The three-component reaction of aromatic aldehyde,malononitrile and aliphatic amine in a mixed solvent of methanol and water exhibited very interesting molecular diversity and gave the derivatives of polysubstituted N...The three-component reaction of aromatic aldehyde,malononitrile and aliphatic amine in a mixed solvent of methanol and water exhibited very interesting molecular diversity and gave the derivatives of polysubstituted N-methyldihydropyridines,2-dialkylaminopyridines and 2-methoxypyridines as main products according to the structure of aliphatic amines used.展开更多
A fast, high efficiency and environmentally friendly procedure for the synthesis of 2-aryl benzim-idazole derivatives has been reported. Reaction between 1,2-phenylenediamine derivatives and arylidene malononitrile un...A fast, high efficiency and environmentally friendly procedure for the synthesis of 2-aryl benzim-idazole derivatives has been reported. Reaction between 1,2-phenylenediamine derivatives and arylidene malononitrile under aqueous media and also solvent-free conditions generates 2-aryl benzimidazole derivatives with a high yield.展开更多
Reaction of 4-carboxaldehyde-2-phenyl-2H-1,2,3-triazole 1 with malononitrile in presence of piperidine afforded the triazolomalonitrile 2 which on treatment with hydrazine hydrate, gave 3-amino-5-(2-phenyl-2H-1,2,3-tr...Reaction of 4-carboxaldehyde-2-phenyl-2H-1,2,3-triazole 1 with malononitrile in presence of piperidine afforded the triazolomalonitrile 2 which on treatment with hydrazine hydrate, gave 3-amino-5-(2-phenyl-2H-1,2,3-triazol-4-yl)-4,5-dihydro-1-H-pyrazole-4-carbonitrile 3 and with hydroxylamine, gave 5-amino-3-(2-phenyl-2H-1,2,3-triazol-4-yl)-2,3-dihydroisoxazole-4-carbonitrile 4, and with thiourea, gave?2,4-diamino-6-(2-phenyl-2H-1,2,3-triazol-4-yl)-6H-1,3-thiazine-5-carbonitrile 5. Similarly, reaction of 2 with ethanol amine, gave 2-amino-4-(2-phenyl-2H-1,2,3-triazol-4-yl)nicotinonitrile 6, and with thiosemicarbazide,?gave 4-amino-2-hydrazinyl-6-(2-phnyl-2H-1,2,3-triazol-4-yl)-6H-1,3-thiazine-carbonitrile?7. Similary reaction of 2 with cyclopentanone gave, 2-amino-4-(2-phenyl-2H-1,2,3-triazol-4-yl)-4,5,6,7-tetrahydrocyclopenta [6] pyran-3-carbonitrile 8. In addition, reaction of 1 with hydrazine hydrate, gave the 4 hydrazone which on treatment with another mole of 1 gave 10 and with 3-carboxaldehyde-1-phenyl-4,5-pyrazolinedione 4 phenylhydrazone gave compound 11.展开更多
An efficient and facile approach for tetrachlorosilane as an in situ mediated transformation via a one-pot, synthesis of vicinal bromoazides through the generation of BrN3 from azidochlorosilane and N-bromosuccinimide...An efficient and facile approach for tetrachlorosilane as an in situ mediated transformation via a one-pot, synthesis of vicinal bromoazides through the generation of BrN3 from azidochlorosilane and N-bromosuccinimide in acetonitrile as solvent at ambient temperature is achieved. This catalytic process represents a highly regioselective and high yielding method for the synthesis of 1,2- bromoazides. Thiamine pyrophosphate (TPP) riboswitches regulate essential genes in bacteria by changing conformation upon binding intracellular TPP. Molecular docking studies are conducted to understand the orientation and the interaction of each synthesized molecules with TPP riboswitches, 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academv of Medical Sciences.展开更多
A convenient synthetic protocol for the hexasubstituted benzene derivatives was successfully developed by DABCO promoted domino reaction of arylidene malononitrile with two molecules of dialkyl but-2-ynedioates.The do...A convenient synthetic protocol for the hexasubstituted benzene derivatives was successfully developed by DABCO promoted domino reaction of arylidene malononitrile with two molecules of dialkyl but-2-ynedioates.The domino reaction resulted in tetraalkyl 6-cyano-[1,1'-biphenyl]-2,3,4,5-tetracarboxylates in good to high yields.This formal[2+2+2]cycloaddition was believed to proceed with sequential nucleophilic addition.Michael addition,annulation and aromatization processes.展开更多
The first direct asymmetric Mannich reaction of malononitrile to N-Boc-protected imines has been developed with cinchona alkaloid as catalyst. The procedure could tolerate a relatively wide range of substrates, and re...The first direct asymmetric Mannich reaction of malononitrile to N-Boc-protected imines has been developed with cinchona alkaloid as catalyst. The procedure could tolerate a relatively wide range of substrates, and results in excellent yields and good enantioselectivities even in the presence of only 1 mol% of catalyst loading. The present work provides an easy access to β-amino malononitrile derivatives.展开更多
A green and highly efficient strategy for the preparation of bridged spirocyclic compounds via visible-light-induced cyclization of 2-(2-(arylethynyl)benzylidene)malononitrile derivatives with 2,6-di(tert-butyl)-4-met...A green and highly efficient strategy for the preparation of bridged spirocyclic compounds via visible-light-induced cyclization of 2-(2-(arylethynyl)benzylidene)malononitrile derivatives with 2,6-di(tert-butyl)-4-methylphenol(BHT)at room temperature was developed.The photoinduced radical reactions generated the corresponding products in good yields under simple and mild reaction conditions.展开更多
Electrochemical oxidation of paracetamol has been studied in the presence of malononitrile as a nucleophile in a phosphate buffer solution (0.15 tool/L, pH 7), using cyclic voltammetric techniques. The results indic...Electrochemical oxidation of paracetamol has been studied in the presence of malononitrile as a nucleophile in a phosphate buffer solution (0.15 tool/L, pH 7), using cyclic voltammetric techniques. The results indicated that the N-acetyl-p-benzoquinone-imine derived from paracetamol participates in a 1,4-Michael-ts, pe addition reaction with the malononitrile to form the corresponding paracetamol derivatives (6a, 7a). The present study has led to the development of a simple, green, non-catalyst and one-pot electrochemical method with high atom economy under mild conditions.展开更多
A facile and efficient 1, 4-conjungate addition(Michael addition) reaction of active methylene compounds to aft-unsaturated compounds, catalyzed by guanidinium lactate ionic liquid(IL9), has been developed. A rang...A facile and efficient 1, 4-conjungate addition(Michael addition) reaction of active methylene compounds to aft-unsaturated compounds, catalyzed by guanidinium lactate ionic liquid(IL9), has been developed. A range of chalcones and nitroalkenes together with active methylene compounds have been converted smoothly to the corresponding products in high yields.展开更多
Silica‐bonded N‐propylpiperazine sodium n‐propionate(SBPPSP) was found to act as an efficient solid base for the preparation of a series of 4H‐benzo[b]pyran derivatives. SBPPSP was used as a recyclable heterogeneo...Silica‐bonded N‐propylpiperazine sodium n‐propionate(SBPPSP) was found to act as an efficient solid base for the preparation of a series of 4H‐benzo[b]pyran derivatives. SBPPSP was used as a recyclable heterogeneous solid base catalyst for the synthesis of 3,4‐dihydropyrano[c]chromenes, 2‐amino‐4H‐pyrans, 1,4‐dihydropyrano[2,3‐c]pyrazoles, and 2‐amino‐4H‐benzo[e]‐chromenes via the condensation reaction of dimedone, ethyl acetoacetate, 3‐methyl‐1‐phenyl‐1H‐pyrazol‐5(4H)‐ one, and α‐naphthol, respectively, with aromatic aldehydes and malononitrile in refluxing aqueous ethanol. The heterogeneous solid base showed similar efficiency when reused in consecutive reactions.展开更多
Reaction of acetylacetone with 1 mole of dimethylformamide dimethyl acetal (DMFDMA) affords enamine 2a which reacts with cyanothioacetamide to give pyridinethione 3a. Pyridinethione 3a reacts with methyl iodide, halog...Reaction of acetylacetone with 1 mole of dimethylformamide dimethyl acetal (DMFDMA) affords enamine 2a which reacts with cyanothioacetamide to give pyridinethione 3a. Pyridinethione 3a reacts with methyl iodide, halogenated compounds, aromatic aldehyde and malononitrile/elemental sulfur to yiled compounds 7-10 respectively. Reactions of thioether 7 in ethanolic K2CO3, 1 mole DMFDMA and 4-(dimethylamino)benzaldehyde give compounds 11, 13, 14 respectively. Enaminone 12 can be prepared by reaction of compound 11 with DMFDMA. We have demonstrated some reactions in order to show the potential usefulness of the prepared compounds for the preparation of new bipyridyl compounds 15, 16, 18, bicyclic compounds 17 and uncommon tricyclic compounds 20, 21, 22 and 23 respectively using DMFDMA.展开更多
Reaction of N,N’-dimethylformamide dimethyl acetal (DMFDMA) with malononitrile dimer 8 (1:1) mole afforded 9 while, this reaction when carried out in (2:1) mole to give amidine 11 which can be used for the preparatio...Reaction of N,N’-dimethylformamide dimethyl acetal (DMFDMA) with malononitrile dimer 8 (1:1) mole afforded 9 while, this reaction when carried out in (2:1) mole to give amidine 11 which can be used for the preparation of pyrimidine 13, amidine 14 and pyridine 19 when reacted with 4-nitroaniline, 4-methylaniline and alkoxide respectively. Malononitrile dimer reacted with diazonium chloride to give pyridazine 21, which can be reacted with DMFDMA, AcOH/HCl and cyanoacetamide to give pyridazine 22, 23 and pyrido[4,3-c] pyridazine 24 respectively. The latter reacted with DMFDMA to afford tricyclic compound 25.展开更多
Aqueous starfruit juice catalyzed a simple and efficient Knoevenagel condensation of aromatic aldehydes with malononitrile has been developed under visible light. Products were obtained in yields up to 98% after short...Aqueous starfruit juice catalyzed a simple and efficient Knoevenagel condensation of aromatic aldehydes with malononitrile has been developed under visible light. Products were obtained in yields up to 98% after short reaction times and they were isolated by simple filtration in pure crystallization states. The method is green and economically viable. A plausible mechanism for photochemical Knoevenagel condensation reaction catalyzed by starfruit juice was also predicted.展开更多
A mild,chemoselective,redox-neutral ipso/ortho alkenylcyanation of arylboronic acids with homopropargylic malononitriles via 1,4-rhodium migration and fragmentation is reported.A variety of 2-vinyl arylnitriles are ob...A mild,chemoselective,redox-neutral ipso/ortho alkenylcyanation of arylboronic acids with homopropargylic malononitriles via 1,4-rhodium migration and fragmentation is reported.A variety of 2-vinyl arylnitriles are obtained in good yields(51examples,ava.69%yields)through this strategy,which is characterized by its broad substrate scope,great functional group tolerance,and mild conditions.Mechanism studies indicate that the fragmentation is temperature dependent.The primary asymmetric exploration for the non-fragmentation product already shows promising results.The separation of the two cyano groups of homopropargylic malononitriles results in the formation of aromatic nitrile and aliphatic nitrile in one molecule,which enables the further transformations of the products.展开更多
The functionalized spiro[indoline-3,40-pyrano[3,2-h]quinolines] were efficiently prepared in high yields from three-component reaction of 8-hydroxyquinoline, isatins and malononitrile or ethyl cyanoacetate in ethanol ...The functionalized spiro[indoline-3,40-pyrano[3,2-h]quinolines] were efficiently prepared in high yields from three-component reaction of 8-hydroxyquinoline, isatins and malononitrile or ethyl cyanoacetate in ethanol at room temperature for about 12 h in the presence of piperidine.展开更多
An efficient three-component synthesis of 6-amino-4-aryl-5-cyano-3-metriyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazoles via a reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one,aromatic aldehydes and malononitrile usi...An efficient three-component synthesis of 6-amino-4-aryl-5-cyano-3-metriyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazoles via a reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one,aromatic aldehydes and malononitrile using tungstate sulfuric acid as a catalyst was described.Mild conditions,good to excellent yields,easily available catalyst and easy work-up are the key features of this method.展开更多
A simple and efficient method has been developed for highly diastcreoselective synthesis of trans-1,1-disubstituted-2,6-diarylcyclohexane-4-ones from dibenzalacetone and malononitril with trans-1,2-diaminocyclohexane ...A simple and efficient method has been developed for highly diastcreoselective synthesis of trans-1,1-disubstituted-2,6-diarylcyclohexane-4-ones from dibenzalacetone and malononitril with trans-1,2-diaminocyclohexane as catalyst. The substrate 1,5-diaryl-1,4-pentadien-3-ones and active methylene compounds proceeded to give the products with good to excellent yield within a short time.展开更多
基金Supported by the National Natural Science Foundation of China(No.20972132)
文摘The three-component reaction of aromatic aldehyde,malononitrile and aliphatic amine in a mixed solvent of methanol and water exhibited very interesting molecular diversity and gave the derivatives of polysubstituted N-methyldihydropyridines,2-dialkylaminopyridines and 2-methoxypyridines as main products according to the structure of aliphatic amines used.
文摘A fast, high efficiency and environmentally friendly procedure for the synthesis of 2-aryl benzim-idazole derivatives has been reported. Reaction between 1,2-phenylenediamine derivatives and arylidene malononitrile under aqueous media and also solvent-free conditions generates 2-aryl benzimidazole derivatives with a high yield.
文摘Reaction of 4-carboxaldehyde-2-phenyl-2H-1,2,3-triazole 1 with malononitrile in presence of piperidine afforded the triazolomalonitrile 2 which on treatment with hydrazine hydrate, gave 3-amino-5-(2-phenyl-2H-1,2,3-triazol-4-yl)-4,5-dihydro-1-H-pyrazole-4-carbonitrile 3 and with hydroxylamine, gave 5-amino-3-(2-phenyl-2H-1,2,3-triazol-4-yl)-2,3-dihydroisoxazole-4-carbonitrile 4, and with thiourea, gave?2,4-diamino-6-(2-phenyl-2H-1,2,3-triazol-4-yl)-6H-1,3-thiazine-5-carbonitrile 5. Similarly, reaction of 2 with ethanol amine, gave 2-amino-4-(2-phenyl-2H-1,2,3-triazol-4-yl)nicotinonitrile 6, and with thiosemicarbazide,?gave 4-amino-2-hydrazinyl-6-(2-phnyl-2H-1,2,3-triazol-4-yl)-6H-1,3-thiazine-carbonitrile?7. Similary reaction of 2 with cyclopentanone gave, 2-amino-4-(2-phenyl-2H-1,2,3-triazol-4-yl)-4,5,6,7-tetrahydrocyclopenta [6] pyran-3-carbonitrile 8. In addition, reaction of 1 with hydrazine hydrate, gave the 4 hydrazone which on treatment with another mole of 1 gave 10 and with 3-carboxaldehyde-1-phenyl-4,5-pyrazolinedione 4 phenylhydrazone gave compound 11.
文摘An efficient and facile approach for tetrachlorosilane as an in situ mediated transformation via a one-pot, synthesis of vicinal bromoazides through the generation of BrN3 from azidochlorosilane and N-bromosuccinimide in acetonitrile as solvent at ambient temperature is achieved. This catalytic process represents a highly regioselective and high yielding method for the synthesis of 1,2- bromoazides. Thiamine pyrophosphate (TPP) riboswitches regulate essential genes in bacteria by changing conformation upon binding intracellular TPP. Molecular docking studies are conducted to understand the orientation and the interaction of each synthesized molecules with TPP riboswitches, 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academv of Medical Sciences.
基金This work was financially supported by the National Natural Science Foundation of China(No.21572196)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘A convenient synthetic protocol for the hexasubstituted benzene derivatives was successfully developed by DABCO promoted domino reaction of arylidene malononitrile with two molecules of dialkyl but-2-ynedioates.The domino reaction resulted in tetraalkyl 6-cyano-[1,1'-biphenyl]-2,3,4,5-tetracarboxylates in good to high yields.This formal[2+2+2]cycloaddition was believed to proceed with sequential nucleophilic addition.Michael addition,annulation and aromatization processes.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 21102071) and the Fundamental Research Funds for the Central Universities (Nos. 1107020522 and 1082020502). The Jiangsu 333 program (for Pan) and Changzhou Jin-Feng-Huang program (for Han) are also acknowledged.
文摘The first direct asymmetric Mannich reaction of malononitrile to N-Boc-protected imines has been developed with cinchona alkaloid as catalyst. The procedure could tolerate a relatively wide range of substrates, and results in excellent yields and good enantioselectivities even in the presence of only 1 mol% of catalyst loading. The present work provides an easy access to β-amino malononitrile derivatives.
基金the National Natural Science Foundation of China (No. 22071171)the Natural Science Foundation of Zhejiang Province (No. LZ22B020003)
文摘A green and highly efficient strategy for the preparation of bridged spirocyclic compounds via visible-light-induced cyclization of 2-(2-(arylethynyl)benzylidene)malononitrile derivatives with 2,6-di(tert-butyl)-4-methylphenol(BHT)at room temperature was developed.The photoinduced radical reactions generated the corresponding products in good yields under simple and mild reaction conditions.
基金Semnan University Research Council for financial supports of this work
文摘Electrochemical oxidation of paracetamol has been studied in the presence of malononitrile as a nucleophile in a phosphate buffer solution (0.15 tool/L, pH 7), using cyclic voltammetric techniques. The results indicated that the N-acetyl-p-benzoquinone-imine derived from paracetamol participates in a 1,4-Michael-ts, pe addition reaction with the malononitrile to form the corresponding paracetamol derivatives (6a, 7a). The present study has led to the development of a simple, green, non-catalyst and one-pot electrochemical method with high atom economy under mild conditions.
基金Supported by the Jilin University Innovation Fund(No.419070200033).
文摘A facile and efficient 1, 4-conjungate addition(Michael addition) reaction of active methylene compounds to aft-unsaturated compounds, catalyzed by guanidinium lactate ionic liquid(IL9), has been developed. A range of chalcones and nitroalkenes together with active methylene compounds have been converted smoothly to the corresponding products in high yields.
文摘Silica‐bonded N‐propylpiperazine sodium n‐propionate(SBPPSP) was found to act as an efficient solid base for the preparation of a series of 4H‐benzo[b]pyran derivatives. SBPPSP was used as a recyclable heterogeneous solid base catalyst for the synthesis of 3,4‐dihydropyrano[c]chromenes, 2‐amino‐4H‐pyrans, 1,4‐dihydropyrano[2,3‐c]pyrazoles, and 2‐amino‐4H‐benzo[e]‐chromenes via the condensation reaction of dimedone, ethyl acetoacetate, 3‐methyl‐1‐phenyl‐1H‐pyrazol‐5(4H)‐ one, and α‐naphthol, respectively, with aromatic aldehydes and malononitrile in refluxing aqueous ethanol. The heterogeneous solid base showed similar efficiency when reused in consecutive reactions.
文摘Reaction of acetylacetone with 1 mole of dimethylformamide dimethyl acetal (DMFDMA) affords enamine 2a which reacts with cyanothioacetamide to give pyridinethione 3a. Pyridinethione 3a reacts with methyl iodide, halogenated compounds, aromatic aldehyde and malononitrile/elemental sulfur to yiled compounds 7-10 respectively. Reactions of thioether 7 in ethanolic K2CO3, 1 mole DMFDMA and 4-(dimethylamino)benzaldehyde give compounds 11, 13, 14 respectively. Enaminone 12 can be prepared by reaction of compound 11 with DMFDMA. We have demonstrated some reactions in order to show the potential usefulness of the prepared compounds for the preparation of new bipyridyl compounds 15, 16, 18, bicyclic compounds 17 and uncommon tricyclic compounds 20, 21, 22 and 23 respectively using DMFDMA.
文摘Reaction of N,N’-dimethylformamide dimethyl acetal (DMFDMA) with malononitrile dimer 8 (1:1) mole afforded 9 while, this reaction when carried out in (2:1) mole to give amidine 11 which can be used for the preparation of pyrimidine 13, amidine 14 and pyridine 19 when reacted with 4-nitroaniline, 4-methylaniline and alkoxide respectively. Malononitrile dimer reacted with diazonium chloride to give pyridazine 21, which can be reacted with DMFDMA, AcOH/HCl and cyanoacetamide to give pyridazine 22, 23 and pyrido[4,3-c] pyridazine 24 respectively. The latter reacted with DMFDMA to afford tricyclic compound 25.
文摘Aqueous starfruit juice catalyzed a simple and efficient Knoevenagel condensation of aromatic aldehydes with malononitrile has been developed under visible light. Products were obtained in yields up to 98% after short reaction times and they were isolated by simple filtration in pure crystallization states. The method is green and economically viable. A plausible mechanism for photochemical Knoevenagel condensation reaction catalyzed by starfruit juice was also predicted.
基金supported by the National Natural Science Foundation of China(21971074)the Natural Science Foundation of Guangdong Province(2022A1515010660,2021A1515220024)Natural Science Foundation of Guang Zhou(202102020982)。
文摘A mild,chemoselective,redox-neutral ipso/ortho alkenylcyanation of arylboronic acids with homopropargylic malononitriles via 1,4-rhodium migration and fragmentation is reported.A variety of 2-vinyl arylnitriles are obtained in good yields(51examples,ava.69%yields)through this strategy,which is characterized by its broad substrate scope,great functional group tolerance,and mild conditions.Mechanism studies indicate that the fragmentation is temperature dependent.The primary asymmetric exploration for the non-fragmentation product already shows promising results.The separation of the two cyano groups of homopropargylic malononitriles results in the formation of aromatic nitrile and aliphatic nitrile in one molecule,which enables the further transformations of the products.
基金supported by the National Natural Science Foundation of China (Nos. 21172189, 21572196)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The functionalized spiro[indoline-3,40-pyrano[3,2-h]quinolines] were efficiently prepared in high yields from three-component reaction of 8-hydroxyquinoline, isatins and malononitrile or ethyl cyanoacetate in ethanol at room temperature for about 12 h in the presence of piperidine.
文摘An efficient three-component synthesis of 6-amino-4-aryl-5-cyano-3-metriyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazoles via a reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one,aromatic aldehydes and malononitrile using tungstate sulfuric acid as a catalyst was described.Mild conditions,good to excellent yields,easily available catalyst and easy work-up are the key features of this method.
基金the Key Projects in the National Science & Technology Pillar Program of China,the Program for New Century Excellent Talents in University,China,the National Natural Science Foundation of China,the Natural Science Foundation of Tianjin City,China
文摘A simple and efficient method has been developed for highly diastcreoselective synthesis of trans-1,1-disubstituted-2,6-diarylcyclohexane-4-ones from dibenzalacetone and malononitril with trans-1,2-diaminocyclohexane as catalyst. The substrate 1,5-diaryl-1,4-pentadien-3-ones and active methylene compounds proceeded to give the products with good to excellent yield within a short time.