Polyurea Modified with 4‐Dihydropyrimidone‐2‐ketone Rings by Biginelli Reaction and its Boostered AIE Characteristic

Objective: A facile and efficient method for synthesis of 3, 4-dihydropyrimidin-2(1H)-ones via Biginelli reaction catalyzed by a novel dicationic Brönsted acidic ionic liquid, [(EtNH2)2SO][HSO4]2, has been successfully developed. Material and Method:: 3, 4-Dihydropyrimidin-2(1H)-ones were synthesized through one-pot condensation of aromatic aldehydes, ethyl acetoacetate, and urea under solvent-free conditions using [(EtNH2)2SO][HSO4]2 as a novel catalyst. The progress of the reaction was monitored by thin-layer chromatography (ethyl acetate / n-hexane = 1 / 5). The products have been characterized by IR, 1H NMR, 13C NMR, and also by their melting points. Results: In this research, a library of dihydropyrimidinone derivatives was synthesized via Biginelli reaction under solvent-free conditions at 120oC using [(EtNH2)2SO][HSO4]2 as a catalyst. Various aromatic aldehydes, as well as heteroaromatic aldehydes, were employed, affording good to high yields of the corresponding products and illustrating the substrate generality of the present method. In addition, the prepared dicationic Brönsted acidic ionic liquid can be easily recovered and reused. Conclusion: 1, 1’-Sulfinyldiethylammonium bis (hydrogen sulfate), as a novel dicationic ionic liquid, can act as a highly efficient catalyst for the synthesis of 3, 4-dihydropyrimidin-2(1H)-ones under solvent-free conditions.

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Ascorbic acid-Catalyzed One-Pot Three-Component Biginelli Reaction: A Practical and Green Approach towards Synthesis of 3,4-dihydropyrimidin- 2(1H)-ones/thiones

Letters in Organic Chemistry ◽

10.2174/15701786113109990014 ◽

2013 ◽

Vol 10 (7) ◽

pp. 463-467 ◽

Cited By ~ 4

Author(s):

Imene Sehout ◽

Raouf Boulcina ◽

Boudjemaa Boumoud ◽

Fabienne Berree ◽

Bertrand Carboni ◽

...

Keyword(s):

Ascorbic Acid ◽

Biginelli Reaction ◽

One Pot ◽

Green Approach ◽

Acid Catalyzed

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Synthesis of Dihydropyrimidinones (DHPMs) and Hexahydro Xanthene Catalyzed by 1,4-Diazabicyclo [2.2.2] Octane Triflate Under Solvent-Free Condition

Current Organic Synthesis ◽

10.2174/1570179415666181113154232 ◽

2019 ◽

Vol 16 (5) ◽

pp. 776-786 ◽

Cited By ~ 1

Author(s):

Deepa ◽

Geeta D. Yadav ◽

Mohd J. Aalam ◽

Pooja Chaudhary ◽

Surendra Singh

Keyword(s):

Ethyl Acetoacetate ◽

Biginelli Reaction ◽

Solvent Free ◽

Efficient Catalyst ◽

Solvent Free Condition ◽

Solvent Free Conditions ◽

Xanthene Derivatives ◽

Different Temperatures ◽

Flash Column Chromatography ◽

Biginelli Condensation

Objective:DABCO salts were evaluated as catalysts for the Biginelli reaction between 4- methoxybenzaldehyde, urea and ethyl acetoacetate under solvent-free conditions. 1,4-Diazabicyclo [2.2.2] octane triflate was found to be a simple, inexpensive, highly efficient catalyst for Biginelli reaction for a variety aromatic aldehyde with urea and ethyl acetoacetate at 80°C afforded corresponding 3,4-dihydropyrimidinones in 50-99% yields after 30-120 minutes. 1,3-Cyclohexadione was used in place of ethyl acetoacetate in the absence of urea this methodology is giving hexahydro xanthene derivatives in good to excellent yields after 3-4 hours.Methods:DABCO salt 4 (5 mol%), 4-methoxybenzaldehyde (0.73 mmol) and urea (0.73 mmol) were stirred for 10 minutes at 80°C, then ethyl acetoacetate (1.5 equiv.) was added and reaction mixture was stirred at 80°C for specified time. The resulting solution was stirred continuously and progress of the reaction was followed by TLC. The crude reaction mixture was purified by flash column chromatography on silica gel (hexane/ethyl acetate (1:2)) to give pure desired product.Results:Reaction conditions of the Biginelli reaction were optimized using 4-methoxybenzaldehyde (0.73 mmol), urea (0.73 mmol), and ethyl acetoacetate (5 equiv.) as model substrates catalyzed by 1,4-Diazabicyclo [2.2.2] octane triflate (5 mol%) in a different solvents, screening of different catalysts and different temperatures. Neat condition was found to be the best for the Biginelli condensation and corresponding 3,4- dihydropyrimidinones was obtained in good to excellent yields. When the reaction was carried out with benzaldehyde derivatives and cyclohexane-1,3-dione in place of ethyl acetoacetate in the absence of urea, solely corresponding hexahydro xanthene derivatives were obtained in 61-91% yields.Conclusion:In conclusion, we have applied salts of 1,4-Diaza-bicyclo [2.2.2] octane as catalysts in the Biginelli condensation and corresponding 3,4-dihydropyrimidinones were obtained in 50- 99% yields under solvent free conditions. This methodology is having advantages like simple work-up; low loading of catalyst and reaction was performed at moderate temperature under solvent-free conditions.

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Sulfonic Acid and Ionic Liquid Functionalized Covalent Organic Framework for Efficient Catalysis of the Biginelli Reaction

The Journal of Organic Chemistry ◽

10.1021/acs.joc.0c02423 ◽

2021 ◽

Vol 86 (3) ◽

pp. 3024-3032 ◽

Cited By ~ 1

Author(s):

Bing-Jian Yao ◽

Wen-Xiu Wu ◽

Luo-Gang Ding ◽

Yu-Bin Dong

Keyword(s):

Ionic Liquid ◽

Sulfonic Acid ◽

Biginelli Reaction ◽

Covalent Organic Framework ◽

Organic Framework

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Vegetable oil as a highly effective 100% bio-based alternative solvent for the one-pot multicomponent Biginelli reaction

Green Chemistry ◽

10.1039/d1gc00872b ◽

2021 ◽

Author(s):

Pakin Noppawan ◽

Suwiwat Sangon ◽

Nontipa Supanchaiyamat ◽

Andrew J. Hunt

Keyword(s):

Vegetable Oil ◽

Palm Oil ◽

Biginelli Reaction ◽

Environmentally Friendly ◽

One Pot ◽

Highly Effective ◽

The One ◽

Biginelli Reactions

Multicomponent one-pot Biginelli reactions have been successfully performed using vegetable oil as bio-based, non-toxic, and environmentally friendly solvents. Palm oil was demonstrated to be a highly effective greener solvent as...

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Sulfamic acid pyromellitic diamide-functionalized MCM-41 as a multifunctional hybrid catalyst for melting-assisted solvent-free synthesis of bioactive 3,4-dihydropyrimidin-2-(1H)-ones

Scientific Reports ◽

10.1038/s41598-021-89572-y ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Ehsan Valiey ◽

Mohammad G. Dekamin ◽

Zahra Alirezvani

Keyword(s):

Structural Characteristics ◽

Biginelli Reaction ◽

High Surface ◽

High Surface Area ◽

Sulfamic Acid ◽

Solvent Free ◽

Biologically Active ◽

Green Protocol ◽

Solvent Free Conditions ◽

Mcm 41

AbstractThis study introduces a practical approach to fabricate a novel hybrid acidic catalyst, namely sulfamic acid pyromellitic diamide-functionalized MCM-41 (MCM-41-APS-PMDA-NHSO3H). Various techniques such as FTIR, TGA, XRD, BET, FESEM, and EDX were used to confirm its structural characteristics. The efficiency of the new MCM-41-APS-PMDA-NHSO3H organosilica nanomaterials, as a heterogenous nanocatalyst, was examined in the synthesis of biologically active 3,4-dihydropyrimidin-2-(1H)-one derivatives under solvent-free conditions. It was found that the nanoporous MCM-41-APS-PMDA-NHSO3H, demonstrating acidic nature and high surface area, can activate all the Biginelli reaction components to afford desired 3,4-dihydropyrimidin-2-(1H)-ones under solvent-free conditions in short reaction time. Furthermore, easy and quick isolation of the new introduced hybrid organosilica from the reaction mixture as well as its reusability with negligible loss of activity in at least five consecutive runs are another advantages of this green protocol.

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