A Sulfonic Acid Polyvinyl Pyridinium Ionic Liquid Catalyzes the Multi-Component Synthesis of Spiro-indoline-3,5′-pyrano[2,3-d]-pyrimidines and -Pyrazines
Abstract
:1. Introduction
2. Results and Discussion
2.1. Catalyst Preparation and Characterization
2.2. Synthesis of Spiro-Indoline-3,5′-pyrano[2,3-d]pyrimidines—Optimization
2.3. Mechanistical Considerations
2.4. Synthesis of Spiro-Indoline-3,5′-pyrano[2,3-d]pyrimidine Derivatives—Substrate Scope
2.5. Synthesis of Spiro-Indoline-3,5′-pyrano[2,3-d]pyrazole Derivatives—Substrate Scope
3. Materials and Methods
3.1. Syntheses
3.1.1. Preparation of PVP IL-B-SO3H
3.1.2. Acidity Measurement Using the Barium Sulfate Test
3.1.3. General Procedure for the Preparation of the Pyrimidines (1–6)c
3.1.4. General Procedure for the Preparation of (1–8)d
3.1.5. Catalyst Recovery and Re-Use Tests
3.2. Instrumentation
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Entry | Catalyst (g) b | Conditions c | Time (min) | Yield (%) d |
1 | - | US; EtOH; reflux | 70 | - |
2 | 0.04 | US; EtOH; r.t. | 70 | - |
3 | 0.04 | US; EtOH; 50 ℃ | 50 | 55 |
4 | 0.04 | US; EtOH; reflux | 50 | 95 |
5 | 0.02 | US; EtOH; reflux | 70 | 53 |
6 | 0.06 | US; EtOH; reflux | 45 | 94 |
7 | 0.04 | US; H2O; reflux | 60 | 45 |
8 | 0.04 | US; CH3CN; reflux | 60 | 48 |
9 | 0.04 | US; Et2O; reflux | 70 | - |
10 | 0.04 | US; n-hexane; reflux | 70 | - |
11 | 0.04 | US; EtOAc; reflux | 60 | - |
12 | 0.04 | US; toluene; 80 °C | 60 | - |
13 | 0.04 | US; DMF; 80 °C | 60 | 23 |
14 | 0.04 | US; CH2Cl2; reflux | 70 | - |
Product | R | R1 | Time (min) | Yield (%) b | M.p. (°C) |
1c | CH3CH2 | CH3 | 50 | 95 | 289–291 |
2c | CH3CH2 | CH3CH2 | 50 | 94 | 285–287 |
3c | CH3CH2 | Ph–CH2 | 60 | 93 | ˃300 |
4c | CH3CH2CH2 | CH3 | 50 | 89 | 278–280 |
5c | Ph–CH2 | CH3 | 50 | 93 | ˃300 |
6c | Ph–CH2CH2 | CH3 | 60 | 97 | ˃300 |
Product | R | X | Time (min) | Yield (%) b | M.p. (°C) |
1d | H | 5-CH3 | 90 | 95 | 269–271 |
2d | H | 5-OCH3 | 90 | 93 | 273–275 |
3d | H | 5-Cl | 70 | 96 | 286–288 |
4d | H | 5-Br | 80 | 94 | ˃300 |
5d | H | 5,7-CH3 | 90 | 95 | ˃300 |
6d | H | 5,7-Br | 60 | 97 | ˃300 |
7d | H | 5,7-Cl | 80 | 95 | ˃300 |
8d | Ph | 5,7-Cl | 75 | 89 | ˃300 |
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Khalaj, M.; Taherkhani, M.; Payen, L.; Klein, A. A Sulfonic Acid Polyvinyl Pyridinium Ionic Liquid Catalyzes the Multi-Component Synthesis of Spiro-indoline-3,5′-pyrano[2,3-d]-pyrimidines and -Pyrazines. Molecules 2023, 28, 3663. https://doi.org/10.3390/molecules28093663
Khalaj M, Taherkhani M, Payen L, Klein A. A Sulfonic Acid Polyvinyl Pyridinium Ionic Liquid Catalyzes the Multi-Component Synthesis of Spiro-indoline-3,5′-pyrano[2,3-d]-pyrimidines and -Pyrazines. Molecules. 2023; 28(9):3663. https://doi.org/10.3390/molecules28093663
Chicago/Turabian StyleKhalaj, Mehdi, Mahboubeh Taherkhani, Leo Payen, and Axel Klein. 2023. "A Sulfonic Acid Polyvinyl Pyridinium Ionic Liquid Catalyzes the Multi-Component Synthesis of Spiro-indoline-3,5′-pyrano[2,3-d]-pyrimidines and -Pyrazines" Molecules 28, no. 9: 3663. https://doi.org/10.3390/molecules28093663