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2018 Volume 38 Issue 2
2018, 38(2): 291-303
doi: 10.6023/cjoc201708055
Abstract:
C-H bonds are widely existed in almost all the organic compounds. Transition-metal-catalyzed C-H functionalizations usually have high reaction efficiency and high atom-economy. However, traditional strategies based on such transition-metal catalyzed C-H activations generally result in poor selectivities, because C-H bonds in one molecule facilely display similar reactivity. It is difficult to be utilized in preparation of natural products, pharmaceuticals and biomolecules. However, directing group can induce the metal to activate proximal C-H bonds via cyclometallated intermediates, improve the regioselectivity of the transformations. Therefore, it is extremely significant to deveplop auxiliary-induced C-H bonds activations. The research progress of directing group-induced C-H activation reactions and mechanisms for recent ten years are sumarized.
C-H bonds are widely existed in almost all the organic compounds. Transition-metal-catalyzed C-H functionalizations usually have high reaction efficiency and high atom-economy. However, traditional strategies based on such transition-metal catalyzed C-H activations generally result in poor selectivities, because C-H bonds in one molecule facilely display similar reactivity. It is difficult to be utilized in preparation of natural products, pharmaceuticals and biomolecules. However, directing group can induce the metal to activate proximal C-H bonds via cyclometallated intermediates, improve the regioselectivity of the transformations. Therefore, it is extremely significant to deveplop auxiliary-induced C-H bonds activations. The research progress of directing group-induced C-H activation reactions and mechanisms for recent ten years are sumarized.
2018, 38(2): 304-315
doi: 10.6023/cjoc201707002
Abstract:
Halobenzonitrile is an important raw material in the fields of medicine, pesticide and materials. Halobenzonitrile has a nitrile group and a halo group which all could react with nucleophile reagents. The law for the selective synthesis of halothiobenzamide or mercaptobenzonitrile from the reaction of halobenzonitrile and different sulfur source is summarized. It is found that the halothiobenzamide product could be synthesized under protonic acid condition from halobenzonitrile, while the mercaptobenzonitrile product would be formed under the alkaline conditions.
Halobenzonitrile is an important raw material in the fields of medicine, pesticide and materials. Halobenzonitrile has a nitrile group and a halo group which all could react with nucleophile reagents. The law for the selective synthesis of halothiobenzamide or mercaptobenzonitrile from the reaction of halobenzonitrile and different sulfur source is summarized. It is found that the halothiobenzamide product could be synthesized under protonic acid condition from halobenzonitrile, while the mercaptobenzonitrile product would be formed under the alkaline conditions.
2018, 38(2): 316-327
doi: 10.6023/cjoc201708058
Abstract:
Arylated coumarin derivatives are a kind of heterocyclic compounds, which play important roles in medicine, biology and material science, and their synthetic methods have attracted much attention. In recent years, many efficient, green synthetic approaches of arylated coumarin derivatives have been reported using transition-metal or metal-free catalytic systems. The recent progress in the synthesis of arylated coumarin derivatives is reviewed according to differences of reaction positions and arylation sources.
Arylated coumarin derivatives are a kind of heterocyclic compounds, which play important roles in medicine, biology and material science, and their synthetic methods have attracted much attention. In recent years, many efficient, green synthetic approaches of arylated coumarin derivatives have been reported using transition-metal or metal-free catalytic systems. The recent progress in the synthesis of arylated coumarin derivatives is reviewed according to differences of reaction positions and arylation sources.
2018, 38(2): 328-340
doi: 10.6023/cjoc201708024
Abstract:
The C (sp3)-H adjacent to heteroatoms can be readily functionalized to C-C, C-N, C-O bonds etc. via cascade[1, n]-hydride transfer/cyclization, which shows high potency to construct 5-membered, 6-membered and all carbon rings. This intriguing cascade process can be employed to synthesize common skeletons of significant natural products and pharmaceutical molecules. Chiral amines, Lewis acids and Brønsted acids have been successfully utilized to catalyze the asymmetric cascade reaction.
The C (sp3)-H adjacent to heteroatoms can be readily functionalized to C-C, C-N, C-O bonds etc. via cascade[1, n]-hydride transfer/cyclization, which shows high potency to construct 5-membered, 6-membered and all carbon rings. This intriguing cascade process can be employed to synthesize common skeletons of significant natural products and pharmaceutical molecules. Chiral amines, Lewis acids and Brønsted acids have been successfully utilized to catalyze the asymmetric cascade reaction.
2018, 38(2): 341-349
doi: 10.6023/cjoc201708040
Abstract:
Organo-phosphorus chemistry is an important branch of organic chemistry and life science research. P-Stereogenic organophosphorus compounds have attracted great interest due to their potential applications in the fields of pharmaceutical chemistry, agrochemistry, material science and as ligands for asymmetric catalysis. The preparation of enantiomerically enriched phosphorus compounds with P-stereogenic centers using natural chiral compounds as chiral auxiliary has received considerable attention. The recent development of the asymmetric synthesis of P-stereogenic organophosphoryl compounds employing menthol, sparteine, ephedrine, and carbohydrates as chiral auxiliary is summarized.
Organo-phosphorus chemistry is an important branch of organic chemistry and life science research. P-Stereogenic organophosphorus compounds have attracted great interest due to their potential applications in the fields of pharmaceutical chemistry, agrochemistry, material science and as ligands for asymmetric catalysis. The preparation of enantiomerically enriched phosphorus compounds with P-stereogenic centers using natural chiral compounds as chiral auxiliary has received considerable attention. The recent development of the asymmetric synthesis of P-stereogenic organophosphoryl compounds employing menthol, sparteine, ephedrine, and carbohydrates as chiral auxiliary is summarized.
2018, 38(2): 350-362
doi: 10.6023/cjoc201706018
Abstract:
Recently, the fluorescent bio-probe based on water-soluble boron-dipyrromethene (BODIPY) obtains enormous progress on structural optimization and functional modification, and becomes novel high-performance biological imaging materials owing to the development of hydrophilic modification. Focusing on the methods for improving the hydrophilicity of BODIPY, the water-soluble BODIPYs have been classified as ionic probe, electrically-neutral probe and amphiphilic probe. The research progress on the application of water-soluble BODIPY dyes in field of biology and medicine since 2006 has been summarized in this review, such as detection of necessary and pathogenicbiological chemical components, early detection and intervention of cancer, labelling drug delivery, marking specific organelles, real-time monitoring of biochemical and property changes with cells, andphotodynamic therapy. The merits of methods for improving the hydrophilicity and main issues of current studies have been summed up. The hypothesis for future directions has also been put forward.
Recently, the fluorescent bio-probe based on water-soluble boron-dipyrromethene (BODIPY) obtains enormous progress on structural optimization and functional modification, and becomes novel high-performance biological imaging materials owing to the development of hydrophilic modification. Focusing on the methods for improving the hydrophilicity of BODIPY, the water-soluble BODIPYs have been classified as ionic probe, electrically-neutral probe and amphiphilic probe. The research progress on the application of water-soluble BODIPY dyes in field of biology and medicine since 2006 has been summarized in this review, such as detection of necessary and pathogenicbiological chemical components, early detection and intervention of cancer, labelling drug delivery, marking specific organelles, real-time monitoring of biochemical and property changes with cells, andphotodynamic therapy. The merits of methods for improving the hydrophilicity and main issues of current studies have been summed up. The hypothesis for future directions has also been put forward.
2018, 38(2): 363-377
doi: 10.6023/cjoc201707031
Abstract:
The indoles motifs are widely found in the nature. One of the efficient strategy to access the indole derivatives is through the direct C-H functionalization of indole framework itself under transition-metal catalysis. Herein, the research advances on the transition-metal-catalyzed C-H arylation of indoles are reviewed.
The indoles motifs are widely found in the nature. One of the efficient strategy to access the indole derivatives is through the direct C-H functionalization of indole framework itself under transition-metal catalysis. Herein, the research advances on the transition-metal-catalyzed C-H arylation of indoles are reviewed.
2018, 38(2): 378-400
doi: 10.6023/cjoc201708013
Abstract:
Spiroisoxazoline compounds have so extensive biological activity that they are important drug intermediates, and they are also important organic synthetic intermediates. The relevant reports for forty years are reviewed in this paper. On the basis of reaction mechanisms, the synthetic methods of spiroisoxazoline compounds are classified into the following five types:oxidation, intramolecular condensation, nucleophilic addition, 1, 3-dipolar cycloaddition, and other methods. Among them, the most widely used method is 1, 3-dipolar cycloadditio. This method is of simple operation, high yield and good stereoselectivity, but one of its synthons-carbon dipolarophiles is not easy to get, and generally goes through many steps of reaction to prepare. In addition, their biological activities are summarized as six categories:the activity of inhibiting the growth of the larvae, the activity of slowing hardening of the arteries, the activity for the treatment of pain, the activity of lowering blood sugar, the anticancer activity and the antibacterial activity.
Spiroisoxazoline compounds have so extensive biological activity that they are important drug intermediates, and they are also important organic synthetic intermediates. The relevant reports for forty years are reviewed in this paper. On the basis of reaction mechanisms, the synthetic methods of spiroisoxazoline compounds are classified into the following five types:oxidation, intramolecular condensation, nucleophilic addition, 1, 3-dipolar cycloaddition, and other methods. Among them, the most widely used method is 1, 3-dipolar cycloadditio. This method is of simple operation, high yield and good stereoselectivity, but one of its synthons-carbon dipolarophiles is not easy to get, and generally goes through many steps of reaction to prepare. In addition, their biological activities are summarized as six categories:the activity of inhibiting the growth of the larvae, the activity of slowing hardening of the arteries, the activity for the treatment of pain, the activity of lowering blood sugar, the anticancer activity and the antibacterial activity.
2018, 38(2): 401-415
doi: 10.6023/cjoc201708034
Abstract:
As one type of organic synthetic materials and intermediates, 1, 1-dibromo-1-alkenes have been widely researched in C-C, C-N, C-O, C-P, and C-S bond formations. The couple of C-Br bonds in the molecule makes it reactive to afford bromoalkenes, bromoalkynes, terminal alkynes, and to prepare poly-substituted alkenes, fused aromatic rings and internal alkynes through coupling reactions. Various organic reactions with 1, 1-dibromo-1-alkenes as the starting materials are mainly reviewed.
As one type of organic synthetic materials and intermediates, 1, 1-dibromo-1-alkenes have been widely researched in C-C, C-N, C-O, C-P, and C-S bond formations. The couple of C-Br bonds in the molecule makes it reactive to afford bromoalkenes, bromoalkynes, terminal alkynes, and to prepare poly-substituted alkenes, fused aromatic rings and internal alkynes through coupling reactions. Various organic reactions with 1, 1-dibromo-1-alkenes as the starting materials are mainly reviewed.
2018, 38(2): 416-424
doi: 10.6023/cjoc201707007
Abstract:
A multiple synthetic strategy is employed to furnish the synthesis of 6, 12, 18-triaryldibenzo[b, j]quinoline[2, 3-f] [1, 7]phenanthroline. The key intermediate 6, 12, 18-trichlorobenzotriquinoline was prepared by Buchwald-Hartwig reaction of 1, 3, 5-tribromobenzene with methyl anthranilate, followed by hydrolysis and POCl3-promoted ring closure reaction. The palladium-catalyzed Suzuki coupling was carried out with a novel catalyst Pd-132 to form fourteen C3-symmetric 9-aryl acridine derivatives. The reactions can be performed at low catalyst loading (0.1 mol%, ca. 0.03 mol% per site).
A multiple synthetic strategy is employed to furnish the synthesis of 6, 12, 18-triaryldibenzo[b, j]quinoline[2, 3-f] [1, 7]phenanthroline. The key intermediate 6, 12, 18-trichlorobenzotriquinoline was prepared by Buchwald-Hartwig reaction of 1, 3, 5-tribromobenzene with methyl anthranilate, followed by hydrolysis and POCl3-promoted ring closure reaction. The palladium-catalyzed Suzuki coupling was carried out with a novel catalyst Pd-132 to form fourteen C3-symmetric 9-aryl acridine derivatives. The reactions can be performed at low catalyst loading (0.1 mol%, ca. 0.03 mol% per site).
2018, 38(2): 425-431
doi: 10.6023/cjoc201708062
Abstract:
Spiropyran compound is widely used as an important class of photochromic compounds. Three new types of 1, 8-naphthalimide compounds with spiropyran unit were synthesized and the structures were characterized. The photochromic characteristics research shows that their response time of the ring opening process is long even difficult to be detected comparing the classical spiropyran. And the reason of their prolonged ring opening reaction is analyzed theoretically and structurally. The photochromic properties of SP3 are more obvious both in solid medium and organic solvents due to the presence of the strong electro-withdraw substituent. It turned into orange red from yellow in polyethylene glycol (200) and from yellow to grey purple in acetone. The investigation of the UV-Vis absorption spectra also showed its negative solvent effect in different organic solvents. There is no significant difference in the absorption wavelength of the spiropyran unit ring opened after irradiation compared with the standard one. The fluorescence properties of the three compounds were investigated to find that SP1 and SP2 showed obvious fluorescence color changes prior and after the UV irradiation in the silica gel, and no fluorescence color changes were detected in polymethylmethacrylate (PMMA) and organic solvents. Fluorescence changes of compound SP3 in acetone were not detected after the UV irradiation. The compound SP3 emitted green fluorescence and became orange yellow fluorescence after ultrasonic irradiation in polyethylene glycol (200). The changing process was detected by fluorescence spectrum. The fluorescence color change of SP3 is more obvious in the thin layer silica gel before and after irradiation. As time elapses, the green fluorescence converted to red one and turned into red from orange yellow eventually. The fluorescence spectrum of the compounds in PMMA film showed that the compound SP3 played the role of a dual-color fluorescent molecular switch. Because of the amino-group in its molecular structure, this dual-color fluorescent molecular switch is suitable for application in labeling biological system.
Spiropyran compound is widely used as an important class of photochromic compounds. Three new types of 1, 8-naphthalimide compounds with spiropyran unit were synthesized and the structures were characterized. The photochromic characteristics research shows that their response time of the ring opening process is long even difficult to be detected comparing the classical spiropyran. And the reason of their prolonged ring opening reaction is analyzed theoretically and structurally. The photochromic properties of SP3 are more obvious both in solid medium and organic solvents due to the presence of the strong electro-withdraw substituent. It turned into orange red from yellow in polyethylene glycol (200) and from yellow to grey purple in acetone. The investigation of the UV-Vis absorption spectra also showed its negative solvent effect in different organic solvents. There is no significant difference in the absorption wavelength of the spiropyran unit ring opened after irradiation compared with the standard one. The fluorescence properties of the three compounds were investigated to find that SP1 and SP2 showed obvious fluorescence color changes prior and after the UV irradiation in the silica gel, and no fluorescence color changes were detected in polymethylmethacrylate (PMMA) and organic solvents. Fluorescence changes of compound SP3 in acetone were not detected after the UV irradiation. The compound SP3 emitted green fluorescence and became orange yellow fluorescence after ultrasonic irradiation in polyethylene glycol (200). The changing process was detected by fluorescence spectrum. The fluorescence color change of SP3 is more obvious in the thin layer silica gel before and after irradiation. As time elapses, the green fluorescence converted to red one and turned into red from orange yellow eventually. The fluorescence spectrum of the compounds in PMMA film showed that the compound SP3 played the role of a dual-color fluorescent molecular switch. Because of the amino-group in its molecular structure, this dual-color fluorescent molecular switch is suitable for application in labeling biological system.
2018, 38(2): 457-463
doi: 10.6023/cjoc201708018
Abstract:
The Beckmann rearrangement reactions generally require strong acids, and always suffer from harsh conditions and serious environmental pollutions which go against the principle of green chemistry. Base on the green zinc catalyst, highly efficient catalytic reaction of ketoxime by Beckmann rearrangement was developed. The acid-additives-free reactions proceed under mild conditions, and show broad functional-group compatibility. Moreover, through this highly active and available zinc catalyst, the Beckmann rearrangement reaction is further extended to a one-pot protocol using ketone and hydroxylamine hydrochloride as reactive materials. Featuring high atom-economy and broad substrate scopes, this novel method provided an attractive route for the Beckmann rearrangement reactions.
The Beckmann rearrangement reactions generally require strong acids, and always suffer from harsh conditions and serious environmental pollutions which go against the principle of green chemistry. Base on the green zinc catalyst, highly efficient catalytic reaction of ketoxime by Beckmann rearrangement was developed. The acid-additives-free reactions proceed under mild conditions, and show broad functional-group compatibility. Moreover, through this highly active and available zinc catalyst, the Beckmann rearrangement reaction is further extended to a one-pot protocol using ketone and hydroxylamine hydrochloride as reactive materials. Featuring high atom-economy and broad substrate scopes, this novel method provided an attractive route for the Beckmann rearrangement reactions.
2018, 38(2): 464-470
doi: 10.6023/cjoc201709005
Abstract:
Equilin and its derivatives are important active ingredients of conjugated estrogens, extracted from pregnant horse urine. However, they are still challenge synthetic targets due to the presence of an unstable non-conjugated double bond. Equilin (7), 17β-dihydroequilin (8) and 17α-dihydroequilin (9) were efficiently synthesized from commercially available 19-hydroxyandrost-4-ene-3, 17-dione via retro-aldol aromatization with the overall yields of 32%, 37% and 25%, respectively.
Equilin and its derivatives are important active ingredients of conjugated estrogens, extracted from pregnant horse urine. However, they are still challenge synthetic targets due to the presence of an unstable non-conjugated double bond. Equilin (7), 17β-dihydroequilin (8) and 17α-dihydroequilin (9) were efficiently synthesized from commercially available 19-hydroxyandrost-4-ene-3, 17-dione via retro-aldol aromatization with the overall yields of 32%, 37% and 25%, respectively.
2018, 38(2): 471-477
doi: 10.6023/cjoc201704016
Abstract:
Bent-core liquid crystal has attracted much attention because of its unique photoelectric performance. However, the bent-Core liquid crystal has been developed slowly because of its narrow temperature range and high phase transformation temperature. In this paper, a series of novel bent-core liquid crystal compounds were designed and synthesized, which were based on 2, 5-disubstitueted-1, 3, 4-thiadiazole as the central units, difluorooxymethylene (CF2O) as the linking group and straight alkyl as the terminal chain. The chemical structures of the target compounds were confirmed by IR, 1H NMR, 13C NMR, and 19F NMR. Then, their transition temperatures and phase textures were investigated by using differential scanning calorimetric (DSC) and polarizing optical microscopy (POM). The result suggested that all the target compounds exhibited nematic phase and existed wide temperature range of nematic phase, and the widest range of nematic phase was 92.74℃. Compared with the structure oxadiazole bend-core liquid crystal, the melting point is slightly higher and liquid crystal phase temperature range is wider, which could provide material and theoretical basis for the further design and synthesis of novel wide-temperature nematic phase bent-core liquid crystal.
Bent-core liquid crystal has attracted much attention because of its unique photoelectric performance. However, the bent-Core liquid crystal has been developed slowly because of its narrow temperature range and high phase transformation temperature. In this paper, a series of novel bent-core liquid crystal compounds were designed and synthesized, which were based on 2, 5-disubstitueted-1, 3, 4-thiadiazole as the central units, difluorooxymethylene (CF2O) as the linking group and straight alkyl as the terminal chain. The chemical structures of the target compounds were confirmed by IR, 1H NMR, 13C NMR, and 19F NMR. Then, their transition temperatures and phase textures were investigated by using differential scanning calorimetric (DSC) and polarizing optical microscopy (POM). The result suggested that all the target compounds exhibited nematic phase and existed wide temperature range of nematic phase, and the widest range of nematic phase was 92.74℃. Compared with the structure oxadiazole bend-core liquid crystal, the melting point is slightly higher and liquid crystal phase temperature range is wider, which could provide material and theoretical basis for the further design and synthesis of novel wide-temperature nematic phase bent-core liquid crystal.
2018, 38(2): 478-485
doi: 10.6023/cjoc201705042
Abstract:
Based on the reported phosphodiesterase-4(PDE-4) inhibitor of crisaborole, seven compounds with structural novelty were designed and synthesized according to the pharmacophore-combination strategy. The structures of them were identified by NMR and HRMS. Their inhibitory activities against phosphodiesterase-4A (PDE-4A) have been investigated. The inhibitory activities of inflammatory factor induced by lipopolysaccharide (LPS) or phorbol ester have been measured by mouse model. The results showed that all compounds exhibited high anti-inflammatory activities. In particular, one compound activity was significantly better than that of positive control drug.
Based on the reported phosphodiesterase-4(PDE-4) inhibitor of crisaborole, seven compounds with structural novelty were designed and synthesized according to the pharmacophore-combination strategy. The structures of them were identified by NMR and HRMS. Their inhibitory activities against phosphodiesterase-4A (PDE-4A) have been investigated. The inhibitory activities of inflammatory factor induced by lipopolysaccharide (LPS) or phorbol ester have been measured by mouse model. The results showed that all compounds exhibited high anti-inflammatory activities. In particular, one compound activity was significantly better than that of positive control drug.
2018, 38(2): 432-442
doi: 10.6023/cjoc201709016
Abstract:
A microporous organic polymer bearing 2, 2'-bipyridine functional group (MOP-bipy), has been synthesized. After treating with Pd (CH3CN)2Cl2, a composite material Pd/MOP-bipy was obtained. The materials have been characterized by 13C CP/MAS NMR, FT-IR, PXRD, SEM, TEM, nitrogen adsorption and thermogravimetric (TG) techniques. The content and valence of palladium in Pd/MOP-bipy have been determined by ICP and XPS. The composite material Pd/MOP-bipy exhibits excellent catalytic activity for Suzuki-Miyaura reaction in water and Sonogashira coupling reaction in methanol/water. The catalyst can be recycled at least five times without significant loss of the activity.
A microporous organic polymer bearing 2, 2'-bipyridine functional group (MOP-bipy), has been synthesized. After treating with Pd (CH3CN)2Cl2, a composite material Pd/MOP-bipy was obtained. The materials have been characterized by 13C CP/MAS NMR, FT-IR, PXRD, SEM, TEM, nitrogen adsorption and thermogravimetric (TG) techniques. The content and valence of palladium in Pd/MOP-bipy have been determined by ICP and XPS. The composite material Pd/MOP-bipy exhibits excellent catalytic activity for Suzuki-Miyaura reaction in water and Sonogashira coupling reaction in methanol/water. The catalyst can be recycled at least five times without significant loss of the activity.
2018, 38(2): 443-450
doi: 10.6023/cjoc201707018
Abstract:
A metal-free, operationally simple synthetic protocol for the buildup of unsymmetric 1, 1'-biaryl-2, 2'-diamine compounds was reported. This reaction was performed by the treatment of 2-naphthols with aryl hydrazines under no transition metal catalyst and no ligand conditions, which has the advantages of simple operation and one-step synthesis.
A metal-free, operationally simple synthetic protocol for the buildup of unsymmetric 1, 1'-biaryl-2, 2'-diamine compounds was reported. This reaction was performed by the treatment of 2-naphthols with aryl hydrazines under no transition metal catalyst and no ligand conditions, which has the advantages of simple operation and one-step synthesis.
2018, 38(2): 451-456
doi: 10.6023/cjoc201707025
Abstract:
In order to find more efficient and economical antitumor drugs, a series of 1-phenyl-4-substituted phthalazine derivatives were synthesized and evaluated for antiproliferative activity in vivo. The structures of the synthesized compounds were confirmed by 1H NMR, 13C NMR and HRMS. The antitumor activity of the target compounds was performed against four cancer cell lines by 3-(4, 5-dimethyl-2-thiazolyl)-2, 5-diphenyl-2-H-tetrazolium bromide (MTT). The results showed that some compounds had a good antitumor activity, especially, N-(4-methoxyphenyl)-2-((4-phenylphthalazin-1-yl) thio) acetamide (5f) and N-(3-chloro-4-fluorophenyl)-2-(4-(4-phenylphthalazin-1-yl) piperazin-1-yl) acetamide (8c), exhibited better antitumor activities with IC50 values of 8.13 and 9.31 μmol•L-1 against the human esophageal cancer cells, which were superior to 5-fuorouracil.
In order to find more efficient and economical antitumor drugs, a series of 1-phenyl-4-substituted phthalazine derivatives were synthesized and evaluated for antiproliferative activity in vivo. The structures of the synthesized compounds were confirmed by 1H NMR, 13C NMR and HRMS. The antitumor activity of the target compounds was performed against four cancer cell lines by 3-(4, 5-dimethyl-2-thiazolyl)-2, 5-diphenyl-2-H-tetrazolium bromide (MTT). The results showed that some compounds had a good antitumor activity, especially, N-(4-methoxyphenyl)-2-((4-phenylphthalazin-1-yl) thio) acetamide (5f) and N-(3-chloro-4-fluorophenyl)-2-(4-(4-phenylphthalazin-1-yl) piperazin-1-yl) acetamide (8c), exhibited better antitumor activities with IC50 values of 8.13 and 9.31 μmol•L-1 against the human esophageal cancer cells, which were superior to 5-fuorouracil.
2018, 38(2): 486-491
doi: 10.6023/cjoc201707017
Abstract:
Several facile metal molybdates were prepared by hydrothermal method and characterized by X-ray diffraction (XRD). Meanwhile, the bimetallic combination effect of these metal molybdates as bimetallic catalysts applied to the selective oxidation of various olefins and alcohols was investigated. It was found that there was the existence of bimetallic combination effect and the combination of Co and Mo had benignant effect compared with the individual metal catalysts and other metal molybdates in the reaction of oxidizing olefins to aldehydes. This bimetallic catalyst also showed very prominent performance (selectivity is 100%) in the oxidation of the alcohols to corresponding carbonyl compounds. The combination of double metal provides a method for the catalytic oxidation of olefins and alcohols.
Several facile metal molybdates were prepared by hydrothermal method and characterized by X-ray diffraction (XRD). Meanwhile, the bimetallic combination effect of these metal molybdates as bimetallic catalysts applied to the selective oxidation of various olefins and alcohols was investigated. It was found that there was the existence of bimetallic combination effect and the combination of Co and Mo had benignant effect compared with the individual metal catalysts and other metal molybdates in the reaction of oxidizing olefins to aldehydes. This bimetallic catalyst also showed very prominent performance (selectivity is 100%) in the oxidation of the alcohols to corresponding carbonyl compounds. The combination of double metal provides a method for the catalytic oxidation of olefins and alcohols.
2018, 38(2): 492-497
doi: 10.6023/cjoc201707029
Abstract:
A facile and convenient ultrasonic-assisted method for the synthesis of 2-sulfonyl nitrogen heterocyclics has been developed. Using bromo-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBroP) as catalyst, the reactions were carried out under ultrasound irradiation condition at room temperature for 1.0 h, and the 2-sulfonyl nitrogen heterocyclics were obtained in good yields with nitrogen heterocyclic N-oxides and sulfinic acid as raw materials. The reaction has the advantages of good substrate suitability, short reaction times and high yields, which provides a efficient approach for the synthesis of 2-sulfonyl nitrogen heterocyclics and their derivatives.
A facile and convenient ultrasonic-assisted method for the synthesis of 2-sulfonyl nitrogen heterocyclics has been developed. Using bromo-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBroP) as catalyst, the reactions were carried out under ultrasound irradiation condition at room temperature for 1.0 h, and the 2-sulfonyl nitrogen heterocyclics were obtained in good yields with nitrogen heterocyclic N-oxides and sulfinic acid as raw materials. The reaction has the advantages of good substrate suitability, short reaction times and high yields, which provides a efficient approach for the synthesis of 2-sulfonyl nitrogen heterocyclics and their derivatives.
2018, 38(2): 498-503
doi: 10.6023/cjoc201709019
Abstract:
A novel approach for the synthesis of nicotinate derivatives has been developed by using Lewis acidic ionic liquid[Bmim]ZnBr3, which acts as dual solvent-catalyst in promoting the tandem reaction of enaminoester and allenic ketones. In the reaction process, no catalysts or other organic solvents are used, and[Bmim]ZnBr3 can be readily reused for three times without noticeable decrease in the catalytic activity after simple treatment. Furthermore, our method offers several advantages such as short reaction times, simple work-up procedure, environment-friendly solvent and good yields. The current methodology could also be conveniently applied to the synthesis of natural products and complex therapeutic agents occurring niacin frameworks.
A novel approach for the synthesis of nicotinate derivatives has been developed by using Lewis acidic ionic liquid[Bmim]ZnBr3, which acts as dual solvent-catalyst in promoting the tandem reaction of enaminoester and allenic ketones. In the reaction process, no catalysts or other organic solvents are used, and[Bmim]ZnBr3 can be readily reused for three times without noticeable decrease in the catalytic activity after simple treatment. Furthermore, our method offers several advantages such as short reaction times, simple work-up procedure, environment-friendly solvent and good yields. The current methodology could also be conveniently applied to the synthesis of natural products and complex therapeutic agents occurring niacin frameworks.
2018, 38(2): 504-508
doi: 10.6023/cjoc201708054
Abstract:
A high efficient method for the synthesis of 2, 3-dicarboxylic ester quinoline derivatives which employed o-amino diphenyl methylone derivatives and acetylenedicarboxylic esters as the reaction substrates was developed. This method possessed the character of catalyst-free and mild reaction conditions. Proposed mechanism was also studied according to the reaction result.
A high efficient method for the synthesis of 2, 3-dicarboxylic ester quinoline derivatives which employed o-amino diphenyl methylone derivatives and acetylenedicarboxylic esters as the reaction substrates was developed. This method possessed the character of catalyst-free and mild reaction conditions. Proposed mechanism was also studied according to the reaction result.
2018, 38(2): 509-518
doi: 10.6023/cjoc201708004
Abstract:
Based on the structure of lead compound of 7-hydroxy-4-methyl-coumarin, a series of novel fluorinated amide coumarin derivatives were designed and synthesized through the principle of bioactive substructure combination. Their structures were characterized by 1H NMR, 13C NMR and HRMS. N-(n-Butyryl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluo-romethyl-coumarin (f1) and N-(p-methylbenzoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f9) were further confirmed by X-ray single crystal diffraction. The results of herbicidal activity indicated that compounds f1, N-phenylacetyl-N-(m-fluorobenzyl)-6-amino-7-methyloxy-4-trifluoromethyl-coumarin (f13), N-methylacryloyl-N-(m-fluoro-benzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f5), N-(cyclopropylcarbonyl)-N-(m-fluorobenzyl)-6-amino-7-meth-oxy-4-trifluoromethyl-coumarin (f7), N-(6-chloronicotinoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-cou-marin (f20), exhibited marked inhibition against the stem growth of Digitaria sanguinalis. And f9, f7, N-(naphthalene-2-carbonyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f17) showed excellent inhibition on the stem of Chenopodium glaucum. The herbicidal activities of the compounds mentioned above were more active than the commercial herbicide acetochlor. The results of crop safety evaluation showed that compounds f1、f9 and f13 were safe to Brassica pekinensis and Brassica napus but sensitive to Triticum aestivum and Sorghum bicolor. Furthermore, N-(m-bromobenzoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f12), f7 and f9 were medium active against the mycelium of phytopathogenic fungi Botrytis cinerea. And N-(hydrocinnamoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f14) was medium active to Valsa mali.
Based on the structure of lead compound of 7-hydroxy-4-methyl-coumarin, a series of novel fluorinated amide coumarin derivatives were designed and synthesized through the principle of bioactive substructure combination. Their structures were characterized by 1H NMR, 13C NMR and HRMS. N-(n-Butyryl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluo-romethyl-coumarin (f1) and N-(p-methylbenzoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f9) were further confirmed by X-ray single crystal diffraction. The results of herbicidal activity indicated that compounds f1, N-phenylacetyl-N-(m-fluorobenzyl)-6-amino-7-methyloxy-4-trifluoromethyl-coumarin (f13), N-methylacryloyl-N-(m-fluoro-benzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f5), N-(cyclopropylcarbonyl)-N-(m-fluorobenzyl)-6-amino-7-meth-oxy-4-trifluoromethyl-coumarin (f7), N-(6-chloronicotinoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-cou-marin (f20), exhibited marked inhibition against the stem growth of Digitaria sanguinalis. And f9, f7, N-(naphthalene-2-carbonyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f17) showed excellent inhibition on the stem of Chenopodium glaucum. The herbicidal activities of the compounds mentioned above were more active than the commercial herbicide acetochlor. The results of crop safety evaluation showed that compounds f1、f9 and f13 were safe to Brassica pekinensis and Brassica napus but sensitive to Triticum aestivum and Sorghum bicolor. Furthermore, N-(m-bromobenzoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f12), f7 and f9 were medium active against the mycelium of phytopathogenic fungi Botrytis cinerea. And N-(hydrocinnamoyl)-N-(m-fluorobenzyl)-6-amino-7-methoxy-4-trifluoromethyl-coumarin (f14) was medium active to Valsa mali.
Synthesis of Cyclic Phenyl Polyynes: Ph2P-Deprotection/Intramolecular Eglington Coupling Cyclization
2018, 38(2): 519-525
doi: 10.6023/cjoc201708011
Abstract:
Ph2P (O)-deprotection/intramolecular Eglington coupling cyclization, proceeding in one-pot manner, can be applied to synthesize cyclic phenyl polyynes. Compared to Micheal M. Haley's stepwise desilylation/Eglington coupling reaction, the polar Ph2P (O) protecting group enabled facile seperation of product from remaining starting compound for their different polarity, and it also led to easy separation of target compound because the amont of by-products which showed similar Rf to target compound decreased. Furthermore, our one-pot reaction, avoiding the workup after Ph2P (O)-deprotection and reducing losses of materials, increased the yield of cyclic aromatic polyynes. This method showed some other outstanding features including easy synthesis of intermediates and mild reaction conditions.
Ph2P (O)-deprotection/intramolecular Eglington coupling cyclization, proceeding in one-pot manner, can be applied to synthesize cyclic phenyl polyynes. Compared to Micheal M. Haley's stepwise desilylation/Eglington coupling reaction, the polar Ph2P (O) protecting group enabled facile seperation of product from remaining starting compound for their different polarity, and it also led to easy separation of target compound because the amont of by-products which showed similar Rf to target compound decreased. Furthermore, our one-pot reaction, avoiding the workup after Ph2P (O)-deprotection and reducing losses of materials, increased the yield of cyclic aromatic polyynes. This method showed some other outstanding features including easy synthesis of intermediates and mild reaction conditions.
2018, 38(2): 526-530
doi: 10.6023/cjoc201708017
Abstract:
Three new compounds were isolated from the leaves and stems of Passiflora edulis Sims by means of various chromatographic techniques. Their structures were identified as cyclopassifloside XVI (1), lanopassiflosideI (2), and luteolin-8-C-β-boivinopyranosyl-4'-O-β-D-glucopyranoside (3) on the basis of extensive spectroscopic analyses, including HR-MS, 1D-and 2D-NMR.
Three new compounds were isolated from the leaves and stems of Passiflora edulis Sims by means of various chromatographic techniques. Their structures were identified as cyclopassifloside XVI (1), lanopassiflosideI (2), and luteolin-8-C-β-boivinopyranosyl-4'-O-β-D-glucopyranoside (3) on the basis of extensive spectroscopic analyses, including HR-MS, 1D-and 2D-NMR.
2018, 38(2): 531-538
doi: 10.6023/cjoc201708051
Abstract:
A total of twenty novel 1, 2, 4-triazole-acylhydrazone derivatives containing the quinazolin-4-one moiety were synthesized via the condensation reaction of triazole hydrazide with various aromatic aldehydes, and fully characterized by 1H NMR, 13C NMR and HRMS spectra. Antimicrobial assaysin vitro indicated that most of the target compounds exhibited good antibacterial activities against the pathogenic phytobacteriaXanthomonas oryzae pv. oryzae(Xoo) andXanthomonas axonopodis pv.citri(Xac). Notably,N'-(2-methoxybenzylidene)-1-(2-(4-oxoquinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhy-drazone)(7q) displayed the inhibition rate of 100% against the above two bacteria at 100 μg/mL. Additionally, 1-(2-(4-oxo-quinazolin-3(4H)-yl) ethyl)-N'-(4-(trifluoromethyl) benzylidene)-1H-1, 2, 4-triazole-3-acylhydrazone (7i),N'-(2-bromobenzyli-dene)-1-(2-(4-oxoquinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhydrazone (7j),N'-(4-bromobenzylidene)-1-(2-(4-oxo-quinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhydrazone (7l), andN'-(4-methoxybenzylidene)-1-(2-(4-oxoquinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhydrazone (7o) were found to possess the inhibition rate of >55% against the fungusBotrytis cinerea Pers. at 50 μg/mL.
A total of twenty novel 1, 2, 4-triazole-acylhydrazone derivatives containing the quinazolin-4-one moiety were synthesized via the condensation reaction of triazole hydrazide with various aromatic aldehydes, and fully characterized by 1H NMR, 13C NMR and HRMS spectra. Antimicrobial assaysin vitro indicated that most of the target compounds exhibited good antibacterial activities against the pathogenic phytobacteriaXanthomonas oryzae pv. oryzae(Xoo) andXanthomonas axonopodis pv.citri(Xac). Notably,N'-(2-methoxybenzylidene)-1-(2-(4-oxoquinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhy-drazone)(7q) displayed the inhibition rate of 100% against the above two bacteria at 100 μg/mL. Additionally, 1-(2-(4-oxo-quinazolin-3(4H)-yl) ethyl)-N'-(4-(trifluoromethyl) benzylidene)-1H-1, 2, 4-triazole-3-acylhydrazone (7i),N'-(2-bromobenzyli-dene)-1-(2-(4-oxoquinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhydrazone (7j),N'-(4-bromobenzylidene)-1-(2-(4-oxo-quinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhydrazone (7l), andN'-(4-methoxybenzylidene)-1-(2-(4-oxoquinazolin-3(4H)-yl) ethyl)-1H-1, 2, 4-triazole-3-acylhydrazone (7o) were found to possess the inhibition rate of >55% against the fungusBotrytis cinerea Pers. at 50 μg/mL.
