild conditions, simple operation, the ready accessibility of the catalyst, and short reaction times.
2018, 38(8): 1993-2001
doi: 10.6023/cjoc201803054
Abstract:
α-(N-Sulfonyl)amino amide derivatives are directly synthesized in 71%~89% yields by the reaction of carbamoylsilanes with various N-sulfonylimines in benzene under catalyst-free conditions. The procedure can prepare both tertiary and secondary α-amino amides. A comparison of the results obtained from the N-sulfonylimines containing the variety of alkyl, aryl and heterocyclic ring indicated that the electronic effect was an important factor in the addition reaction, which influenced on the rate and yields of the reaction. The new method is simple and mild procedure, no catalysts conditions, less byproducts and good yields for the preparation of α-aminoamides.
α-(N-Sulfonyl)amino amide derivatives are directly synthesized in 71%~89% yields by the reaction of carbamoylsilanes with various N-sulfonylimines in benzene under catalyst-free conditions. The procedure can prepare both tertiary and secondary α-amino amides. A comparison of the results obtained from the N-sulfonylimines containing the variety of alkyl, aryl and heterocyclic ring indicated that the electronic effect was an important factor in the addition reaction, which influenced on the rate and yields of the reaction. The new method is simple and mild procedure, no catalysts conditions, less byproducts and good yields for the preparation of α-aminoamides.
2018, 38(8): 2002-2007
doi: 10.6023/cjoc201804042
Abstract:
The supramolecular functional system based on host-guet interaction between monosubstituted ferrocene derivatives and pillararene-based macromolecule molecules has made impressive progress in many different fields. The host-guet interaction between 1, 1'-disubstituted ferrocene derivatives and water-soluble pillar[6]arene was preliminarily explored and studied. This work may give some support for the subsequent development of supramolecular functional systems, such as rotaxane, pseudorotaxane systems, based on the host-guet interaction between 1, 1'-disubstituted ferrocene derivatives and water-soluble pillar[6]arene.
The supramolecular functional system based on host-guet interaction between monosubstituted ferrocene derivatives and pillararene-based macromolecule molecules has made impressive progress in many different fields. The host-guet interaction between 1, 1'-disubstituted ferrocene derivatives and water-soluble pillar[6]arene was preliminarily explored and studied. This work may give some support for the subsequent development of supramolecular functional systems, such as rotaxane, pseudorotaxane systems, based on the host-guet interaction between 1, 1'-disubstituted ferrocene derivatives and water-soluble pillar[6]arene.
2018, 38(8): 2008-2016
doi: 10.6023/cjoc201804007
Abstract:
A novel, convenient and efficient protocol to N-heterocyclic derivatives of 1, 3-diaryl or diaklyl-2H-isoin-dole-4, 7-dione has been developed via the Barbier-Grignard-type reaction. Good to excellent yields up to 96% have been achieved by performing the reaction in one pot using Ta2O5 as the catalyst. The protocol displays good tolerance to different aryl and alkyl bromides. Based on some experimental results, a plausible mechanism involving nucleophilic addition and electron transfer has been proposed. The quinone structure in 1, 3-diphenyl-2H-isoindole-4, 7-dione (3a) makes it coupling with amine to form more complicated structure.
A novel, convenient and efficient protocol to N-heterocyclic derivatives of 1, 3-diaryl or diaklyl-2H-isoin-dole-4, 7-dione has been developed via the Barbier-Grignard-type reaction. Good to excellent yields up to 96% have been achieved by performing the reaction in one pot using Ta2O5 as the catalyst. The protocol displays good tolerance to different aryl and alkyl bromides. Based on some experimental results, a plausible mechanism involving nucleophilic addition and electron transfer has been proposed. The quinone structure in 1, 3-diphenyl-2H-isoindole-4, 7-dione (3a) makes it coupling with amine to form more complicated structure.
2018, 38(8): 2028-2035
doi: 10.6023/cjoc201803036
Abstract:
A highly efficient TfOH-catalyzed addition of C3-substituted indole derivatives with (1H-indol-2-yl)diphenyl-methanols has been established, leading to the synthesis of a series of potentially bioactive 2, 3'-bisindols in moderate to high yields (48%~89%) and with broad substrate scope under mild conditions. In addition, the furan-2-yldiphenylmethanol could also be applied in the reaction and afforded 2-(5-benzhydrylfuran-2-yl)-1H-indole in good yield.
A highly efficient TfOH-catalyzed addition of C3-substituted indole derivatives with (1H-indol-2-yl)diphenyl-methanols has been established, leading to the synthesis of a series of potentially bioactive 2, 3'-bisindols in moderate to high yields (48%~89%) and with broad substrate scope under mild conditions. In addition, the furan-2-yldiphenylmethanol could also be applied in the reaction and afforded 2-(5-benzhydrylfuran-2-yl)-1H-indole in good yield.
2018, 38(8): 2036-2044
doi: 10.6023/cjoc201801039
Abstract:
Herein, Michael addition-condensation of isatin-3-imines with mercaptoacetic acid to afford a new simple and efficient synthesis of spiro[indole-thiazolidine] derivatives in high yield (up to 99%) by using of MCM-41@Schiff base-Cu(ClO4)2·6H2O as heterogeneous catalyst is reported. In addition, it is found that heterogeneous catalyst exhibits better activity than homogeneous catalyst in the same functional groups. The effect of the pore structure on mesoporous molecular sieve nanoreactor MCM-41 for this reaction is further explored. Consistent activity of recovered catalyst was found to be almost same up to six cycles in 93% yield.
Herein, Michael addition-condensation of isatin-3-imines with mercaptoacetic acid to afford a new simple and efficient synthesis of spiro[indole-thiazolidine] derivatives in high yield (up to 99%) by using of MCM-41@Schiff base-Cu(ClO4)2·6H2O as heterogeneous catalyst is reported. In addition, it is found that heterogeneous catalyst exhibits better activity than homogeneous catalyst in the same functional groups. The effect of the pore structure on mesoporous molecular sieve nanoreactor MCM-41 for this reaction is further explored. Consistent activity of recovered catalyst was found to be almost same up to six cycles in 93% yield.
2018, 38(8): 2045-2053
doi: 10.6023/cjoc201802003
Abstract:
Benzynes undergo insertion reaction with C=S bond of the stable sulfur ylide through a cascade[2+2] cycloaddition and ring-opening reaction to construct a new C-S bond, producing ortho-substituted aryl-alkyl thioether derivatives in moderate to good yields.
Benzynes undergo insertion reaction with C=S bond of the stable sulfur ylide through a cascade[2+2] cycloaddition and ring-opening reaction to construct a new C-S bond, producing ortho-substituted aryl-alkyl thioether derivatives in moderate to good yields.
2018, 38(8): 2054-2059
doi: 10.6023/cjoc201801015
Abstract:
A series of 4-hydroxyl-2-pyridone derivatives were synthesized via a one-pot and multicomponent reaction of dimethyl 3-oxopentanedioate, N, N-dimethylformamide dimethyl acetal (DMF-DMA) and primary amine in aliphatic alcohol by using L-proline as catalyst. The structures of these compounds were confirmed by NMR and HRMS. This work provides a convenient method for construction of pyridones with the advantages of operation simplicity, free of isolating intermediates etc. Moreover, the participation of solvent in the reaction enriched the diversity of 5-substitution in the pyridone backbone.
A series of 4-hydroxyl-2-pyridone derivatives were synthesized via a one-pot and multicomponent reaction of dimethyl 3-oxopentanedioate, N, N-dimethylformamide dimethyl acetal (DMF-DMA) and primary amine in aliphatic alcohol by using L-proline as catalyst. The structures of these compounds were confirmed by NMR and HRMS. This work provides a convenient method for construction of pyridones with the advantages of operation simplicity, free of isolating intermediates etc. Moreover, the participation of solvent in the reaction enriched the diversity of 5-substitution in the pyridone backbone.
2018, 38(8): 2060-2066
doi: 10.6023/cjoc201712043
Abstract:
Long aromatic polymer chains which based on 3, 5-diaminobenzoic acid derivatives and 4, 6-dihydroxyisophthalic acid derivatives are designed and synthesized. The results of solubility, NMR, UV-Vis spectrum and circular dichroism (CD) experments indicate that the polymer adopts a hollow helical conformation that is stablized by intramolecular H-bonding interaction between side chains.
Long aromatic polymer chains which based on 3, 5-diaminobenzoic acid derivatives and 4, 6-dihydroxyisophthalic acid derivatives are designed and synthesized. The results of solubility, NMR, UV-Vis spectrum and circular dichroism (CD) experments indicate that the polymer adopts a hollow helical conformation that is stablized by intramolecular H-bonding interaction between side chains.
2018, 38(8): 2076-2084
doi: 10.6023/cjoc201802008
Abstract:
Palladium-catalyzed cross-dehydrogenative coupling of uracil or caffeine with unactivated arenes has been developed. The approach was characterized by using atmospheric pressure of molecular oxygen as the sole oxidant. Functional groups such as halo, ester, nitro, nitrile and ether are well-tolerated under the reaction conditions. This novel strategy provides a straightforward, facile and economical route to C6-aryl uracil derivatives or C8-aryl caffeine derivatives.
Palladium-catalyzed cross-dehydrogenative coupling of uracil or caffeine with unactivated arenes has been developed. The approach was characterized by using atmospheric pressure of molecular oxygen as the sole oxidant. Functional groups such as halo, ester, nitro, nitrile and ether are well-tolerated under the reaction conditions. This novel strategy provides a straightforward, facile and economical route to C6-aryl uracil derivatives or C8-aryl caffeine derivatives.
2018, 38(8): 2093-2100
doi: 10.6023/cjoc201712022
Abstract:
We tried combining dodecahydrodecaborane anion (B12H122-) with aminotetrazole cation into a series of new borohydrino-tetrazolium salt as a kind of energetic materials. Firstly, by using 1-or 2-5-aminotetrazole (5-ATZ) as the raw material, dialkylated 5-aminotetrazolium iodide was synthesized via dialkylation reaction with methyl iodide and ethyl iodide. And then, the dialkylated 5-aminotetrazolium iodides was used to react with potassium dodecylhydrodecaborate in an aqueous solution by metathesis. Finally, eleven novel bis(dialkyl-5-aminotetrazolium) dodecahydrododecaborates were synthesized. All of them were in yield of above 70%, and their chemical properties were stable under the conditions of purification and drying. These compounds have been characterized by FT-IR, 1H NMR, 13C NMR, 11B NMR, mass spectrometry, and elemental analysis. In inspecting their thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) technologies, the results showed that eleven kinds of bis(dialkyl-5-aminotetrazolium) dodecahydrododecaborates have higher thermal stability and the thermal decomposition temperatures of them are mostly above 200℃. In molecular structures, their thermal stability decrease with the increase of the 4-position alkyl when the 1-position alkyl maintains the same. The rapid thermal decomposition of the five compounds, 1, 4-dimethyl, 1-methyl-4-ethyl, 1, 3-dimethyl, 1-methyl-3-ethyl, and 1-ethyl-3-methyl, occurred before the melting, and the rapid thermal decomposition of the other 6 compounds occurred after the crystals melting. These high-energetic compounds are of great importance in developing new high-performance propellants.
We tried combining dodecahydrodecaborane anion (B12H122-) with aminotetrazole cation into a series of new borohydrino-tetrazolium salt as a kind of energetic materials. Firstly, by using 1-or 2-5-aminotetrazole (5-ATZ) as the raw material, dialkylated 5-aminotetrazolium iodide was synthesized via dialkylation reaction with methyl iodide and ethyl iodide. And then, the dialkylated 5-aminotetrazolium iodides was used to react with potassium dodecylhydrodecaborate in an aqueous solution by metathesis. Finally, eleven novel bis(dialkyl-5-aminotetrazolium) dodecahydrododecaborates were synthesized. All of them were in yield of above 70%, and their chemical properties were stable under the conditions of purification and drying. These compounds have been characterized by FT-IR, 1H NMR, 13C NMR, 11B NMR, mass spectrometry, and elemental analysis. In inspecting their thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) technologies, the results showed that eleven kinds of bis(dialkyl-5-aminotetrazolium) dodecahydrododecaborates have higher thermal stability and the thermal decomposition temperatures of them are mostly above 200℃. In molecular structures, their thermal stability decrease with the increase of the 4-position alkyl when the 1-position alkyl maintains the same. The rapid thermal decomposition of the five compounds, 1, 4-dimethyl, 1-methyl-4-ethyl, 1, 3-dimethyl, 1-methyl-3-ethyl, and 1-ethyl-3-methyl, occurred before the melting, and the rapid thermal decomposition of the other 6 compounds occurred after the crystals melting. These high-energetic compounds are of great importance in developing new high-performance propellants.
2018, 38(8): 2109-2115
doi: 10.6023/cjoc201804034
Abstract:
A novel fluorescent "turn-on" probe 7-(dibutylamino)-2'-((2-hydroxybenzylidene)amino)-3-methyl-1-phenyl-1H-spiro[chromeno[2, 3-c]pyrazole-4, 1'-isoindolin]-3'-one (SCPz-S) with Schiff base structure was designed and synthesized, and characterized by 1H NMR, 13C NMR and high resolution mass spectrometry (HRMS). The UV-Vis and fluorescence spectra were used to investigate the ions recognition capability of probe SCPz-S. It was excavated that the probe SCPz-S has a dual colorimetric and fluorescence response to CN- in THF/H2O (V:V=1930:50, 5 mmol/L Tris-HCl, pH=7.4). After adding CN-, the system of probe SCPz-S will change from colorless to yellow, and fluorescence enhance 1060-fold at 575 nm. The sensor SCPz-S also has good anti-interference ability and a wide pH range from 3 to 12 applicable. Its LOD for CN- is 1.121×10-8 mol/L, and the recognition mechanism has been investigated.
A novel fluorescent "turn-on" probe 7-(dibutylamino)-2'-((2-hydroxybenzylidene)amino)-3-methyl-1-phenyl-1H-spiro[chromeno[2, 3-c]pyrazole-4, 1'-isoindolin]-3'-one (SCPz-S) with Schiff base structure was designed and synthesized, and characterized by 1H NMR, 13C NMR and high resolution mass spectrometry (HRMS). The UV-Vis and fluorescence spectra were used to investigate the ions recognition capability of probe SCPz-S. It was excavated that the probe SCPz-S has a dual colorimetric and fluorescence response to CN- in THF/H2O (V:V=1930:50, 5 mmol/L Tris-HCl, pH=7.4). After adding CN-, the system of probe SCPz-S will change from colorless to yellow, and fluorescence enhance 1060-fold at 575 nm. The sensor SCPz-S also has good anti-interference ability and a wide pH range from 3 to 12 applicable. Its LOD for CN- is 1.121×10-8 mol/L, and the recognition mechanism has been investigated.
2018, 38(8): 1972-1976
doi: 10.6023/cjoc201804008
Abstract:
A novel supramolecular host-guest complex of the anticancer drug capecitabine (CAP) with symmetrical α, α', δ, δ'-tetramethyl-cucurbit[6 ]uril (TMeQ[6]) has been characterized using nuclear magnetic resonance spectroscopy, MALDI-TOF mass spectrometry, isothermal titration calorimetryand fluorescence spectroscopy analyses. The result revealed that the alkyl chain of CAP is located inside the cavities of TMeQ[6], whereas the other part of CAP remains outside the portal. Our results suggest that TMeQ[6] could be a promising candidate for use as an excipient in the pharmaceutical and medical research fields.
A novel supramolecular host-guest complex of the anticancer drug capecitabine (CAP) with symmetrical α, α', δ, δ'-tetramethyl-cucurbit[
2018, 38(8): 1977-1984
doi: 10.6023/cjoc201805027
Abstract:
An unprecedented method for the transformation of 2-substituted acrylates into β-ketophosphine oxides has successfully been developed via hydrochloric acid-promoted copper/iron-cocatalyzed deesterificative oxyphosphorylation under dioxygen atmosphere, simultaneously inhibiting the formation of the preceding hydroxyphosphorylation products. Through this convenient and practical process, a library of structurally diverse β-ketophosphine oxides could be selectively and effectively obtained with broad substrate scope and good functional group tolerance under mild conditions, accompanied by chemoselective cleavage of C(sp2)-C(C=O) bonds.
An unprecedented method for the transformation of 2-substituted acrylates into β-ketophosphine oxides has successfully been developed via hydrochloric acid-promoted copper/iron-cocatalyzed deesterificative oxyphosphorylation under dioxygen atmosphere, simultaneously inhibiting the formation of the preceding hydroxyphosphorylation products. Through this convenient and practical process, a library of structurally diverse β-ketophosphine oxides could be selectively and effectively obtained with broad substrate scope and good functional group tolerance under mild conditions, accompanied by chemoselective cleavage of C(sp2)-C(C=O) bonds.
2018, 38(8): 2017-2027
doi: 10.6023/cjoc201804023
Abstract:
The cationic ruthenium allenylidene complexes[RuCl(=C=C=CR2)(DPPQ)2] [BPh4] (3a:R=Ph; 3b:CR2=FN=9H-fluoren-9-ylidene) supported by the heterobidentate P, N-donor ligand 8-(diphenylphosphanyl)quinoline (DPPQ) have been synthesized from the reactions of the dimeric complex[Ru(μ-Cl)(DPPQ)2]2[BPh4]2 (1) with excess 1, 1-diphenylprop-2-yn-1-ol (2a) or 9-ethynyl-9H-fluoren-9-ol (2b), respectively. Addition of hydrazines to the ruthenium-allenylidenes 3 led to the facile formation of ruthenium-bound acrylonitrile complexes[RuCl(N≡C-CH=CR2)(DPPQ)2] [BPh4] (4a:R=Ph; 4b:CR2=FN) at room temperature. This reaction involves the intermolecular nucleophilic attack of hydrazines at the Cα atom of the allenylidene ligand, which represents the first examples of addition of hydrazines to metal-allenylidenes affording acrylonitrile derivatives. Reaction of acrylonitrile complex 4 with an excess of propargyl alcohols 2a or 2b (4 equiv.) could release the organic acrylonitriles 3, 3-diphenylacrylonitrile (5a) or 2-(9H-fluoren-9-ylidene)-acetonitrile (5b) along with regeneration of allenylidene complex 3. In addition, the catalytic activity of 1 for the transformation of terminal propargyl alcohols and hydrazines into acrylonitriles has been investigated preliminarily. The results showed that the catalytic reaction did proceed to give the desired acrylonitrile products, albeit the yield not good. Nevertheless, our results of the catalytic reactions demonstrated that it is very promised to develop new catalytic reactions for the transformation of terminal propargylic alcohols and hydrazines into acrylonitriles via allenylidene intermediates.
The cationic ruthenium allenylidene complexes[RuCl(=C=C=CR2)(DPPQ)2] [BPh4] (3a:R=Ph; 3b:CR2=FN=9H-fluoren-9-ylidene) supported by the heterobidentate P, N-donor ligand 8-(diphenylphosphanyl)quinoline (DPPQ) have been synthesized from the reactions of the dimeric complex[Ru(μ-Cl)(DPPQ)2]2[BPh4]2 (1) with excess 1, 1-diphenylprop-2-yn-1-ol (2a) or 9-ethynyl-9H-fluoren-9-ol (2b), respectively. Addition of hydrazines to the ruthenium-allenylidenes 3 led to the facile formation of ruthenium-bound acrylonitrile complexes[RuCl(N≡C-CH=CR2)(DPPQ)2] [BPh4] (4a:R=Ph; 4b:CR2=FN) at room temperature. This reaction involves the intermolecular nucleophilic attack of hydrazines at the Cα atom of the allenylidene ligand, which represents the first examples of addition of hydrazines to metal-allenylidenes affording acrylonitrile derivatives. Reaction of acrylonitrile complex 4 with an excess of propargyl alcohols 2a or 2b (4 equiv.) could release the organic acrylonitriles 3, 3-diphenylacrylonitrile (5a) or 2-(9H-fluoren-9-ylidene)-acetonitrile (5b) along with regeneration of allenylidene complex 3. In addition, the catalytic activity of 1 for the transformation of terminal propargyl alcohols and hydrazines into acrylonitriles has been investigated preliminarily. The results showed that the catalytic reaction did proceed to give the desired acrylonitrile products, albeit the yield not good. Nevertheless, our results of the catalytic reactions demonstrated that it is very promised to develop new catalytic reactions for the transformation of terminal propargylic alcohols and hydrazines into acrylonitriles via allenylidene intermediates.
2018, 38(8): 2067-2075
doi: 10.6023/cjoc201801001
Abstract:
In this work, a series of dithiocarbamate derivatives bearing diverse quinazolinones, benzoxazinones, and coumarin moieties were designed and synthesized via a one-pot three-component reaction. These compounds produced good yields and functioned quickly under mild conditions, and the desired products were readily isolated. Their in vitro antitumor activities were evaluated by the methyl thiazolyl tetrazolium (MTT) method against hepatoma carcinoma cells HCCLM-7, cervical carcinoma cells Hela, mammary adenocarcinoma cells MDA-MB-435S, colon carcinoma cells SW-480, laryngocarcinoma cells Hep-2, and mammary adenocarcinoma cells MCF-7. 3 compounds were identified as the most promising candidates, due to their high potency and broad-spectrum antiproliferative activity (IC50:3.5~13.5 μmol·L-1). The activities of some lead compounds were more than 10-fold more potent than that of positive control 5-fluorouracil (5-FU) (IC50:8.1~128.7 μmol·L-1). These results indicated that the dithiocarbamate (DTC) derivatives bearing fused heterocyclic moieties could be used as lead for further developing new antitumor active compounds.
In this work, a series of dithiocarbamate derivatives bearing diverse quinazolinones, benzoxazinones, and coumarin moieties were designed and synthesized via a one-pot three-component reaction. These compounds produced good yields and functioned quickly under mild conditions, and the desired products were readily isolated. Their in vitro antitumor activities were evaluated by the methyl thiazolyl tetrazolium (MTT) method against hepatoma carcinoma cells HCCLM-7, cervical carcinoma cells Hela, mammary adenocarcinoma cells MDA-MB-435S, colon carcinoma cells SW-480, laryngocarcinoma cells Hep-2, and mammary adenocarcinoma cells MCF-7. 3 compounds were identified as the most promising candidates, due to their high potency and broad-spectrum antiproliferative activity (IC50:3.5~13.5 μmol·L-1). The activities of some lead compounds were more than 10-fold more potent than that of positive control 5-fluorouracil (5-FU) (IC50:8.1~128.7 μmol·L-1). These results indicated that the dithiocarbamate (DTC) derivatives bearing fused heterocyclic moieties could be used as lead for further developing new antitumor active compounds.
2018, 38(8): 2085-2092
doi: 10.6023/cjoc201801043
Abstract:
Sixteen novel myrtenal-derived 2-acyl-1, 2, 4-triazole-3-thione compounds were designed and synthesized in search of new bioactive compounds. Their structures were confirmed by FTIR, NMR, ESI-MS and elemental analysis. The in vitro antifungal and herbicidal activities of the target compounds were preliminarily evaluated. Some target compounds exhibited favourable antifungal activity at 50 mg/L. Myrtenal-derived 2-(p-methylbenzoyl)-1, 2, 4-triazole-3-thione (7i) held 83.7% and 72.5% inhibition rates against corn southern leaf blight (Bipolaris maydis) and apple root spot (Physalospora piricola), respectively, and myrtenal-derived 2-(3', 5'-dimethylbenzoyl)-1, 2, 4-triazole-3-thione (7j) had 72.5% inhibition rate against P. piricola (the positive control commercial fungicide chlorothalonil with growth inhibition rates of 90.4% and 75.0% against B. maydis and P. piricola, respectively). Besides, most of the target compounds displayed excellent herbicidal activity against the root-growth of rape (Brassica. campestris). At 100 mg/L, 15 compounds held growth inhibition rates in the range of 80.2%~99.1%, exhibiting much better herbicidal activity than that of the commercial herbicide flumioxazin (positive control) with 63.0% growth inhibition rate.
Sixteen novel myrtenal-derived 2-acyl-1, 2, 4-triazole-3-thione compounds were designed and synthesized in search of new bioactive compounds. Their structures were confirmed by FTIR, NMR, ESI-MS and elemental analysis. The in vitro antifungal and herbicidal activities of the target compounds were preliminarily evaluated. Some target compounds exhibited favourable antifungal activity at 50 mg/L. Myrtenal-derived 2-(p-methylbenzoyl)-1, 2, 4-triazole-3-thione (7i) held 83.7% and 72.5% inhibition rates against corn southern leaf blight (Bipolaris maydis) and apple root spot (Physalospora piricola), respectively, and myrtenal-derived 2-(3', 5'-dimethylbenzoyl)-1, 2, 4-triazole-3-thione (7j) had 72.5% inhibition rate against P. piricola (the positive control commercial fungicide chlorothalonil with growth inhibition rates of 90.4% and 75.0% against B. maydis and P. piricola, respectively). Besides, most of the target compounds displayed excellent herbicidal activity against the root-growth of rape (Brassica. campestris). At 100 mg/L, 15 compounds held growth inhibition rates in the range of 80.2%~99.1%, exhibiting much better herbicidal activity than that of the commercial herbicide flumioxazin (positive control) with 63.0% growth inhibition rate.
2018, 38(8): 2101-2108
doi: 10.6023/cjoc201803039
Abstract:
Para-xylene (p-xylene) is an important bulk chemical in petrochemical industry, and the production of biomass-based p-xylene is of great significance in both academic and industrial arenas. This work proves the one step process for the production of p-xylene through the catalytic pyrolysis of lignin into the aromatic monomers, together with the alkylation of light aromatics and the isomerization of xylenes isomers into p-xylene over metal oxides-modified HZSM-5 catalysts. The modified catalysts by adding the La, Mg, Ce, and Zn elements into HZSM-5 promoted the alkylation of light aromatics (like benzene and toluene) into xylenes, and the isomerization of m-/o-xylenes to p-xylene, due to the modulations of the acid strength and the strong acid sites. Co-catalytic pyrolysis of lignin and methanol significantly enhanced the production of p-xylene during the catalytic pyrolysis of lignin. The highest p-xylene yield of 13.9% with a p-xylene/xylenes ratio of 82.7% was obtained by the co-catalytic pyrolysis of lignin with 33 wt% methanol over the 20% La2O3/HZSM-5 catalyst. The reaction pathway for the formation of p-xylene from lignin was addressed based on the identified products and the characterization of catalysts.
Para-xylene (p-xylene) is an important bulk chemical in petrochemical industry, and the production of biomass-based p-xylene is of great significance in both academic and industrial arenas. This work proves the one step process for the production of p-xylene through the catalytic pyrolysis of lignin into the aromatic monomers, together with the alkylation of light aromatics and the isomerization of xylenes isomers into p-xylene over metal oxides-modified HZSM-5 catalysts. The modified catalysts by adding the La, Mg, Ce, and Zn elements into HZSM-5 promoted the alkylation of light aromatics (like benzene and toluene) into xylenes, and the isomerization of m-/o-xylenes to p-xylene, due to the modulations of the acid strength and the strong acid sites. Co-catalytic pyrolysis of lignin and methanol significantly enhanced the production of p-xylene during the catalytic pyrolysis of lignin. The highest p-xylene yield of 13.9% with a p-xylene/xylenes ratio of 82.7% was obtained by the co-catalytic pyrolysis of lignin with 33 wt% methanol over the 20% La2O3/HZSM-5 catalyst. The reaction pathway for the formation of p-xylene from lignin was addressed based on the identified products and the characterization of catalysts.
2018, 38(8): 2116-2121
doi: 10.6023/cjoc201803055
Abstract:
Tetrathiafulvalene vinylogues (TTFV) have attracted for organic-based electronics as their excellent electron donating properties. The most commonly used synthetic access to TTFV is by the oxidative dimerization of corresponding dithiafulvene (DTF) precursors, the oxidants like as I2 and AgBF4 have been reported to promote the dimerization reaction in most cases. However, this method is very limited to lower yield and higher toxicity. Due to the naphthyl fluorescence property and cyanoethylthiolate reactive feature, and through trimethylphosphite-mediated cross-coupling reaction, 4, 5-bis(2-cyanoethylsulfanyl)-1, 3-dithiole-2-thione (1) reacted with 1-naphthaldehyde to give the dithiafulvalene compound (DTF 2) with the yield of 48%. The dithiafulvalene compound 2 has subjected to an p-chloranil (CA)/methanesulfonic acid (MSA) oxidative dimerization reaction and then a brief reductive aqueous workup with Na2S2O3 to gain tetrathiafulvalene vinylogues (TTFV 3). The optimal reaction conditions achieved for the oxidative TTFV formation are 1.5 equiv. of CA catalyst, the 1:10 volume ratio of MSA and DCM, under nitrogen atomsphere and room temperature, 2.0 h reaction time, and the yield of TTFV 3 with up to 86.7%. All novel compounds were characterized by 1H NMR, 13C NMR, FT-IR and MS methods. Meanwhile, the structure of 3 was identified by X-ray diffraction analysis. Compared with the traditional I2 oxidative dimerization method, the results show that this method is simple, economic and efficient.
Tetrathiafulvalene vinylogues (TTFV) have attracted for organic-based electronics as their excellent electron donating properties. The most commonly used synthetic access to TTFV is by the oxidative dimerization of corresponding dithiafulvene (DTF) precursors, the oxidants like as I2 and AgBF4 have been reported to promote the dimerization reaction in most cases. However, this method is very limited to lower yield and higher toxicity. Due to the naphthyl fluorescence property and cyanoethylthiolate reactive feature, and through trimethylphosphite-mediated cross-coupling reaction, 4, 5-bis(2-cyanoethylsulfanyl)-1, 3-dithiole-2-thione (1) reacted with 1-naphthaldehyde to give the dithiafulvalene compound (DTF 2) with the yield of 48%. The dithiafulvalene compound 2 has subjected to an p-chloranil (CA)/methanesulfonic acid (MSA) oxidative dimerization reaction and then a brief reductive aqueous workup with Na2S2O3 to gain tetrathiafulvalene vinylogues (TTFV 3). The optimal reaction conditions achieved for the oxidative TTFV formation are 1.5 equiv. of CA catalyst, the 1:10 volume ratio of MSA and DCM, under nitrogen atomsphere and room temperature, 2.0 h reaction time, and the yield of TTFV 3 with up to 86.7%. All novel compounds were characterized by 1H NMR, 13C NMR, FT-IR and MS methods. Meanwhile, the structure of 3 was identified by X-ray diffraction analysis. Compared with the traditional I2 oxidative dimerization method, the results show that this method is simple, economic and efficient.
2018, 38(8): 2122-2129
doi: 10.6023/cjoc201805036
Abstract:
In order to find novel cyanoacrylate derivatives possessing potent bioactivities, a series of novel cyanoacrylates bearing substituted oxazole unit were designed and prepared. The bioassay data indicated that most title compounds had satisfactory herbicidal activities. At the dosage of 750 g/ha, some compounds showed herbicidal activity against Brassica juncea with 80%~100%, Chenopodium serotinum L. with 90%~100%, and Rumex acetosa L. with 80%~100%. 2-Cyano-3-me-thylthio-3-{[4-(2-(4-fluorophenyl)oxazole-4-yl)methylthio]-benzylanimo}acrylic acid (2-methoxy)ethyl ester (11a) and 2-cyano-3-methylthio-3-{[4-(2-(3, 4-difluorophenyl)oxazole-4-yl)methylthio]-benzylanimo}acrylic acid (2-methoxy)ethyl ester (11e) displayed herbicidal activity against Alopecurus aequalis Sobol with 70% and 60%, and Polypogon fugax Nees ex Steud with 70% and 60%. Compound 11a showed herbicidal activity against Poa acroleuca Steud with 70%. In addition, the inhibitory rates of compound 11a against Brassica juncea and Rumex acetosa L. were both 40% at the dosage of 150 g/ha.
In order to find novel cyanoacrylate derivatives possessing potent bioactivities, a series of novel cyanoacrylates bearing substituted oxazole unit were designed and prepared. The bioassay data indicated that most title compounds had satisfactory herbicidal activities. At the dosage of 750 g/ha, some compounds showed herbicidal activity against Brassica juncea with 80%~100%, Chenopodium serotinum L. with 90%~100%, and Rumex acetosa L. with 80%~100%. 2-Cyano-3-me-thylthio-3-{[4-(2-(4-fluorophenyl)oxazole-4-yl)methylthio]-benzylanimo}acrylic acid (2-methoxy)ethyl ester (11a) and 2-cyano-3-methylthio-3-{[4-(2-(3, 4-difluorophenyl)oxazole-4-yl)methylthio]-benzylanimo}acrylic acid (2-methoxy)ethyl ester (11e) displayed herbicidal activity against Alopecurus aequalis Sobol with 70% and 60%, and Polypogon fugax Nees ex Steud with 70% and 60%. Compound 11a showed herbicidal activity against Poa acroleuca Steud with 70%. In addition, the inhibitory rates of compound 11a against Brassica juncea and Rumex acetosa L. were both 40% at the dosage of 150 g/ha.
2018, 38(8): 2130-2136
doi: 10.6023/cjoc201802027
Abstract:
A novel synthetic method for 1, 2, 6-trisubstituted benzimidazole derivatives was developed, which started from 3-fluoro-4-nitrobenzonitrile and aromatic amines to give the intermediates N-substituted-2-nitro-4-cyanoaniline (1) with high yield and short reaction time under microwave irradiation condition. Then, compound 1 reacted with different aldehydes in the presence of Na2S2O4 to provide the final compounds. Meanwhile, the process of the reactions was optimized in this study and the optimized conditions are described as:dimethyl sulfoxide (DMSO)-H2O as solvent, n(compound 1):n(4-chlorobenzaldehyde):n(sodium dithionite)=1:1:9 at 80℃ for 2 h. Employing the same synthetic method, 21 1, 2, 6-trisubstituted benzimidazole derivatives were synthesized.
A novel synthetic method for 1, 2, 6-trisubstituted benzimidazole derivatives was developed, which started from 3-fluoro-4-nitrobenzonitrile and aromatic amines to give the intermediates N-substituted-2-nitro-4-cyanoaniline (1) with high yield and short reaction time under microwave irradiation condition. Then, compound 1 reacted with different aldehydes in the presence of Na2S2O4 to provide the final compounds. Meanwhile, the process of the reactions was optimized in this study and the optimized conditions are described as:dimethyl sulfoxide (DMSO)-H2O as solvent, n(compound 1):n(4-chlorobenzaldehyde):n(sodium dithionite)=1:1:9 at 80℃ for 2 h. Employing the same synthetic method, 21 1, 2, 6-trisubstituted benzimidazole derivatives were synthesized.
2018, 38(8): 2137-2142
doi: 10.6023/cjoc201802013
Abstract:
Sixteen novel 1, 2, 4-triazole triazene derivatives were synthesized in multiple steps from the p-aminobenzoic acid. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All the target compounds were evaluated for their anticancer activity. Among them, 2-[4-(3, 3-dimethyltriazol-1-yl)phenyl]-3-amino-4-S-(4-chlorobenzyl)-1, 2, 4-triazole (6g), 2-[4-(3, 3-dimethyltriazol-1-yl)phenyl]-3-amino-4-S-(2, 4-dichlorobenzyl)-1, 2, 4-triazole (6h), 2-[4-(3, 3-methylbenzyltriazen-1-yl)-phenyl]-3-amino-4-S-benzyl-1, 2, 4-trioxazole (6i), 2-[4-(3, 3-methylbenzyltriazen-1-yl)phenyl]-3-amino-4-S-(4-methylbenzyl)-1, 2, 4-triazole (6j), 2-[4-(3, 3-methylbenzyltriazen-1-yl)phenyl]-3-amino-4-S-(4-methoxybenzyl)-1, 2, 4-triazole (6l), 2-[4-(3, 3-methylbenzyltriazen-1-yl)phenyl]-3-amino-4-S-(2, 4-di-chlorobenzyl)-1, 2, 4-triazole (6p) exhibited good anti-cancer activity against J82 cells with the IC50 values of 23.883, 5.512, 8.731, 8.077, 5.590 and 12.195 μmol/L, respectively. And compounds 6h, 6i, 6j, 6l exhibited good anti-cancer activity against DU145 cells with the IC50 values of 13.690, 21.908, 10.772 and 4.827 μmol/L, respectively.
Sixteen novel 1, 2, 4-triazole triazene derivatives were synthesized in multiple steps from the p-aminobenzoic acid. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All the target compounds were evaluated for their anticancer activity. Among them, 2-[4-(3, 3-dimethyltriazol-1-yl)phenyl]-3-amino-4-S-(4-chlorobenzyl)-1, 2, 4-triazole (6g), 2-[4-(3, 3-dimethyltriazol-1-yl)phenyl]-3-amino-4-S-(2, 4-dichlorobenzyl)-1, 2, 4-triazole (6h), 2-[4-(3, 3-methylbenzyltriazen-1-yl)-phenyl]-3-amino-4-S-benzyl-1, 2, 4-trioxazole (6i), 2-[4-(3, 3-methylbenzyltriazen-1-yl)phenyl]-3-amino-4-S-(4-methylbenzyl)-1, 2, 4-triazole (6j), 2-[4-(3, 3-methylbenzyltriazen-1-yl)phenyl]-3-amino-4-S-(4-methoxybenzyl)-1, 2, 4-triazole (6l), 2-[4-(3, 3-methylbenzyltriazen-1-yl)phenyl]-3-amino-4-S-(2, 4-di-chlorobenzyl)-1, 2, 4-triazole (6p) exhibited good anti-cancer activity against J82 cells with the IC50 values of 23.883, 5.512, 8.731, 8.077, 5.590 and 12.195 μmol/L, respectively. And compounds 6h, 6i, 6j, 6l exhibited good anti-cancer activity against DU145 cells with the IC50 values of 13.690, 21.908, 10.772 and 4.827 μmol/L, respectively.
2018, 38(8): 2143-2150
doi: 10.6023/cjoc201801024
Abstract:
Based on the scaffold of 4-substituted quinoline, twenty-four 4-thioquinoline compounds were designed and synthesized by molecular hybridization. Their structures were identified by 1H NMR, 13C NMR and HRMS. Meanwhile, all target compounds were evaluated for antifungal activities. The results indicated that the majority of target compounds displayed some activity against each of the fungi. Among them, 4-(ethylthio)-2-phenylquinoline (4a), 4-(isopropylthio)-2-phenylquinoline (4c) and 4-(allylthio)-2-phenylquinoline (4h) were more potent than others, whose inhibition rates against some fungi were comparable to the positive drug azoxystrobin. The structure-activity relationship (SAR) showed that different substituents on 4-position could significantly affect activities. Generally, the presence of aliphatic group could be more beneficial to antifungal activity than aromatic group, and the activity weakened with an increase of steric hindrance. Moreover, the kinds and positions of substituents on the aromatic ring had little or negative effects on the activity.
Based on the scaffold of 4-substituted quinoline, twenty-four 4-thioquinoline compounds were designed and synthesized by molecular hybridization. Their structures were identified by 1H NMR, 13C NMR and HRMS. Meanwhile, all target compounds were evaluated for antifungal activities. The results indicated that the majority of target compounds displayed some activity against each of the fungi. Among them, 4-(ethylthio)-2-phenylquinoline (4a), 4-(isopropylthio)-2-phenylquinoline (4c) and 4-(allylthio)-2-phenylquinoline (4h) were more potent than others, whose inhibition rates against some fungi were comparable to the positive drug azoxystrobin. The structure-activity relationship (SAR) showed that different substituents on 4-position could significantly affect activities. Generally, the presence of aliphatic group could be more beneficial to antifungal activity than aromatic group, and the activity weakened with an increase of steric hindrance. Moreover, the kinds and positions of substituents on the aromatic ring had little or negative effects on the activity.
2018, 38(8): 2161-2166
doi: 10.6023/cjoc201803037
Abstract:
Supramolecular polymer can be formed from amphiphilic block copolymer polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and 4'-iodo-4-dimethylaminoazobenzene molecule through halogen bond. In this paper, honeycomb ordered porous films were prepared by static breath figure (BF) method by this supramolecular polymer. The effects of IAzo content and light illumination conditions on the morphology of supramolecular polymer porous film were studied in detail. The formation of the supramolecular polymer, the surface and the fracture morphology of the porous film were characterized by infrared spectroscopy and scanning electron microscopy. These results showed that with the increase of IAzo content, the pore size of supramolecular polymer porous film gradually increased. In addition, under the irradiation of linearly polarized light, the round hole structure of the porous film can be converted into rectangular holes or rhombic holes according to the change of polarization direction of linearly polarized light. The degree of deformation increases with the increase of azobenzene content and the extension of illumination time. The porous film prepared from this azobenzene-containing supramolecular polymer realizes the light regulation of porous structure by non-synthetic means.
Supramolecular polymer can be formed from amphiphilic block copolymer polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and 4'-iodo-4-dimethylaminoazobenzene molecule through halogen bond. In this paper, honeycomb ordered porous films were prepared by static breath figure (BF) method by this supramolecular polymer. The effects of IAzo content and light illumination conditions on the morphology of supramolecular polymer porous film were studied in detail. The formation of the supramolecular polymer, the surface and the fracture morphology of the porous film were characterized by infrared spectroscopy and scanning electron microscopy. These results showed that with the increase of IAzo content, the pore size of supramolecular polymer porous film gradually increased. In addition, under the irradiation of linearly polarized light, the round hole structure of the porous film can be converted into rectangular holes or rhombic holes according to the change of polarization direction of linearly polarized light. The degree of deformation increases with the increase of azobenzene content and the extension of illumination time. The porous film prepared from this azobenzene-containing supramolecular polymer realizes the light regulation of porous structure by non-synthetic means.
2018, 38(8): 2167-2173
doi: 10.6023/cjoc201802010
Abstract:
Pyrazole is a five-membered heterocyclic molecule with a broad range of biological activities. In this study, a series of new 3-aryl-5-furanyl-4, 5-dihydropyrazole derivatives have been designed and synthesized by the general principle of molecular hybridization. The structures were characterized by 1H NMR, 13C NMR and HRMS. We screened in vitro anti-inflammatory in lipopolysaccharide (LPS)-stimulated RAW-264.7 macrophages and anticancer activity against 3 strains human tumor cell lines (A549, Hela and SGC7901) by the methyl thiazolyl tetrazolium (MTT) assay. The result indicated that dihydropyrazole compounds showed good inhibitory effect on the generation of NO and selective cytotoxic activity against tumor cell lines, and the acyl moieties of amides had an obvious influence on biological activities. Especially, 3 compounds were found to be similar anti-inflammatory to positive control dexamethasone, and 3 compounds displayed similar selective anti-tumor activity to positive control 5-fluorouracil (5-FU), which were to be lead compounds for further SAR research.
Pyrazole is a five-membered heterocyclic molecule with a broad range of biological activities. In this study, a series of new 3-aryl-5-furanyl-4, 5-dihydropyrazole derivatives have been designed and synthesized by the general principle of molecular hybridization. The structures were characterized by 1H NMR, 13C NMR and HRMS. We screened in vitro anti-inflammatory in lipopolysaccharide (LPS)-stimulated RAW-264.7 macrophages and anticancer activity against 3 strains human tumor cell lines (A549, Hela and SGC7901) by the methyl thiazolyl tetrazolium (MTT) assay. The result indicated that dihydropyrazole compounds showed good inhibitory effect on the generation of NO and selective cytotoxic activity against tumor cell lines, and the acyl moieties of amides had an obvious influence on biological activities. Especially, 3 compounds were found to be similar anti-inflammatory to positive control dexamethasone, and 3 compounds displayed similar selective anti-tumor activity to positive control 5-fluorouracil (5-FU), which were to be lead compounds for further SAR research.
2018, 38(8): 2174-2181
doi: 10.6023/cjoc201802012
Abstract:
The catalyst-free addition of 2-methylazaarenes benzylic C(sp3)-H to electron-deficient olefins in neutral ionic liquid aqueous solution was reported, and a series of azaarene derivatives were obtained in good yields. This method is easy to operate and the reaction conditions are mild, which not only expands the application of ionic liquid in C(sp3)-H functionalization reaction, but also has positive significance for promoting the development of the green chemistry.
The catalyst-free addition of 2-methylazaarenes benzylic C(sp3)-H to electron-deficient olefins in neutral ionic liquid aqueous solution was reported, and a series of azaarene derivatives were obtained in good yields. This method is easy to operate and the reaction conditions are mild, which not only expands the application of ionic liquid in C(sp3)-H functionalization reaction, but also has positive significance for promoting the development of the green chemistry.
2018, 38(8): 2151-2160
doi: 10.6023/cjoc201803035
Abstract:
Mono-and bisdiphenyl substituted heteroarylphosphines R-PPh2[R=2-pyridyl (3a), 2-thienyl (3b) and 2-furyl (3c)] and Ph2P-R'-PPh2[R'=2, 6-pyridyl (6a), 2, 5-thienyl (6b) and 2, 5-furyl (6c)] were synthesized. After Staudinger reaction with Me3SiN3, those heteroarylphosphines were converted into the heteroarylphosphinimine ligands, R-PPh2(NSiMe3) and (Me3SiN)Ph2P-R"-PPh2(NSiMe3). The subsequently dehalosilylation reaction with CpTiCl3 afforded the corresponding Ti heteroarylphosphinimine halfmetallocenes as olefin polymerization catalysts. The structures of all the complexes were determined by means of 1H NMR, 13C NMR and 31P NMR spectroscopic methods and further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane (MAO) at a ratio of Al/Ti=600 and under 0.5 MPa of ethylene, these bimetallic Ti phosphinimine complexes displayed a higher catalytic activity compared to the monometallic analogues, but resulted in polymers with bimodal molecular weight distributions. Unexpectedly, 6b produced ultrahigh Mw polyethylene at lower polymerization temperature.
Mono-and bisdiphenyl substituted heteroarylphosphines R-PPh2[R=2-pyridyl (3a), 2-thienyl (3b) and 2-furyl (3c)] and Ph2P-R'-PPh2[R'=2, 6-pyridyl (6a), 2, 5-thienyl (6b) and 2, 5-furyl (6c)] were synthesized. After Staudinger reaction with Me3SiN3, those heteroarylphosphines were converted into the heteroarylphosphinimine ligands, R-PPh2(NSiMe3) and (Me3SiN)Ph2P-R"-PPh2(NSiMe3). The subsequently dehalosilylation reaction with CpTiCl3 afforded the corresponding Ti heteroarylphosphinimine halfmetallocenes as olefin polymerization catalysts. The structures of all the complexes were determined by means of 1H NMR, 13C NMR and 31P NMR spectroscopic methods and further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane (MAO) at a ratio of Al/Ti=600 and under 0.5 MPa of ethylene, these bimetallic Ti phosphinimine complexes displayed a higher catalytic activity compared to the monometallic analogues, but resulted in polymers with bimodal molecular weight distributions. Unexpectedly, 6b produced ultrahigh Mw polyethylene at lower polymerization temperature.
