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2016 Volume 36 Issue 5
2016, 36(5): 875-888
doi: 10.6023/cjoc201601013
Abstract:
Due to the diverse biological activities of indolinones, especially 3,3-disubstituted indolinones, their researches of synthesis have been attracting considerable interest in the areas of organic chemistry. Recently, the radical addition and cyclization reaction of N-arylacrylamides with different radical precursors for the efficient construction of indolinones motifs have attracted much attention. This review summarizes the recent advances of the access to 3,3-disubstituted indolinones based on C—H bond functionalization/cyclization cascade strategy. These reaction mechanisms have also been introduced.
Due to the diverse biological activities of indolinones, especially 3,3-disubstituted indolinones, their researches of synthesis have been attracting considerable interest in the areas of organic chemistry. Recently, the radical addition and cyclization reaction of N-arylacrylamides with different radical precursors for the efficient construction of indolinones motifs have attracted much attention. This review summarizes the recent advances of the access to 3,3-disubstituted indolinones based on C—H bond functionalization/cyclization cascade strategy. These reaction mechanisms have also been introduced.
2016, 36(5): 889-912
doi: 10.6023/cjoc201511017
Abstract:
Diazo compounds had been widely employed as a class of environment friendly and highly efficient coupling reagents in transition-metal-catalyzed C—H bonds insertion reactions. Recently, C—H alkylation of various arenes and heteroarenes has been achieved enormous successes using diazo compounds as the alkylation reagents under a new catalytic model. The recent progress in diazo compounds mediated transition-metal-catalyzed C—H alkylation and tandem C—H alkylation/cyclization is reviewed, including reaction mechanism and synthetic applications. Furthermore, the prospects of this reaction are also discussed.
Diazo compounds had been widely employed as a class of environment friendly and highly efficient coupling reagents in transition-metal-catalyzed C—H bonds insertion reactions. Recently, C—H alkylation of various arenes and heteroarenes has been achieved enormous successes using diazo compounds as the alkylation reagents under a new catalytic model. The recent progress in diazo compounds mediated transition-metal-catalyzed C—H alkylation and tandem C—H alkylation/cyclization is reviewed, including reaction mechanism and synthetic applications. Furthermore, the prospects of this reaction are also discussed.
2016, 36(5): 913-926
doi: 10.6023/cjoc201511047
Abstract:
Münchnones are mesoionic five-membered heterocycles, which play an important role in heterocycles as well as in organic chemistry. Since they were discovered by Huisgen in 1964, there has been growing interest in syntheses, properties and application of münchnones. One of the most significant properties of münchnones is that they can undergo cycloaddition reactions to unsaturated bonds as 1,3-dipoles. This reaction has become an important method for the synthesis of pyrroles and other heterocycles. Recently, remarkable progresses have been achieved in the synthesis of münchnones by means of organo-metallic reactions, the new reactive properties of münchnones have also been explored, and the application of münchnones in organic synthesis has been widely reported. In this review, these recent progresses in the chemistry of münchnone are summarized.
Münchnones are mesoionic five-membered heterocycles, which play an important role in heterocycles as well as in organic chemistry. Since they were discovered by Huisgen in 1964, there has been growing interest in syntheses, properties and application of münchnones. One of the most significant properties of münchnones is that they can undergo cycloaddition reactions to unsaturated bonds as 1,3-dipoles. This reaction has become an important method for the synthesis of pyrroles and other heterocycles. Recently, remarkable progresses have been achieved in the synthesis of münchnones by means of organo-metallic reactions, the new reactive properties of münchnones have also been explored, and the application of münchnones in organic synthesis has been widely reported. In this review, these recent progresses in the chemistry of münchnone are summarized.
2016, 36(5): 927-938
doi: 10.6023/cjoc201511024
Abstract:
Mannich reaction is very important in organic chemistry, especially plays a very important role in the synthesis of drugs. In addition, Mannich base has widespread attention because of it is more significant and specific biological activity. Mannich reaction, diastereoselectivity Mannich reaction, enantioselective Mannich reaction and the application of Mannich reaction are introduced. Finally, the development aspect of this research is brought forward.
Mannich reaction is very important in organic chemistry, especially plays a very important role in the synthesis of drugs. In addition, Mannich base has widespread attention because of it is more significant and specific biological activity. Mannich reaction, diastereoselectivity Mannich reaction, enantioselective Mannich reaction and the application of Mannich reaction are introduced. Finally, the development aspect of this research is brought forward.
2016, 36(5): 939-953
doi: 10.6023/cjoc201511039
Abstract:
The recent progress in the cycloaddition reactions of aziridines is reviewed, mainly including [3+2] and [3+3] cycloaddition reactions. At the same time, several [3+4], [3+2+2], [5+2] and [6+3] cycloaddition reactions are also introduced. Moreover, the prospects of future development are also discussed.
The recent progress in the cycloaddition reactions of aziridines is reviewed, mainly including [3+2] and [3+3] cycloaddition reactions. At the same time, several [3+4], [3+2+2], [5+2] and [6+3] cycloaddition reactions are also introduced. Moreover, the prospects of future development are also discussed.
2016, 36(5): 954-961
doi: 10.6023/cjoc201512014
Abstract:
The biomass-derivable ethyl lactate has been attracting daily increasing attention as a green medium in organic synthesis. The unique advantages of nontoxicity, low cost, complete biodegradability, high boiling point, and excellent compatibility to water and most organic compounds of this solvent cater well to the property of a green reaction medium. In recent years, ethyl lactate (EL) has been successfully used as medium in different types of organic reactions, including Suzuki-Miyaura reaction, Glaser reaction as well as cascade synthesis of heterocyclic compounds with biological activities. Based on our own research interest in this issue, the advances in organic synthesis employing EL as a green medium are summarized.
The biomass-derivable ethyl lactate has been attracting daily increasing attention as a green medium in organic synthesis. The unique advantages of nontoxicity, low cost, complete biodegradability, high boiling point, and excellent compatibility to water and most organic compounds of this solvent cater well to the property of a green reaction medium. In recent years, ethyl lactate (EL) has been successfully used as medium in different types of organic reactions, including Suzuki-Miyaura reaction, Glaser reaction as well as cascade synthesis of heterocyclic compounds with biological activities. Based on our own research interest in this issue, the advances in organic synthesis employing EL as a green medium are summarized.
2016, 36(5): 962-975
doi: 10.6023/cjoc201510012
Abstract:
Over the past few years, many bifunctional fluorescent probes based on small organic molecules, which can be located on the mitochondria to detect specific reactive small molecules (RSMs), including reactive oxygen species, reducing species, metal ions, proton and small anions, have been reported to be successful in achieving visual imaging in mitochondria. For further detection and imaging of the reactive small molecules in tissue, the design and synthesis of two-photon fluorescent probes and near-infrared fluorescent probes bearing good optical properties become increasingly popular. The recently reported mitochondrial fluorescent probes are classified, summarized and reviewed. The bright prospects of these probes in the application of preliminary diagnosis and therapy of some diseases are also discussed.
Over the past few years, many bifunctional fluorescent probes based on small organic molecules, which can be located on the mitochondria to detect specific reactive small molecules (RSMs), including reactive oxygen species, reducing species, metal ions, proton and small anions, have been reported to be successful in achieving visual imaging in mitochondria. For further detection and imaging of the reactive small molecules in tissue, the design and synthesis of two-photon fluorescent probes and near-infrared fluorescent probes bearing good optical properties become increasingly popular. The recently reported mitochondrial fluorescent probes are classified, summarized and reviewed. The bright prospects of these probes in the application of preliminary diagnosis and therapy of some diseases are also discussed.
2016, 36(5): 976-986
doi: 10.6023/cjoc201511021
Abstract:
Diazo compounds are the most commonly used carbene precursors. They can be dediazonized to obtain highly reactive free carbene intermediates or metal cabenoid under transition metal catalysts. Then varieties of chemical transformations can be proceeded, such as X—H (X=C, N, O, S, Si, etc.) insertions, 1,2-hydrogen migration reactions and cyclopropanations. Varieties of pharmaceuticals, natural products and other bioactive moleculars could be synthesized through these methods. As one of the most important diazo compounds α-diazophosphonates could also proceed various chemical transformations and be used to synthesize varieties of organic functional phosphorous compounds. Because organic phosphorous compounds exhibit extensive bioactivities and pharmaceutic activities, the research of α-diazophosphonates has attracted lots of attentions of scientists. The recent development of the reactions of α-diazophosphonates catalyzed by various kinds of catalysts is summarized.
Diazo compounds are the most commonly used carbene precursors. They can be dediazonized to obtain highly reactive free carbene intermediates or metal cabenoid under transition metal catalysts. Then varieties of chemical transformations can be proceeded, such as X—H (X=C, N, O, S, Si, etc.) insertions, 1,2-hydrogen migration reactions and cyclopropanations. Varieties of pharmaceuticals, natural products and other bioactive moleculars could be synthesized through these methods. As one of the most important diazo compounds α-diazophosphonates could also proceed various chemical transformations and be used to synthesize varieties of organic functional phosphorous compounds. Because organic phosphorous compounds exhibit extensive bioactivities and pharmaceutic activities, the research of α-diazophosphonates has attracted lots of attentions of scientists. The recent development of the reactions of α-diazophosphonates catalyzed by various kinds of catalysts is summarized.
2016, 36(5): 987-999
doi: 10.6023/cjoc201509028
Abstract:
Hydrosilylation catalyzed by transition metals or their complexes is one of the most important ways to synthesize organosilicones, and platinum catalysts are widely used. Inorganic carriers supported platinum catalysts not only can avoid the disadvantages of homogeneous catalysts, such as corroding reactor, pain platinum recovery and low reaction selectivity, but also can be available for sequential reactions due to the good mechanical strength and stability in reaction medium. A lot of literatures relating to platinum catalysts supported by inorganic carriers for hydrosilylation have been published. The platinum compounds have been supported by carbon carriers, silica, metallic oxide, molecular sieve or other inorganic carriers via direct load method or complexation between platinum and vinyl, phosphino, amino, arsino or mercapto functional group modified on the surface of the carriers. The research progresses in preparation, structure and properties of inorganic carriers supported platinum catalysts for hydrosilylation during recent 15 years are summarized with the description of their development trend.
Hydrosilylation catalyzed by transition metals or their complexes is one of the most important ways to synthesize organosilicones, and platinum catalysts are widely used. Inorganic carriers supported platinum catalysts not only can avoid the disadvantages of homogeneous catalysts, such as corroding reactor, pain platinum recovery and low reaction selectivity, but also can be available for sequential reactions due to the good mechanical strength and stability in reaction medium. A lot of literatures relating to platinum catalysts supported by inorganic carriers for hydrosilylation have been published. The platinum compounds have been supported by carbon carriers, silica, metallic oxide, molecular sieve or other inorganic carriers via direct load method or complexation between platinum and vinyl, phosphino, amino, arsino or mercapto functional group modified on the surface of the carriers. The research progresses in preparation, structure and properties of inorganic carriers supported platinum catalysts for hydrosilylation during recent 15 years are summarized with the description of their development trend.
2016, 36(5): 1000-1013
doi: 10.6023/cjoc201510032
Abstract:
Functionalized multi-substituted oxazoles including di-and tri-substituted oxazoles, play important roles in the field of pharmaceutical, catalysis and supramolecular chemistry, etc. Based on different starting materials and different methods, the recent advances in synthesis of functionalized multi-substituted oxazoles are reviewed.
Functionalized multi-substituted oxazoles including di-and tri-substituted oxazoles, play important roles in the field of pharmaceutical, catalysis and supramolecular chemistry, etc. Based on different starting materials and different methods, the recent advances in synthesis of functionalized multi-substituted oxazoles are reviewed.
2016, 36(5): 1014-1020
doi: 10.6023/cjoc201601002
Abstract:
The skeleton of 1,1-diarylethane exists in many biologically important molecules. So, the synthesis of 1,1-diarylethanes has absorbed great attention from the chemists. This work has established a reaction of ortho-hydroxylstyrenes with indoles in the presence of racemic phosphoric acid, leading to the efficient synthesis of a series of 1,1-diarylethanes with structural diversity in high yields (up to 99%). This reaction is based on the fact that ortho-hydroxylstyrenes could transform into ortho-quinone methide under the catalysis of racemic phosphoric acid. The dual activation mode of racemic phosphoric acid to ortho-quinone methide and indole via forming two hydrogen bonds contributed greatly to the efficiency of the reaction. The mild reaction condition and wide substrate scope of the reaction will not only provide a useful strategy for solving the problems of residual metal and harsh reaction condition associated with metal catalysis, but also expand the applicability of organocatalytic reactions for the synthesis of 1,1-diarylethanes.
The skeleton of 1,1-diarylethane exists in many biologically important molecules. So, the synthesis of 1,1-diarylethanes has absorbed great attention from the chemists. This work has established a reaction of ortho-hydroxylstyrenes with indoles in the presence of racemic phosphoric acid, leading to the efficient synthesis of a series of 1,1-diarylethanes with structural diversity in high yields (up to 99%). This reaction is based on the fact that ortho-hydroxylstyrenes could transform into ortho-quinone methide under the catalysis of racemic phosphoric acid. The dual activation mode of racemic phosphoric acid to ortho-quinone methide and indole via forming two hydrogen bonds contributed greatly to the efficiency of the reaction. The mild reaction condition and wide substrate scope of the reaction will not only provide a useful strategy for solving the problems of residual metal and harsh reaction condition associated with metal catalysis, but also expand the applicability of organocatalytic reactions for the synthesis of 1,1-diarylethanes.
2016, 36(5): 1021-1027
doi: 10.6023/cjoc201603011
Abstract:
A general and efficient method for the synthesis of diaryl ethers via nano-CuI catalyzed coupling reaction of phenols with nitroarenes was developed. The efficiency of this reaction was demonstrated by its compatibility with a range of functional groups in good to excellent yields. The catalyst could be recycled for three times without significant loss of the catalytic activity.
A general and efficient method for the synthesis of diaryl ethers via nano-CuI catalyzed coupling reaction of phenols with nitroarenes was developed. The efficiency of this reaction was demonstrated by its compatibility with a range of functional groups in good to excellent yields. The catalyst could be recycled for three times without significant loss of the catalytic activity.
2016, 36(5): 1028-1033
doi: 10.6023/cjoc201511041
Abstract:
A series of α-chloroketones were obtained from silyl enol ethers of aryl ketones using trimethylchlorosilane as chlorine source and diacetoxyiodobenzene as promoter. The reaction occurs under mild condition yielding the product in moderate to good yields, and has the potential possibility for the synthesis of α-bromoketone by using trimethyl bromosilane as bromine source.
A series of α-chloroketones were obtained from silyl enol ethers of aryl ketones using trimethylchlorosilane as chlorine source and diacetoxyiodobenzene as promoter. The reaction occurs under mild condition yielding the product in moderate to good yields, and has the potential possibility for the synthesis of α-bromoketone by using trimethyl bromosilane as bromine source.
2016, 36(5): 1034-1043
doi: 10.6023/cjoc201512018
Abstract:
A copper-silver nanoparticles-catalyzed addition of terminal alkynes to aldehydes was developed for the synthesis of propargyl alcohols. With the promotion of bipyridine ligand, the bimetallic catalyst showed highly efficient to the reaction under neat condition, and good to excellent yields were achieved for various propargylic alcohols. In this catalytic reaction, a remarkable bimetallic synergistic effect was observed, in which Ag NPs worked as the co-catalyst and improved the catalytic activity of Cu NPs significantly. The nanoparticle catalyst could be recovered and reused effectively, and no obvious reduction on catalytic activity was observed after four recycles. Furthermore, a gram-scale reaction was also carried out successfully.
A copper-silver nanoparticles-catalyzed addition of terminal alkynes to aldehydes was developed for the synthesis of propargyl alcohols. With the promotion of bipyridine ligand, the bimetallic catalyst showed highly efficient to the reaction under neat condition, and good to excellent yields were achieved for various propargylic alcohols. In this catalytic reaction, a remarkable bimetallic synergistic effect was observed, in which Ag NPs worked as the co-catalyst and improved the catalytic activity of Cu NPs significantly. The nanoparticle catalyst could be recovered and reused effectively, and no obvious reduction on catalytic activity was observed after four recycles. Furthermore, a gram-scale reaction was also carried out successfully.
2016, 36(5): 1044-1050
doi: 10.6023/cjoc201510018
Abstract:
A series of 2-substituted aniline quinazoline derivatives were prepared with the starting material of quinazoline-2,4(1H,3H)-dione, and then followed by the reaction of chlorination, Suzuki reaction and nucleophilic substitution. The structures of target compounds were identified by 1H NMR, 13C NMR and HRMS. The preliminary biological evaluations were performed using thiazolyl blue tetrazolium bromide (MTT) method to test their antiproliferative activities against some tumor cell lines. The results suggest that some compounds have the abilities to inhibit the growth of Hela tumor cell lines, and most potent compounds 4u and 4v alsoexhibit good antiproliferative activities against A549 and MCF-7 tumor cell lines.
A series of 2-substituted aniline quinazoline derivatives were prepared with the starting material of quinazoline-2,4(1H,3H)-dione, and then followed by the reaction of chlorination, Suzuki reaction and nucleophilic substitution. The structures of target compounds were identified by 1H NMR, 13C NMR and HRMS. The preliminary biological evaluations were performed using thiazolyl blue tetrazolium bromide (MTT) method to test their antiproliferative activities against some tumor cell lines. The results suggest that some compounds have the abilities to inhibit the growth of Hela tumor cell lines, and most potent compounds 4u and 4v alsoexhibit good antiproliferative activities against A549 and MCF-7 tumor cell lines.
2016, 36(5): 1051-1059
doi: 10.6023/cjoc201510019
Abstract:
In order to find novel diacylhydrazine derivatives which possessed high activities against pests, 20 novel N-(tert-butyl)-N'-fluorobenzoyl-substitutedpyridylcarbonyl hydrazide derivatives were synthesized by introducing fluoro-contained phenyl and pyridine into the basic structure of diacylhydrazines. Their structures were confirmed by 1H NMR, 13C NMR, IR and HRMS. The bioassay results indicated that most of the compounds exhibited more than 80% mortality against Mythimna separateat the concentration of 500 mg/L. Among these compounds, N-(tert-butyl)-N'-(2,6-difluorobenzoyl)-N-2-chloronico-tinohydrazine (6bb)andN-(tert-butyl)-N'-(2,6-difluorobenzoyl)-N-2,5-dichloronicotinohydrazine (6gb)exhibited 100% and 80% mortality against Mythimna separateat 10 mg/L, respectively. The LC50 of compound 6bb against Mythimna separatawas 8.77 mg/L, and it showed about 0.51 times of toxicity against Mythimna separatethan tebufenozide and had 1.5 times of toxicity against Plutella xylostella than tebufenozide.
In order to find novel diacylhydrazine derivatives which possessed high activities against pests, 20 novel N-(tert-butyl)-N'-fluorobenzoyl-substitutedpyridylcarbonyl hydrazide derivatives were synthesized by introducing fluoro-contained phenyl and pyridine into the basic structure of diacylhydrazines. Their structures were confirmed by 1H NMR, 13C NMR, IR and HRMS. The bioassay results indicated that most of the compounds exhibited more than 80% mortality against Mythimna separateat the concentration of 500 mg/L. Among these compounds, N-(tert-butyl)-N'-(2,6-difluorobenzoyl)-N-2-chloronico-tinohydrazine (6bb)andN-(tert-butyl)-N'-(2,6-difluorobenzoyl)-N-2,5-dichloronicotinohydrazine (6gb)exhibited 100% and 80% mortality against Mythimna separateat 10 mg/L, respectively. The LC50 of compound 6bb against Mythimna separatawas 8.77 mg/L, and it showed about 0.51 times of toxicity against Mythimna separatethan tebufenozide and had 1.5 times of toxicity against Plutella xylostella than tebufenozide.
2016, 36(5): 1060-1064
doi: 10.6023/cjoc201510031
Abstract:
A green, practical and efficient iron-catalyzed, base free cross-coupling reaction of non-activated secondary alkyl halides with the alkynes Grignard reagent has been developed to afford a variety of alkyl alkynes in high yields, using iron(III) chlorides as catalyst. This approach is quick and easy to operate. It exhibits promising in industry since utilizing the low-cost iron as a catalyst instead of expensive palladium or nickel.
A green, practical and efficient iron-catalyzed, base free cross-coupling reaction of non-activated secondary alkyl halides with the alkynes Grignard reagent has been developed to afford a variety of alkyl alkynes in high yields, using iron(III) chlorides as catalyst. This approach is quick and easy to operate. It exhibits promising in industry since utilizing the low-cost iron as a catalyst instead of expensive palladium or nickel.
2016, 36(5): 1065-1072
doi: 10.6023/cjoc201510013
Abstract:
Complex III is an essential component for cellular respiration chain and one of the most important targets of fungicides. According to bioisosterism and combination of bioactive sub-structive, a series of novel triazolesulfonamide derivatives containing quinolin-2-one moiety were designed and synthesized. The structures of the synthesized compounds were confirmed by MS, 1H NMR, 13C NMR and elemental analysis. The antibacterial activities of these compounds against porcine complex III were evaluated, and the bioassay results indicated that the target compound 6f [IC50=(45.75±1.02) μmol/L] showed much higher inhibitory potency (more than one-fold higher) against complex III than that of the control amisulbrom [IC50=(92.96±1.30) μmol/L], thus compound 6f may recognize as a lead for further structure modification.
Complex III is an essential component for cellular respiration chain and one of the most important targets of fungicides. According to bioisosterism and combination of bioactive sub-structive, a series of novel triazolesulfonamide derivatives containing quinolin-2-one moiety were designed and synthesized. The structures of the synthesized compounds were confirmed by MS, 1H NMR, 13C NMR and elemental analysis. The antibacterial activities of these compounds against porcine complex III were evaluated, and the bioassay results indicated that the target compound 6f [IC50=(45.75±1.02) μmol/L] showed much higher inhibitory potency (more than one-fold higher) against complex III than that of the control amisulbrom [IC50=(92.96±1.30) μmol/L], thus compound 6f may recognize as a lead for further structure modification.
2016, 36(5): 1073-1079
doi: 10.6023/cjoc201509040
Abstract:
Claisen-Schmidt condensation of β-diketone and aryl aldehyde is studied. The reaction product could be mono-or di-alkene. C—C bond cleavage is involved in the production of monoalkene. While the dialkene products are three-membered ring analogues of curcumin.
Claisen-Schmidt condensation of β-diketone and aryl aldehyde is studied. The reaction product could be mono-or di-alkene. C—C bond cleavage is involved in the production of monoalkene. While the dialkene products are three-membered ring analogues of curcumin.
2016, 36(5): 1080-1087
doi: 10.6023/cjoc201510034
Abstract:
Ten derivatives were successfully synthesized by the introduction of nitrogen-and oxygen-containing heterocyclic compounds at ring A and the modification of the amidation at C(28) position in the natural product ursolic acid, which structures were characterized by 1H NMR, 13C NMR, MS and elemental analysis. Their anti-tumor activities against KB and SGC7901 cells in vitro were evaluated by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. These results indicated that all of derivatives can inhibit cell proliferation of KB and SGC7901 cells better than ursolic acid (UA), and UA4-1 (IC50=0. 289 μmol/L) and UA4-2 (IC50=0. 04 μmol/L) were also found to have especially more potent inhibitory activity on SGC7901 tumor cells than that of the positive control drug gefitinib (IC50=1. 03 μmol/L).
Ten derivatives were successfully synthesized by the introduction of nitrogen-and oxygen-containing heterocyclic compounds at ring A and the modification of the amidation at C(28) position in the natural product ursolic acid, which structures were characterized by 1H NMR, 13C NMR, MS and elemental analysis. Their anti-tumor activities against KB and SGC7901 cells in vitro were evaluated by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. These results indicated that all of derivatives can inhibit cell proliferation of KB and SGC7901 cells better than ursolic acid (UA), and UA4-1 (IC50=0. 289 μmol/L) and UA4-2 (IC50=0. 04 μmol/L) were also found to have especially more potent inhibitory activity on SGC7901 tumor cells than that of the positive control drug gefitinib (IC50=1. 03 μmol/L).
2016, 36(5): 1088-1093
doi: 10.6023/cjoc201511031
Abstract:
By using calix[4]arene as platform, the construction of calix[4]arene derivatives with unique structures and binding properties is the important research field in organic supramolecular chemistry. In this paper, the chain-opening calix[4]arene bi-thiourea derivative 4 was synthesized by reacting calix[4]arene bi-aromatic amino derivative 3 with phenyl isothiocyanate in yield of 95%. Treating compound 3 with p-phenylene diisothiocyanate (molar ratio=1:1) gave bridging calix[4]arene bi-thiourea derivative 5 in yield of 80%. Treating compound 3 with excess p-phenylene diisothiocyanate afforded calix[4]arene thiourea derivative 6 in yield of 82%and was further converted to multiple-azo calix[4]arene derivative 7 by reacting compound 6 with salicylyl hydrazine in yield of 75%. The experiments of UV titration spectra for four tested dyes (orange I, alizarin green, victorial blue and methylene blue) showed that compounds 4~7 possessed excellent complexation abilities with 1:1 ratios for complexation and 105 magnitudes for the association constants. The chain-opening structure, more amino groups and more aromatic groups were favorable for the improvement of complexation abilities.
By using calix[4]arene as platform, the construction of calix[4]arene derivatives with unique structures and binding properties is the important research field in organic supramolecular chemistry. In this paper, the chain-opening calix[4]arene bi-thiourea derivative 4 was synthesized by reacting calix[4]arene bi-aromatic amino derivative 3 with phenyl isothiocyanate in yield of 95%. Treating compound 3 with p-phenylene diisothiocyanate (molar ratio=1:1) gave bridging calix[4]arene bi-thiourea derivative 5 in yield of 80%. Treating compound 3 with excess p-phenylene diisothiocyanate afforded calix[4]arene thiourea derivative 6 in yield of 82%and was further converted to multiple-azo calix[4]arene derivative 7 by reacting compound 6 with salicylyl hydrazine in yield of 75%. The experiments of UV titration spectra for four tested dyes (orange I, alizarin green, victorial blue and methylene blue) showed that compounds 4~7 possessed excellent complexation abilities with 1:1 ratios for complexation and 105 magnitudes for the association constants. The chain-opening structure, more amino groups and more aromatic groups were favorable for the improvement of complexation abilities.
2016, 36(5): 1094-1098
doi: 10.6023/cjoc201510035
Abstract:
In this paper, a novel air-stable triphenylbismuth bisperfluorooctanesulfonate was synthesized by treatment of moisture-sensitive triphenylbismuth dichloride with silver bisperfluorooctanesulfonate in anhydrous CH2Cl2 at room temperature. Its catalytic assessment results show that the reactions of arylamine and epoxide proceed efficiently in the presence of triphenylbismuth bisperfluorooctanesulfonates 1(5.0 mol%) under solvent-free condition, affording β-amino alcohols in good to excellent yields. The yields of desired products do not reduce obviously after recycling for 4 times of catalyst 1. Hence, a convenient and efficient method for preparation of β-amino alcohols is provided.
In this paper, a novel air-stable triphenylbismuth bisperfluorooctanesulfonate was synthesized by treatment of moisture-sensitive triphenylbismuth dichloride with silver bisperfluorooctanesulfonate in anhydrous CH2Cl2 at room temperature. Its catalytic assessment results show that the reactions of arylamine and epoxide proceed efficiently in the presence of triphenylbismuth bisperfluorooctanesulfonates 1(5.0 mol%) under solvent-free condition, affording β-amino alcohols in good to excellent yields. The yields of desired products do not reduce obviously after recycling for 4 times of catalyst 1. Hence, a convenient and efficient method for preparation of β-amino alcohols is provided.
2016, 36(5): 1099-1103
doi: 10.6023/cjoc201510009
Abstract:
Six kinds of 3,3-dimethyl-diphenyl-2,4-dioxa-8,10-diazaspiro[5.5]-undecane-1,5-dione-9-thione derivatives were sythesized by the three component one-pot reaction of aromatic aldehydes with thiourea and 2,2-dimethyl-1,3-dio-xane-4,6-dione in the presence of molecular iodine under solvent-free conditions. The results indicated that the yields ranged from 73% to 91% at 80 ℃ for 3.0~6.0 h using 10 mol% iodine (relative to the substrate of 2,2-dimethyl-1,3-dioxane-4,6-dione). Furthermore, the present procedure with high yields was milder conditions and simpler post-treatment process.
Six kinds of 3,3-dimethyl-diphenyl-2,4-dioxa-8,10-diazaspiro[5.5]-undecane-1,5-dione-9-thione derivatives were sythesized by the three component one-pot reaction of aromatic aldehydes with thiourea and 2,2-dimethyl-1,3-dio-xane-4,6-dione in the presence of molecular iodine under solvent-free conditions. The results indicated that the yields ranged from 73% to 91% at 80 ℃ for 3.0~6.0 h using 10 mol% iodine (relative to the substrate of 2,2-dimethyl-1,3-dioxane-4,6-dione). Furthermore, the present procedure with high yields was milder conditions and simpler post-treatment process.
2016, 36(5): 1104-1110
doi: 10.6023/cjoc201511019
Abstract:
Four new task-specfic benzothiazolium ionic liquids (ILs) [HBth]HSO4, [HBth]H2PO4, [HBth]ClO4, [HBth]NO3 were synthesized and characterized by NMR and FT-IR, which bear the proton acid groups based on low price benzothiazole as raw material. The catalytic activities of these acidic ionic liquids were investigated by the esterification of ricinoleic acid with ethanol ethylene glycol monobutyl ether (EGBE) and were compared with concentrated sulfuric acid. The results showed that under the optimized conditions: n(Ricinoleic acid):n(EGBE)=1:1.15, catalyst dosage 2% (wt) of ricinoleic acid, reaction temperature 90 ℃ and reaction time 5 h, esterification yield was up to 98.8%. The ionic liquids dried in vacuum till remained high activity after reused for 10 times. Finally, the yields of series of ricinoleic acid binary alcohol ether ester and short-chain fatty acids ester were also high with [HBth]HSO4 as catalyst, and the ionic liquids can form split-phases with ester product. Compared with the traditional sulfuric acid catalytic esterification, catalytic esterification of such ionic liquid has the advantages of low production cost, clean process, low corrosion rate, reusable, and has the potential of replacing the traditional sulfuric acid in catalytic esterification reaction of ricinoleic acid.
Four new task-specfic benzothiazolium ionic liquids (ILs) [HBth]HSO4, [HBth]H2PO4, [HBth]ClO4, [HBth]NO3 were synthesized and characterized by NMR and FT-IR, which bear the proton acid groups based on low price benzothiazole as raw material. The catalytic activities of these acidic ionic liquids were investigated by the esterification of ricinoleic acid with ethanol ethylene glycol monobutyl ether (EGBE) and were compared with concentrated sulfuric acid. The results showed that under the optimized conditions: n(Ricinoleic acid):n(EGBE)=1:1.15, catalyst dosage 2% (wt) of ricinoleic acid, reaction temperature 90 ℃ and reaction time 5 h, esterification yield was up to 98.8%. The ionic liquids dried in vacuum till remained high activity after reused for 10 times. Finally, the yields of series of ricinoleic acid binary alcohol ether ester and short-chain fatty acids ester were also high with [HBth]HSO4 as catalyst, and the ionic liquids can form split-phases with ester product. Compared with the traditional sulfuric acid catalytic esterification, catalytic esterification of such ionic liquid has the advantages of low production cost, clean process, low corrosion rate, reusable, and has the potential of replacing the traditional sulfuric acid in catalytic esterification reaction of ricinoleic acid.
2016, 36(5): 1111-1117
doi: 10.6023/cjoc201511040
Abstract:
(－)-Arctigenin, the main active ingredient of traditional chinese medicine (TCM) arctii fructus, belongs to dibenzyl butyrolactone lignans. In order to study the structure-activity relationship of arctigenin, a new method for asymmetric synthesis of (－)-arctigenin and its enantiomer was developed. Phenylpropanoic acid derivate was used as starting material and the chiral center of beta butyrolactone was constructed by using oxazolidinone chiral auxiliary. The eesof R and S configurations are 98% and 96%, respectively. Then the second chiral center in the alpha position was constructed benefitting from the steric effect. After removal of protecting group, the target compounds were obtained in 58 % and 55% overall yield of (－)-arcti-genin and (+)-arctigenin with 97% and 96% ee,respectively. This work paved the way for further structural optimization of arctigenin.
(－)-Arctigenin, the main active ingredient of traditional chinese medicine (TCM) arctii fructus, belongs to dibenzyl butyrolactone lignans. In order to study the structure-activity relationship of arctigenin, a new method for asymmetric synthesis of (－)-arctigenin and its enantiomer was developed. Phenylpropanoic acid derivate was used as starting material and the chiral center of beta butyrolactone was constructed by using oxazolidinone chiral auxiliary. The eesof R and S configurations are 98% and 96%, respectively. Then the second chiral center in the alpha position was constructed benefitting from the steric effect. After removal of protecting group, the target compounds were obtained in 58 % and 55% overall yield of (－)-arcti-genin and (+)-arctigenin with 97% and 96% ee,respectively. This work paved the way for further structural optimization of arctigenin.
2016, 36(5): 1118-1121
doi: 10.6023/cjoc201511045
Abstract:
The Claisen-Schmidt condensation of acetylferrocene with arylaldehydes in the presence of ionic liquids (ILs) or phase-transfer catalysts (PTCs) provided the corresponding ferrocenylchalcones in high yields, and PTCs can promote the condensation reaction better than those of ILs. Optimum conditions were as follows: molar ratio of acetylferrocene, arylaldehyde, n-Bu4NPF6 and NaOH is 1:1:2.5:0.75, and the appropriate reaction temperature is 35 ℃ in anhydrous EtOH.
The Claisen-Schmidt condensation of acetylferrocene with arylaldehydes in the presence of ionic liquids (ILs) or phase-transfer catalysts (PTCs) provided the corresponding ferrocenylchalcones in high yields, and PTCs can promote the condensation reaction better than those of ILs. Optimum conditions were as follows: molar ratio of acetylferrocene, arylaldehyde, n-Bu4NPF6 and NaOH is 1:1:2.5:0.75, and the appropriate reaction temperature is 35 ℃ in anhydrous EtOH.
2016, 36(5): 1122-1126
doi: 10.6023/cjoc201512013
Abstract:
Chloromethyl methyl ether (MOMCl) is an important protecting agent in organic synthesis. An efficient synthesis of chloromethyl methyl ether is reported and a one-pot hydroxyl protection procedure is developed. The method features mild condition, short reaction time, high yield and simple operation.
Chloromethyl methyl ether (MOMCl) is an important protecting agent in organic synthesis. An efficient synthesis of chloromethyl methyl ether is reported and a one-pot hydroxyl protection procedure is developed. The method features mild condition, short reaction time, high yield and simple operation.
2016, 36(5): 1127-1132
doi: 10.6023/cjoc201511033
Abstract:
Cascade reaction, including nucleophilic substitution and addition cyclization, catalyzed by Cu+ salt between substituted aryl hydrazonoyl halides and terminal alkynes could produce 1,3,5-trisubstituted pyrazoles. The method employed easily available aryl hydrazonoyl halide and terminal alkynes as starting materials under 45 ℃ in green acetonitrile/water solvent, regioselectively generating 1,3,5-trisubstituted pyrazoles in high yield. Above all, functional groups containing active hydrogen would not disturb this reaction, example for carboxyl and hydroxyl. In this work 17 pyrazole derivatives with different substituent group were achieved by this method. So it could be a general method to synthesize 1,3,5-trisubstituted pyrazoles.
Cascade reaction, including nucleophilic substitution and addition cyclization, catalyzed by Cu+ salt between substituted aryl hydrazonoyl halides and terminal alkynes could produce 1,3,5-trisubstituted pyrazoles. The method employed easily available aryl hydrazonoyl halide and terminal alkynes as starting materials under 45 ℃ in green acetonitrile/water solvent, regioselectively generating 1,3,5-trisubstituted pyrazoles in high yield. Above all, functional groups containing active hydrogen would not disturb this reaction, example for carboxyl and hydroxyl. In this work 17 pyrazole derivatives with different substituent group were achieved by this method. So it could be a general method to synthesize 1,3,5-trisubstituted pyrazoles.
2016, 36(5): 1133-1142
doi: 10.6023/cjoc201511034
Abstract:
Starting from N-methylimidazole, 1,2-dimethylimidazole and 2-chloroethanol, a series of imidazolium-based energetic ionic liquids were synthesized via quaternization, nitration and metathesis reactions. All the energetic ionic liquids were characterized by ultraviolet visible spectrum (UV-Vis), infrared spectrum (IR), mass spectrometry (MS), nuclear magnetic resonance (NMR) and elemental analysis. The solubility study of these ionic liquids was carried out with commonly used organic solvents, which showed that the energetic ionic liquids dissolved easily in polar solvents. Moreover, the ionic liquids had good thermo-stabilities indicated by thermal gravimetric analysis (TG-DTG) and differential scanning calorimetry (DSC). TG-DTG analyses showed that N-nitrooxyethylimidazolium nitrate decomposed at about 160 ℃ and N-hydroxyethylimida-zolium ionic salts decomposed above 190 ℃. Furthermore, there was an obvious glass transition process for the energetic ionic liquids based on 1-(2-nitrooxyethyl)-3-methylimidazolium and N-hydroxyethylimidazolium during the secondary heating process of DSC, which was the unique property of ionic liquids. Their densities and standard enthalpies of formation and detonation properties were calculated and analyzed.
Starting from N-methylimidazole, 1,2-dimethylimidazole and 2-chloroethanol, a series of imidazolium-based energetic ionic liquids were synthesized via quaternization, nitration and metathesis reactions. All the energetic ionic liquids were characterized by ultraviolet visible spectrum (UV-Vis), infrared spectrum (IR), mass spectrometry (MS), nuclear magnetic resonance (NMR) and elemental analysis. The solubility study of these ionic liquids was carried out with commonly used organic solvents, which showed that the energetic ionic liquids dissolved easily in polar solvents. Moreover, the ionic liquids had good thermo-stabilities indicated by thermal gravimetric analysis (TG-DTG) and differential scanning calorimetry (DSC). TG-DTG analyses showed that N-nitrooxyethylimidazolium nitrate decomposed at about 160 ℃ and N-hydroxyethylimida-zolium ionic salts decomposed above 190 ℃. Furthermore, there was an obvious glass transition process for the energetic ionic liquids based on 1-(2-nitrooxyethyl)-3-methylimidazolium and N-hydroxyethylimidazolium during the secondary heating process of DSC, which was the unique property of ionic liquids. Their densities and standard enthalpies of formation and detonation properties were calculated and analyzed.
2016, 36(5): 1143-1147
doi: 10.6023/cjoc201509046
Abstract:
A convenient method for the synthesis of oxyresveratrol catalyzed by palladium is described. 2,4-Dihydroxyiodo-benzene underwent Heck reaction with acrylic acid, then decarboxylation, and further underwent Heck reaction with 3,5-dihydroxyiodobenzene, furnishing oxyresveratrol in a high yield. The title compound was characterized by MS and NMR. This synthetic method has several advantages such as less step processes, high yield, simple operations, and promises to be applied in industrial production.
A convenient method for the synthesis of oxyresveratrol catalyzed by palladium is described. 2,4-Dihydroxyiodo-benzene underwent Heck reaction with acrylic acid, then decarboxylation, and further underwent Heck reaction with 3,5-dihydroxyiodobenzene, furnishing oxyresveratrol in a high yield. The title compound was characterized by MS and NMR. This synthetic method has several advantages such as less step processes, high yield, simple operations, and promises to be applied in industrial production.
