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2015 Volume 36 Issue 1
2015, 36(1): 1-42
doi: 10.6023/cjoc201509006
Abstract:
Noncovalent bond forces-based supramolecular chemistry grows quite rapidly and has been revealed to have extensively potential applications and huge development values in chemistry, physics, materials and information science, medicine and so on. Azole compounds such as imidazoles, thiazoles, oxazoles, pyrazoles, triazoles, tetrazoles and carbazoles containing special nitrogen aromatic heterocyclic structure, can exert non-covalent forces to form supramolecular complexes with inorganic and/or organic compounds and exhibit broad biological activity. In recent years, heterocyclic azole-based supramolecular complexes have been expeditiously expanding in the field of medicine, and have become a quite hot topic. Combined with our work and referring to other literature in recent 5 years, this paper systematically reviews the researches and applications of azole-based supermolecules as medicinal agents including anticancer, antibacterial, antifungal, antiparasitic, antidiabetic, antihypertensive, anti-inflammatory drugs and other ones. Finally, the perspectives of the future development of azole-based supermolecules as medicinal agents are also presented.
Noncovalent bond forces-based supramolecular chemistry grows quite rapidly and has been revealed to have extensively potential applications and huge development values in chemistry, physics, materials and information science, medicine and so on. Azole compounds such as imidazoles, thiazoles, oxazoles, pyrazoles, triazoles, tetrazoles and carbazoles containing special nitrogen aromatic heterocyclic structure, can exert non-covalent forces to form supramolecular complexes with inorganic and/or organic compounds and exhibit broad biological activity. In recent years, heterocyclic azole-based supramolecular complexes have been expeditiously expanding in the field of medicine, and have become a quite hot topic. Combined with our work and referring to other literature in recent 5 years, this paper systematically reviews the researches and applications of azole-based supermolecules as medicinal agents including anticancer, antibacterial, antifungal, antiparasitic, antidiabetic, antihypertensive, anti-inflammatory drugs and other ones. Finally, the perspectives of the future development of azole-based supermolecules as medicinal agents are also presented.
2015, 36(1): 43-59
doi: 10.6023/cjoc201508012
Abstract:
The benzo-five-membered heterocycles existed extensively in many important natural products and also showed excellent bioactivites. Therefore, organic chemists around the world made efforts to develop the highly efficient methods of constructing these heterocycles. Recently, the syntheses of them via transition metal-catalyzed tandem reaction, especially palladium-catalyzed reaction, have been reported widely. This review emphasizes on the palladium-catalyzed tandem reaction of the formation of benzo-five-membered heterocycles and their derivatives reported since 2000.
The benzo-five-membered heterocycles existed extensively in many important natural products and also showed excellent bioactivites. Therefore, organic chemists around the world made efforts to develop the highly efficient methods of constructing these heterocycles. Recently, the syntheses of them via transition metal-catalyzed tandem reaction, especially palladium-catalyzed reaction, have been reported widely. This review emphasizes on the palladium-catalyzed tandem reaction of the formation of benzo-five-membered heterocycles and their derivatives reported since 2000.
2015, 36(1): 60-71
doi: 10.6023/cjoc201507037
Abstract:
Hydrosilylation is an important reaction widely used in the silicone industries. Especially, the hydrosilylation of carbonyl compounds is of great value in synthetic organic chemistry. A variety of transition-metal complexes, such as iron, palladium, rhodium, ruthenium, platinum, etc., are now known to show catalytic activity in the hydrosilylation of ketones. Since organohydrosilanes may involve one, two, or three Si—H bonds in tertiary, secondary or primary silanes, respectively. The various types of compounds were produced in their reactions with the unsaturated substrates catalyzed by transition-metal complexes. In this paper, several reaction mechanisms of carbonyl compounds hydrosilylation catalyzed by group VIII transition metal complexes under different reaction conditions are mainly introduced. In particular, the new developments on mechanistic pathways for Rh, Ru, Fe and Ir catalytic systems from the type of reaction mechanism and the influence of reaction conditions are highlighted. In addition, some key intermediates and transition states, and their energetics are presented. Not only a summary of previous work is given, but also some ideas and inspirations are provided for future research.
Hydrosilylation is an important reaction widely used in the silicone industries. Especially, the hydrosilylation of carbonyl compounds is of great value in synthetic organic chemistry. A variety of transition-metal complexes, such as iron, palladium, rhodium, ruthenium, platinum, etc., are now known to show catalytic activity in the hydrosilylation of ketones. Since organohydrosilanes may involve one, two, or three Si—H bonds in tertiary, secondary or primary silanes, respectively. The various types of compounds were produced in their reactions with the unsaturated substrates catalyzed by transition-metal complexes. In this paper, several reaction mechanisms of carbonyl compounds hydrosilylation catalyzed by group VIII transition metal complexes under different reaction conditions are mainly introduced. In particular, the new developments on mechanistic pathways for Rh, Ru, Fe and Ir catalytic systems from the type of reaction mechanism and the influence of reaction conditions are highlighted. In addition, some key intermediates and transition states, and their energetics are presented. Not only a summary of previous work is given, but also some ideas and inspirations are provided for future research.
2015, 36(1): 72-82
doi: 10.6023/cjoc201507015
Abstract:
The valence of the alkaline-earth metals (group 2 metals) usually is 0 and +2. In 2007, the first room temperature stable magnesium(I) complexes were synthesized. Subsequently a series of different organic ligands stablized Mg(I) complexes have been prepared. They can be used as hydrocarbon soluble, stoichiometric, selective, and safe reducing agents in organic and inorganic reactions to replace some traditional reductants. In this review the synthesis of room temperature stable magnesium(I) complexes and their applications in organic and inorganic chemistry are briefly introduced.
The valence of the alkaline-earth metals (group 2 metals) usually is 0 and +2. In 2007, the first room temperature stable magnesium(I) complexes were synthesized. Subsequently a series of different organic ligands stablized Mg(I) complexes have been prepared. They can be used as hydrocarbon soluble, stoichiometric, selective, and safe reducing agents in organic and inorganic reactions to replace some traditional reductants. In this review the synthesis of room temperature stable magnesium(I) complexes and their applications in organic and inorganic chemistry are briefly introduced.
2015, 36(1): 83-104
doi: 10.6023/cjoc201507008
Abstract:
Compared with conventional heating, microwave heating is one of the most useful tools in organic synthesis because of its obviously advantages of fast heating, thermal efficiency, saving energy, clean, and easy operation. Palladium catalyzed Suzuki-Miyaura cross-coupling reaction could tolerate a broad range of functional groups with high stereoselectivity to provide a mild method in preparation of kinds of substituted biaryls. In this paper, the recent research results about the microwave technique applied in Suzuki-Miyaura cross-coupling reaction are reviewed, involving various reaction systems. The applications of the methodology on the synthesis of natural products and bioactive molecules have also been introduced.
Compared with conventional heating, microwave heating is one of the most useful tools in organic synthesis because of its obviously advantages of fast heating, thermal efficiency, saving energy, clean, and easy operation. Palladium catalyzed Suzuki-Miyaura cross-coupling reaction could tolerate a broad range of functional groups with high stereoselectivity to provide a mild method in preparation of kinds of substituted biaryls. In this paper, the recent research results about the microwave technique applied in Suzuki-Miyaura cross-coupling reaction are reviewed, involving various reaction systems. The applications of the methodology on the synthesis of natural products and bioactive molecules have also been introduced.
2015, 36(1): 105-112
doi: 10.6023/cjoc201511013
Abstract:
The first study of oxidative synthesis of simple tert-butyl peresters and amides enabled by N-heterocyclic carbene-catalysis using N-fluorobenzenesulfonimide (NFSI) as oxidant is described. The reaction proceeds with green, high yield, board substrate scope and room temperature.
The first study of oxidative synthesis of simple tert-butyl peresters and amides enabled by N-heterocyclic carbene-catalysis using N-fluorobenzenesulfonimide (NFSI) as oxidant is described. The reaction proceeds with green, high yield, board substrate scope and room temperature.
2015, 36(1): 113-120
doi: 10.6023/cjoc201507017
Abstract:
A convenient procedure for the synthesis of 3-styryl-1, 5-dicarbonyl compounds has been developed under solvent-free grinding conditions. α, β-Unsaturated aldehydes react with aromatic ketones to give the corresponding dienone products, then followed by a Michael addition producing 3-styryl-1, 5-dicarbonyl compounds in the presence of NaOH at room temperature. The advantages of this procedure are solvent-free, catalyst-free, mild reaction conditions, simple procedure, and short reaction time.
A convenient procedure for the synthesis of 3-styryl-1, 5-dicarbonyl compounds has been developed under solvent-free grinding conditions. α, β-Unsaturated aldehydes react with aromatic ketones to give the corresponding dienone products, then followed by a Michael addition producing 3-styryl-1, 5-dicarbonyl compounds in the presence of NaOH at room temperature. The advantages of this procedure are solvent-free, catalyst-free, mild reaction conditions, simple procedure, and short reaction time.
2015, 36(1): 130-136
doi: 10.6023/cjoc201507013
Abstract:
A new magnetic nanoparticle supported palladium catalyst was successfully prepared by attaching palladium acetates to imino-pyridine ligand functionalized silica-coated nano-Fe3O4. The as-prepared catalyst was characterized by element analysis, FTIR, TEM, XPS and ICP-AES. It was found to be an efficient catalyst for Suzuki reactions in aqueous medium. And the reactions of various aryl bromides with arylboronic acids could be carried out under air and low Pd loading conditions with 83%～98% yields. Moreover, the catalyst could be easily recovered by magnetic separation and reused five times without a significant loss of catalytic activity.
A new magnetic nanoparticle supported palladium catalyst was successfully prepared by attaching palladium acetates to imino-pyridine ligand functionalized silica-coated nano-Fe3O4. The as-prepared catalyst was characterized by element analysis, FTIR, TEM, XPS and ICP-AES. It was found to be an efficient catalyst for Suzuki reactions in aqueous medium. And the reactions of various aryl bromides with arylboronic acids could be carried out under air and low Pd loading conditions with 83%～98% yields. Moreover, the catalyst could be easily recovered by magnetic separation and reused five times without a significant loss of catalytic activity.
2015, 36(1): 137-142
doi: 10.6023/cjoc201507020
Abstract:
A simple and efficient method for the conversion of alcohols to the corresponding alkyl chlorides by using dimethylacetamide (DMAc) as a promoter was developed. It provides a new and practical protocol for the synthesis of alkyl chlorides.
A simple and efficient method for the conversion of alcohols to the corresponding alkyl chlorides by using dimethylacetamide (DMAc) as a promoter was developed. It provides a new and practical protocol for the synthesis of alkyl chlorides.
2015, 36(1): 143-150
doi: 10.6023/cjoc201508007
Abstract:
A rapid and efficient ultrasound-promoted one-pot synthesis of 2'-amino-2-oxo-5'H-spiro[indoline-3, 4'-thiochromeno[4, 3-b]pyran]-3'-carbonitrile compounds by one-pot three-component reaction had been developed. Structures of all products were characterized by 1H NMR, 13C NMR and HRMS. The effect of ultrasound on yield and reaction time had been studied to understand the role of ultrasound in the reaction. The antifungal activity was determined by micro dilution method. Compound 4f exhibited inhibitory activity to Cryptococcus neoformans, Epidermophyton floccosum and Mucor racemosus better than the positive control drug fluconazole.
A rapid and efficient ultrasound-promoted one-pot synthesis of 2'-amino-2-oxo-5'H-spiro[indoline-3, 4'-thiochromeno[4, 3-b]pyran]-3'-carbonitrile compounds by one-pot three-component reaction had been developed. Structures of all products were characterized by 1H NMR, 13C NMR and HRMS. The effect of ultrasound on yield and reaction time had been studied to understand the role of ultrasound in the reaction. The antifungal activity was determined by micro dilution method. Compound 4f exhibited inhibitory activity to Cryptococcus neoformans, Epidermophyton floccosum and Mucor racemosus better than the positive control drug fluconazole.
2015, 36(1): 151-157
doi: 10.6023/cjoc201506022
Abstract:
A novel fluorescence probe based on naphthalimide-rhodamine N, N'-rhodamine acyl ethylamino-4-pyridine vinyl-1, 8-naphathlimide (PNRh) was synthesized and characterized by 1H NMR, 13C NMR and HRMS techniques. Fluorescence spectra of PNRh in solid, ethanol/water mixed solution were measured. The results demonstrated that PNRh performed luminous yellow fluorescence in the solid state and the maximum emission wavelength was 592 nm. With the increasing of water content, the fluorescence intensity was enhanced in the ethanol/water mixed solution. When the water content reached 100%, the fluorescence intensity got the highest, and the color of the solution turned from slight blue fluorescence to kermesinus fluorescence. In addition, metal ion probe behavior of PNRh was detected. In a word, PNRh, possessed the characteristic of aggregation-induced emission enhancement (AIEE), was a dual-channel fluorescence sensor for detection Hg2+ and Cr3+ ions.
A novel fluorescence probe based on naphthalimide-rhodamine N, N'-rhodamine acyl ethylamino-4-pyridine vinyl-1, 8-naphathlimide (PNRh) was synthesized and characterized by 1H NMR, 13C NMR and HRMS techniques. Fluorescence spectra of PNRh in solid, ethanol/water mixed solution were measured. The results demonstrated that PNRh performed luminous yellow fluorescence in the solid state and the maximum emission wavelength was 592 nm. With the increasing of water content, the fluorescence intensity was enhanced in the ethanol/water mixed solution. When the water content reached 100%, the fluorescence intensity got the highest, and the color of the solution turned from slight blue fluorescence to kermesinus fluorescence. In addition, metal ion probe behavior of PNRh was detected. In a word, PNRh, possessed the characteristic of aggregation-induced emission enhancement (AIEE), was a dual-channel fluorescence sensor for detection Hg2+ and Cr3+ ions.
2015, 36(1): 158-164
doi: 10.6023/cjoc201507009
Abstract:
In order to find new agrochemical products with high activities, 20 azaindolyl thiazoline compounds were designed and synthesized, and their structures were identified by spectral methods. At the concentration of 50 mg/L, some of the title compounds showed good fungicidal activities. Among those compounds, the EC50 values of 2a and 2d against Phomopsis asparagi and Pyricularia oryzae Cav are 6.55 and 9.66 mg/L, which are superior or comparable to the control pesticides, then they can serve as the lead compounds for new fungicide discovery.
In order to find new agrochemical products with high activities, 20 azaindolyl thiazoline compounds were designed and synthesized, and their structures were identified by spectral methods. At the concentration of 50 mg/L, some of the title compounds showed good fungicidal activities. Among those compounds, the EC50 values of 2a and 2d against Phomopsis asparagi and Pyricularia oryzae Cav are 6.55 and 9.66 mg/L, which are superior or comparable to the control pesticides, then they can serve as the lead compounds for new fungicide discovery.
2015, 36(1): 165-171
doi: 10.6023/cjoc201507010
Abstract:
In this paper, Iron(Ⅲ)-catalyzed aerobic oxidation of imine derivatives and o-phenylenediamine under air condition is studied in detail. With Fe(NO3)3·9H2O as catalyst and air as green and economical oxidant, the reaction could take place in acetonitrile at 80 ℃ and affords benzimidazoles as target compounds in good yields after 10 h, exhibiting good application prospect as well. This process includes three steps: (1) the aerobic oxidative condensation of imine and o-phenylenediamine to form Schiff base, (2) the formation of benzimidazoline via nucleophilic addition of Shift base and amine group on the o-phenylenediamine, and (3) the dehydration of benzimidazoline to form benzimidazole as target compounds.
In this paper, Iron(Ⅲ)-catalyzed aerobic oxidation of imine derivatives and o-phenylenediamine under air condition is studied in detail. With Fe(NO3)3·9H2O as catalyst and air as green and economical oxidant, the reaction could take place in acetonitrile at 80 ℃ and affords benzimidazoles as target compounds in good yields after 10 h, exhibiting good application prospect as well. This process includes three steps: (1) the aerobic oxidative condensation of imine and o-phenylenediamine to form Schiff base, (2) the formation of benzimidazoline via nucleophilic addition of Shift base and amine group on the o-phenylenediamine, and (3) the dehydration of benzimidazoline to form benzimidazole as target compounds.
2015, 36(1): 172-178
doi: 10.6023/cjoc201506012
Abstract:
Polymer solar cells (PSCs) based on fullerene and its derivatives as acceptors are attracting extensive interest due to their advantages of wide materials, low cost and flexibility. The research of the accepting materials is considered to be a key factor to obtain high-efficiency PSCs, especially fullerene derivatives. In this regard, a novel barbell-shaped bifullerene derivative was designed and synthesized, and the structure was identified by 1H NMR, 13C NMR, MS and element analysis. Its absorption, electrochemistry, and geometry were studied systematically by UV, CV and Gaussian. Results showed that the bifullerene derivative can be used as acceptor for PSCs. The solubility of the derivative was effectively changed by increasing the alkyl chain in the molecule. The PSCs were fabricated with the structure of ITO/PEDOT:PSS/P3HT:bifullerene derivative/Ca/Al. After optimization of the ratio of bifullerene derivative and P3HT, the cells with the optimized conditions show that the power conversion efficiency (PCE) was 1.01% with Jsc of 2.73 mA/cm2 and Voc of 0.89 V. It is noteworthy that the open-circuit voltage was up to 0.89 V, which is more than 0.3 V that of PC60BM (Voc＝0.56 V). Our result provides a feasible choice for PSCs with high open-circuit voltage.
Polymer solar cells (PSCs) based on fullerene and its derivatives as acceptors are attracting extensive interest due to their advantages of wide materials, low cost and flexibility. The research of the accepting materials is considered to be a key factor to obtain high-efficiency PSCs, especially fullerene derivatives. In this regard, a novel barbell-shaped bifullerene derivative was designed and synthesized, and the structure was identified by 1H NMR, 13C NMR, MS and element analysis. Its absorption, electrochemistry, and geometry were studied systematically by UV, CV and Gaussian. Results showed that the bifullerene derivative can be used as acceptor for PSCs. The solubility of the derivative was effectively changed by increasing the alkyl chain in the molecule. The PSCs were fabricated with the structure of ITO/PEDOT:PSS/P3HT:bifullerene derivative/Ca/Al. After optimization of the ratio of bifullerene derivative and P3HT, the cells with the optimized conditions show that the power conversion efficiency (PCE) was 1.01% with Jsc of 2.73 mA/cm2 and Voc of 0.89 V. It is noteworthy that the open-circuit voltage was up to 0.89 V, which is more than 0.3 V that of PC60BM (Voc＝0.56 V). Our result provides a feasible choice for PSCs with high open-circuit voltage.
2015, 36(1): 179-184
doi: 10.6023/cjoc201507028
Abstract:
A recyclable palladium catalyst supported on magnetic microporous organic polymer (MOP) of 1, 1'-bi-2-naphthol (Fe3O4@MOPB-Pd) was synthesized by two steps. After being charactered by transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG) and vibrating sample magnetometer (VSM), the palladium catalyst was applied in Suzuki coupling reaction in air atmosphere. With 0.01 g of Fe3O4@MOPB-Pd (0.12 mol% Pd based on bromobenzene) as catalyst, 1.0 mmol of bromobenzene reacted with 1.1 equiv. phenylboronic acid at 60 ℃ for 3 h can give the product with 98% yield. In addition, Fe3O4@MOPB-Pd can be easily separated from reaction system in the presence of magnetic field and the 92% yield was achieved even being used at 7th time for the Suzuki coupling reaction of iodobenzene and phenylboronic acid.
A recyclable palladium catalyst supported on magnetic microporous organic polymer (MOP) of 1, 1'-bi-2-naphthol (Fe3O4@MOPB-Pd) was synthesized by two steps. After being charactered by transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG) and vibrating sample magnetometer (VSM), the palladium catalyst was applied in Suzuki coupling reaction in air atmosphere. With 0.01 g of Fe3O4@MOPB-Pd (0.12 mol% Pd based on bromobenzene) as catalyst, 1.0 mmol of bromobenzene reacted with 1.1 equiv. phenylboronic acid at 60 ℃ for 3 h can give the product with 98% yield. In addition, Fe3O4@MOPB-Pd can be easily separated from reaction system in the presence of magnetic field and the 92% yield was achieved even being used at 7th time for the Suzuki coupling reaction of iodobenzene and phenylboronic acid.
2015, 36(1): 185-190
doi: 10.6023/cjoc201508028
Abstract:
In order to find novel pesticide from pyrazole compounds, a series of new pyrazole derivatives carrying trifluoromethyl benzoyl oxime ester moiety were prepared. The structures of all the title compounds were determined by 1H NMR, 13C NMR, MS and elemental analysis. Preliminary bioassay displayed that most of the target compounds showed certain insecticidal activities at the concentration of 500 μg/mL. When the concentration was reduced to 200 μg/mL, compounds 5b, 5c, 5d, 5i, 5l and 5n werestill active against Aphis craccivora with inhibitory values of 90%, 90%, 80%, 80%, 80% and 80%, respectively.
In order to find novel pesticide from pyrazole compounds, a series of new pyrazole derivatives carrying trifluoromethyl benzoyl oxime ester moiety were prepared. The structures of all the title compounds were determined by 1H NMR, 13C NMR, MS and elemental analysis. Preliminary bioassay displayed that most of the target compounds showed certain insecticidal activities at the concentration of 500 μg/mL. When the concentration was reduced to 200 μg/mL, compounds 5b, 5c, 5d, 5i, 5l and 5n werestill active against Aphis craccivora with inhibitory values of 90%, 90%, 80%, 80%, 80% and 80%, respectively.
2015, 36(1): 191-195
doi: 10.6023/cjoc201509005
Abstract:
(S)-4-Amino-5-mercaptopentanoic acid (glutamate thiol, GluSH) is a derivative of glutamic acid with α-carboxyl group substituted by methanethiol group. Meanwhile, it could be considered as a derivative of cysteine. This amino acid is an important fragment of marine cytotoxic cyclic depsipeptide apratoxin E. Two facile synthetic methods of (S)-4-amino-5-mercaptopentanoic acid are described. For the first strategy, protected D-cysteine derivate was used as starting material. After coupled with Meldrum's acid, the resulting β-keto ester underwent reductive elimination and thermal decarboxylative ring closure to afford 5-substituted pyrrolidinone (γ-lactam). After removal of protecting groups and ring-open, the target compound was obtained in 76.0% overall yield. For the second method, commercial available Boc-Glu(OBzl)-OH was used as starting material. The thiol group was introduced by Mitsunobu reaction after converting the carboxylic acid to its corresponding alcohol. Then the protecting groups of amino, thiol, and carboxylic acid were removed smoothly in one pot to yield (S)-4-amino-5-mercaptopentanoic acid.
(S)-4-Amino-5-mercaptopentanoic acid (glutamate thiol, GluSH) is a derivative of glutamic acid with α-carboxyl group substituted by methanethiol group. Meanwhile, it could be considered as a derivative of cysteine. This amino acid is an important fragment of marine cytotoxic cyclic depsipeptide apratoxin E. Two facile synthetic methods of (S)-4-amino-5-mercaptopentanoic acid are described. For the first strategy, protected D-cysteine derivate was used as starting material. After coupled with Meldrum's acid, the resulting β-keto ester underwent reductive elimination and thermal decarboxylative ring closure to afford 5-substituted pyrrolidinone (γ-lactam). After removal of protecting groups and ring-open, the target compound was obtained in 76.0% overall yield. For the second method, commercial available Boc-Glu(OBzl)-OH was used as starting material. The thiol group was introduced by Mitsunobu reaction after converting the carboxylic acid to its corresponding alcohol. Then the protecting groups of amino, thiol, and carboxylic acid were removed smoothly in one pot to yield (S)-4-amino-5-mercaptopentanoic acid.
2015, 36(1): 196-201
doi: 10.6023/cjoc201507036
Abstract:
Via combination of solid acid SO42-/TiO2 with cinchona alkaloid quinidine (R), the chiral catalyst of SO42-/TiO2/quinidine (R) carrying strong hydrogen-bonding donor has been obtained, which was evaluated on catalytic activity in the asymmetric organocatalysis, as comparing with quinidine (R) and thiourea-quinidine (R) derived from cinchona alkaloids. The result obviously showed that under the same conditions, the catalytic activity of SO42-/TiO2/quinidine (R) is more than that of quinidine (R), but less than that of thiourea-quinidine (R). Simultaneously, chiral β-amino ester derivatives with high optical activities were afforded under the optimum conditions of m-xylene as solvent and stirring for 72 h at －40 ℃. The value of ee was allowed to be the range of 89%～95%.
Via combination of solid acid SO42-/TiO2 with cinchona alkaloid quinidine (R), the chiral catalyst of SO42-/TiO2/quinidine (R) carrying strong hydrogen-bonding donor has been obtained, which was evaluated on catalytic activity in the asymmetric organocatalysis, as comparing with quinidine (R) and thiourea-quinidine (R) derived from cinchona alkaloids. The result obviously showed that under the same conditions, the catalytic activity of SO42-/TiO2/quinidine (R) is more than that of quinidine (R), but less than that of thiourea-quinidine (R). Simultaneously, chiral β-amino ester derivatives with high optical activities were afforded under the optimum conditions of m-xylene as solvent and stirring for 72 h at －40 ℃. The value of ee was allowed to be the range of 89%～95%.
2015, 36(1): 202-206
doi: 10.6023/cjoc201506023
Abstract:
(+)-Oxocamphor is a metabolite of (+)-camphor in vivo, which is used to treat heart failure in clinic. However the present synthetic method has problems of long reaction time, serious pollution and low yield. In this paper we report an efficient synthesis of (+)-oxocamphor was reported via bromination, reduction, esterification, hydrolysis and oxidation using (+)-camphor as starting material. All the intermediates and (+)-oxocamphor were confirmed by 1H NMR, IR and GC-MS. The absolute configuration of 3, 9-dibromocamphor was also ascertained by X-ray diffraction analysis. The overall yield of these 6-step procedures was about 10%.
(+)-Oxocamphor is a metabolite of (+)-camphor in vivo, which is used to treat heart failure in clinic. However the present synthetic method has problems of long reaction time, serious pollution and low yield. In this paper we report an efficient synthesis of (+)-oxocamphor was reported via bromination, reduction, esterification, hydrolysis and oxidation using (+)-camphor as starting material. All the intermediates and (+)-oxocamphor were confirmed by 1H NMR, IR and GC-MS. The absolute configuration of 3, 9-dibromocamphor was also ascertained by X-ray diffraction analysis. The overall yield of these 6-step procedures was about 10%.
2015, 36(1): 207-212
doi: 10.6023/cjoc201506026
Abstract:
Using quinazolin-4-one as the starting compound, nine novel quinazolinone derivatives 6a～6i bearing the 4-phenyl-5-thioxo-1, 2, 4-triazole Mannich base unit were prepared through a five-step synthetic procedure. The structures of target compounds were characterized by 1H NMR, 13C NMR, IR and elemental analysis. 3-((1-Morpholinomethyl-4-phenyl-5-thioxo-4, 5-dihydro-1H-1, 2, 4-triazol-3-yl)methyl)quinazolin-4(3H)-one was further confirmed by X-ray single crystal diffraction method. The preliminary biological test indicated that almost all of the title compounds had excellent antibacterial activities against Xanthomonas oryzae pv. oryzae and Xanthomonas axonopodis pv. citri at the concentration of 200 μg/mL. Moreover, compounds 6a～6i displayed a certain inhibitory effect against six kinds of tested fungi at the concentration of 50 μg/mL.
Using quinazolin-4-one as the starting compound, nine novel quinazolinone derivatives 6a～6i bearing the 4-phenyl-5-thioxo-1, 2, 4-triazole Mannich base unit were prepared through a five-step synthetic procedure. The structures of target compounds were characterized by 1H NMR, 13C NMR, IR and elemental analysis. 3-((1-Morpholinomethyl-4-phenyl-5-thioxo-4, 5-dihydro-1H-1, 2, 4-triazol-3-yl)methyl)quinazolin-4(3H)-one was further confirmed by X-ray single crystal diffraction method. The preliminary biological test indicated that almost all of the title compounds had excellent antibacterial activities against Xanthomonas oryzae pv. oryzae and Xanthomonas axonopodis pv. citri at the concentration of 200 μg/mL. Moreover, compounds 6a～6i displayed a certain inhibitory effect against six kinds of tested fungi at the concentration of 50 μg/mL.
2015, 36(1): 213-217
doi: 10.6023/cjoc201508013
Abstract:
9(10), 16(17), 23(24)-Tris[4-methyl-coumarin-7-yloxy]-2(3)-(1, 5-naphthalene) binuclear zinc phthalocyanine (bi-CPc) based 1, 5-dihydroxynaphthalene, 4-nitro-phthalonitrile, resorcinol, ethyl acetoacetate and zinc acetate on raw material was synthesized. The structures and properties of precursors and bi-CPc were characterized by 1H NMR, FT-IR, UV-Vis, elemental analysis and thermogravimetric analysis. Results showed that strong π-π* transition was demonstrated by UV-Vis absorption spectrum of bi-CPc. At the same time, it existed in a form of monomer in solution of N, N-dimethylformamide (DMF) and possessed excellent thermal stability. Redox behavior of bi-CPc was researched by cyclic voltammetry (CV), and energy level of LUMO and HOMO of bi-CPc matched with energy level of nano-TiO2 after calculating. Through further structural modification, it is expected to use as photosensitive dye with excellent performance for solar cells.
9(10), 16(17), 23(24)-Tris[4-methyl-coumarin-7-yloxy]-2(3)-(1, 5-naphthalene) binuclear zinc phthalocyanine (bi-CPc) based 1, 5-dihydroxynaphthalene, 4-nitro-phthalonitrile, resorcinol, ethyl acetoacetate and zinc acetate on raw material was synthesized. The structures and properties of precursors and bi-CPc were characterized by 1H NMR, FT-IR, UV-Vis, elemental analysis and thermogravimetric analysis. Results showed that strong π-π* transition was demonstrated by UV-Vis absorption spectrum of bi-CPc. At the same time, it existed in a form of monomer in solution of N, N-dimethylformamide (DMF) and possessed excellent thermal stability. Redox behavior of bi-CPc was researched by cyclic voltammetry (CV), and energy level of LUMO and HOMO of bi-CPc matched with energy level of nano-TiO2 after calculating. Through further structural modification, it is expected to use as photosensitive dye with excellent performance for solar cells.
2015, 36(1): 218-221
doi: 10.6023/cjoc201505014
Abstract:
As a newly efficient reagent, Oxyma [ethyl 2-cyano-2-(hydroxyimino)acetate] has a lower rate of racemization and relative higher coupling efficiency as compared with HOBt, HOAt, etc. In this work, as an important polypeptide drug for the treatment of diabetes, liraglutide was firstly chemically synthesized with high efficiency by solid chemical synthesis using Oxyma as coupling reagent. The strategy presented here provides an efficient strategy for the chemical synthesis of liraglutide with enlarged scales.
As a newly efficient reagent, Oxyma [ethyl 2-cyano-2-(hydroxyimino)acetate] has a lower rate of racemization and relative higher coupling efficiency as compared with HOBt, HOAt, etc. In this work, as an important polypeptide drug for the treatment of diabetes, liraglutide was firstly chemically synthesized with high efficiency by solid chemical synthesis using Oxyma as coupling reagent. The strategy presented here provides an efficient strategy for the chemical synthesis of liraglutide with enlarged scales.
2015, 36(1): 222-228
doi: 10.6023/cjoc201507011
Abstract:
A highly efficient strategy for the one-pot synthesis of multi-substituted spirooxindol-pyrano[2, 3-c]pyrazole derivatives was developed. The product formed in good yield from the reaction of acetylenedicarboxylate, hydrazine, isatin, and (E)-1-methylthio-1-methylamino-2-nitroethylene in the presence of Et3N catalyst. This simple and convenient method could also be used to prepare similar types of product.
A highly efficient strategy for the one-pot synthesis of multi-substituted spirooxindol-pyrano[2, 3-c]pyrazole derivatives was developed. The product formed in good yield from the reaction of acetylenedicarboxylate, hydrazine, isatin, and (E)-1-methylthio-1-methylamino-2-nitroethylene in the presence of Et3N catalyst. This simple and convenient method could also be used to prepare similar types of product.
