Citation: Srinivasa Rao Jetti, Anjna Bhatewara, Tanuja Kadre, Shubha Jain. Silica-bonded N-propyl sulfamic acid as an efficient recyclable catalyst for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones/thiones under heterogeneous conditions[J]. Chinese Chemical Letters, ;2014, 25(3): 469-473. doi: 10.1016/j.cclet.2013.12.022 shu

Silica-bonded N-propyl sulfamic acid as an efficient recyclable catalyst for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones/thiones under heterogeneous conditions

1.
Laboratory of Heterocycles, School of Studies in Chemistry & Biochemistry, Vikram University, Ujjain, Madhya Pradesh, 456010, India

Corresponding author: Srinivasa Rao Jetti,
Received Date: 14 October 2013
Available Online: 5 December 2013

Silica-bonded N-propyl sulfamic acid (SBNPSA) catalyzed one-pot three component Biginelli condensation of different substituted aromatic aldehydes with ethyl acetoacetate and urea/thoiurea to the respective 3,4-dihydropyrimidin-2-(1H)-ones and thiones in environment friendly procedure is described. The facile reaction conditions, simple isolation and purification procedures of this method make it a good option for the synthesis of dihydropyrimidinones.
- Silica-bonded N-propyl sulfamic acid,
- 3,4-Dihydropyrimidin-2-(1H)-ones,
- Multi component reactions,
- Heterogeneous catalysis
1. [1]
  [1] C.O. Kappe, 100 years of the Biginelli dihydropyrimidine synthesis, Tetrahedron 49 (32) (1993) 6937-6963.
2. [2]
  [2] K.S. Atwal, B.N. Swanson, S.E. Unger, et al., Dihydropyrimidine calcium channel blockers. 3.3-Carbamoyl-4-aryl-1,2,3,4-tetrahydro-6-methyl-5-pyrimidinecarboxylic acid esters as orally effective antihypertensive agents, J. Med. Chem. 34 (1991) 806-811.
3. [3]
  [3] B.B. Snider, Z.P. Shi, Biomimetic synthesis of (±)-crambines A, B, C1, and C2. Revision of the structure of crambines B and C1, J. Org. Chem. 58 (1993) 3828-3839.
4. [4]
  [4] B.B. Snider, J. Chen, A.D. Patil, A. Freyer, Synthesis of the tricyclic portions of batzelladines A, B and D. Revision of the stereochemistry of batzelladines A and D, Tetrahedron Lett. 37 (1996) 6977-6980.
5. [5]
  [5] C.O. Kappe, Recent advances in Biginelli dihydropyrimidine synthesis. New tricks from an old dog, Acc. Chem. Res. 33 (2000) 879-888.
6. [6]
  [6] K. Folkers, H.J. Harwood, T.B. Johnson, Research on pyrimidines. cxxx. Synthesis of 2-keto-1,2,3,4-tetrahydropyrimidines, J. Am. Chem. Soc. 54 (1932) 3751-3758.
7. [7]
  [7] J.S. Yadav, B.V. Subba Reddy, E. Jagan Reddy, T. Ramalingam, Microwave-assisted efficient synthesis of dihydro pyrimidines: improved high yielding protocol for the Biginelli reaction, J. Chem. Res. Sci. 7 (2000) 354-355.
8. [8]
  [8] K.S. Atwal, B.C. O'Reilly, J.Z. Gougoutas, M.F. Malley, Synthesis of substituted 1,2,3,4-tetrahydro-6-methyl-2-thioxo-5-pyrimidinecarboxylic acid esters, Heterocycles 26 (1987) 1189-1192.
9. [9]
  [9] E.H. Hu, D.R. Sidler, U.H. Dolling, Unprecedented catalytic three component onepot condensation reaction: an efficient synthesis of 5-alkoxycarbonyl-4-aryl-3,4-dihydro pyrimidin-2(1H)-ones, J. Org. Chem. 63 (1998) 3454-3457.
10. [10]
  [10] C.O. Kappe, S.F. Falsone, Polyphosphate ester-mediated synthesis of dihydropyrimidines. Improved conditions for the Biginelli reaction, Synlett 7 (1998) 718-720.
11. [11]
  [11] C.O. Kappe, D. Kumar, R.S. Varma, Microwave-assisted high-speed parallel synthesis of 4-aryl-3,4-dihydropyrimidin-2(1H)-ones using a solventless Biginelli condensation protocol, Synthesis 10 (1999) 1799-1803.
12. [12]
  [12] F. Bigi, S. Carloni, B. Frullanti, R. Maggi, G. Sartori, A revision of the Biginelli reaction under solid acid catalysis. Solvent-free synthesis of dihydropyrimidines over montmorillonite KSF, Tetrahedron Lett. 40 (1999) 3465-3468.
13. [13]
  [13] B.C. Ranu, A. Hajra, U. Jana, Indium(Ⅲ) chloride-catalyzed one-pot synthesis of dihydropyrimidinones by a three-component coupling of 1,3-dicarbonyl compounds, aldehydes, and urea: an improved procedure for the Biginelli reaction, J. Org. Chem. 65 (2000) 6270-6272.
14. [14]
  [14] J. Lu, H. Ma, Iron(Ⅲ)-catalyzed synthesis of dihydropyrimidinones. Improved conditions for the Biginelli reaction, Synlett 1 (2000) 63-64.
15. [15]
  [15] J. Lu, Y.J. Bai, Z.J. Wang, B.Q. Yang, H.R. Ma, One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using lanthanum chloride as a catalyst, Tetrahedron Lett. 41 (2000) 9075-9078.
16. [16]
  [16] Y. Ma, C. Qian, L. Wang, M. Yang, Lanthanide triflate catalyzed Biginelli reaction. One-pot synthesis of dihydropyrimidinones under solvent-free conditions, J. Org. Chem. 65 (2000) 3864-3868.
17. [17]
  [17] J.C. Bussolari, P.A. McDonnell, A new substrate for the Biginelli cyclocondensation: direct preparation of 5-unsubstituted 3,4-dihydropyrimidin-2(1H)-ones from a β-keto carboxylic acid, J. Org. Chem. 65 (2000) 6777-6779.
18. [18]
  [18] J.S. Yadav, B.V.S. Reddy, K.B. Reddy, K.S. Raj, A.R. Prasad, Ultrasound-accelerated synthesis of 3,4-dihydropyrimidin-2(1H)-ones with ceric ammonium nitrate, J. Chem. Soc., Perkin Trans. 1 (2001) 1939-1941.
19. [19]
  [19] K.A. Kumar, M. Kasthuraiah, C.S. Reddy, C.D. Reddy, Mn(OAc)₃·2H₂O-mediated three-component, one-pot, condensation reaction: an efficient synthesis of 4-aryl-substituted 3,4-dihydropyrimidin-2-ones, Tetrahedron Lett. 42 (2001) 7873-7875.
20. [20]
  [20] A. Dondoni, A. Massi, Parallel synthesis of dihydropyrimidinones using Yb(Ⅲ)-resin and polymer-supported scavengers under solvent-free conditions. A green chemistry approach to the Biginelli reaction, Tetrahedron Lett. 42 (2001) 7975-7978.
21. [21]
  [21] J. Peng, Y. Deng, Synthesis and revision of the relative configuration of fudecalone, Tetrahedron Lett. 42 (2001) 917-919.
22. [22]
  [22] K. Ramalinga, P. Vijayalakshmi, T.N.B. Kaimal, Bismuth(Ⅲ)-catalyzed synthesis of dihydropyrimidinones: improved protocol conditions for the Biginelli reaction, Synlett 6 (2001) 863-865.
23. [23]
  [23] J.S. Yadav, B.V. Subba Reddy, R. Srinivas, C. Venugopal, T. Ramalingam, LiClO4-catalyzed one-pot synthesis of dihydropyrimidinones: an improved protocol for Biginelli reaction, Synthesis 9 (2001) 1341-1345.
24. [24]
  [24] N.Y. Fu, Y.F. Yuan, Z. Cao, et al., Indium(Ⅲ) bromide-catalyzed preparation of dihydropyrimidinones: improved protocol conditions for the Biginelli reaction, Tetrahedron 58 (2002) 4801-4807.
25. [25]
  [25] J. Lu, Y.J. Bai, Catalysis of the Biginelli reaction by ferric and nickel chloride hexahydrates. One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones, Synthesis 4 (2002) 466-470.
26. [26]
  [26] Ch.V. Reddy, M. Mahesh, P.V.K. Raju, T.R. Babu, V.V.N. Reddy, Zirconium(IV) chloride catalyzed one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones, Tetrahedron Lett. 43 (2002) 2657-2659.
27. [27]
  [27] A.S. Prabhakar, G.K. Dewkar, A. Sudalai, Cu(OTf)₂: a reusable catalyst for highyield synthesis of 3,4-dihydropyrimidin-2(1H)-ones, Tetrahedron Lett. 44 (2003) 3305-3308.
28. [28]
  [28] A.G. Choghamarani, P. Zamani, Three component reactions: an efficient and green synthesis of 3,4-dihydropyrimidin-2-(1H)-ones and thiones using silica gel-supported L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate, Chin. Chem. Lett. 24 (2013) 804-808.
29. [29]
  [29] S. Rostamnia, F. Pourhassan, The SBA-15/SO₃H nanoreactor as a highly efficient and reusable catalyst for diketene-based, four-component synthesis of polyhydroquinolines and dihydropyridines under neat conditions, Chin. Chem. Lett. 24 (2013) 401-403.
30. [30]
  [30] S. Rostamnia, K. Lamei, Diketene-based neat four-component synthesis of the dihydropyrimidinones and dihydropyridine backbones using silica sulfuric acid (SSA), Chin. Chem. Lett. 23 (2012) 930-932.
31. [31]
  [31] X.C. Wang, L.J. Zhang, Z. Zhang, Z.J. Quan, PEG-OSO₃Has an efficient and recyclable catalyst for the synthesis of β-amino carbonyl compounds via the Mannich reaction in PEG-H₂O, Chem. Lett. 23 (2012) 423-426.
32. [32]
  [32] M.A. Bigdeli, G. Gholami, E. Sheikhhosseini, P-Dodecylbenzenesulfonic acid (DBSA), a Brønsted acid-surfactant catalyst for Biginelli reaction in water and under solvent free conditions, Chem. Lett. 22 (2011) 903-906.
33. [33]
  [33] A. Corma, H. Garcia, Organic reactions catalyzed over solid acids, Catal. Today 38 (1997) 257-308.
34. [34]
  [34] B. Karimi, D. Zareyee, A high loading sulfonic acid-functionalized ordered nanoporous silica as an efficient and recyclable catalyst for chemoselective deprotection of tert-butyldimethylsilyl ethers, Tetrahedron Lett. 46 (2005) 4661-4665.
35. [35]
  [35] B. Karimi, M. Khalkhali, Solid silica-based sulfonic acid as an efficient and recoverable interphase catalyst for selective tetrahydropyranylation of alcohols and phenols, J. Mol. Catal. A: Chem. 232 (2005) 113-117.
36. [36]
  [36] I.K. Mbaraka, D.R. Radu, V.S. Lin, B.H. Shanks, Organosulfonic acid-functionalized mesoporous silicas for the esterification of fatty acid, J. Catal. 219 (2003) 329-336.
37. [37]
  [37] K. Wilson, A.F. Lee, D.J. Macquarrie, J.H. Clark, Structure and reactivity of sol-gel sulphonic acid silicas, Appl. Catal. A: Gen. 228 (2002) 127-133.
38. [38]
  [38] X.L. Shi, H.X. Yang, M.L. Tao, W.Q. Zhang, Sulfonic acid-functionalized polypropylene fiber: highly efficient and recyclable heterogeneous Brønsted acid catalyst, RSC Adv. 3 (2013) 3939-3945.
39. [39]
  [39] J. Peng, Y. Deng, Ionic liquids catalyzed Biginelli reaction under solvent-free conditions, Tetrahedron Lett. 42 (2001) 5917-5919.
40. [40]
  [40] R. Ghosh, S. Maiti, A. Chakraborty, In(OTf)3-catalysed one-pot synthesis of 3,4-dihydropyrimidin-2(lH)-ones, J. Mol. Catal. A: Chem. 217 (2004) 47-50.
1. [1]
  Ruiying Liu , Li Zhao , Baishan Liu , Jiayuan Yu , Yujie Wang , Wanqiang Yu , Di Xin , Chaoqiong Fang , Xuchuan Jiang , Riming Hu , Hong Liu , Weijia Zhou . Modulating pollutant adsorption and peroxymonosulfate activation sites on Co3O4@N,O doped-carbon shell for boosting catalytic degradation activity. Chinese Journal of Structural Chemistry, 2024, 43(8): 100332-100332. doi: 10.1016/j.cjsc.2023.100332
2. [2]
  Heng Yang , Zhijie Zhou , Conghui Tang , Feng Chen . Recent advances in heterogeneous hydrosilylation of unsaturated carbon-carbon bonds. Chinese Chemical Letters, 2024, 35(6): 109257-. doi: 10.1016/j.cclet.2023.109257
3. [3]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
4. [4]
  Xiao-Ming Chen , Lianhui Song , Jun Pan , Fei Zeng , Yi Xie , Wei Wei , Dong Yi . Visible-light-induced four-component difunctionalization of alkenes to construct phosphorodithioate-containing quinoxalin-2(1H)-ones. Chinese Chemical Letters, 2024, 35(11): 110112-. doi: 10.1016/j.cclet.2024.110112
5. [5]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
6. [6]
  Wen-Tao Ouyang , Jun Jiang , Yan-Fang Jiang , Ting Li , Yuan-Yuan Liu , Hong-Tao Ji , Li-Juan Ou , Wei-Min He . Sono-photocatalytic amination of quinoxalin-2(1H)-ones with aliphatic amines. Chinese Chemical Letters, 2024, 35(10): 110038-. doi: 10.1016/j.cclet.2024.110038
7. [7]
  Yuhao Guo , Na Li , Tingjiang Yan . Tandem catalysis for photoreduction of CO2 into multi-carbon fuels on atomically thin dual-metal phosphochalcogenides. Chinese Journal of Structural Chemistry, 2024, 43(7): 100320-100320. doi: 10.1016/j.cjsc.2024.100320
8. [8]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
9. [9]
  Junjun Huang , Ran Chen , Yajian Huang , Hang Zhang , Anran Zheng , Qing Xiao , Dan Wu , Ruxia Duan , Zhi Zhou , Fei He , Wei Yi . Discovery of an enantiopure N-[2-hydroxy-3-phenyl piperazine propyl]-aromatic carboxamide derivative as highly selective α_1D/1A-adrenoceptor antagonist and homology modelling. Chinese Chemical Letters, 2024, 35(11): 109594-. doi: 10.1016/j.cclet.2024.109594
10. [10]
  Kunyao Peng , Xianbin Wang , Xingbin Yan . Converting LiNO₃ additive to single nitrogenous component Li₂N₂O₂ SEI layer on Li metal anode in carbonate-based electrolyte. Chinese Chemical Letters, 2024, 35(9): 109274-. doi: 10.1016/j.cclet.2023.109274
11. [11]
  Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp³)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
12. [12]
  Shuai Li , Liuting Zhang , Fuying Wu , Yiqun Jiang , Xuebin Yu . Efficient catalysis of FeNiCu-based multi-site alloys on magnesium-hydride for solid-state hydrogen storage. Chinese Chemical Letters, 2025, 36(1): 109566-. doi: 10.1016/j.cclet.2024.109566
13. [13]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
14. [14]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
15. [15]
  Xueyang Zhao , Bangwei Deng , Hongtao Xie , Yizhao Li , Qingqing Ye , Fan Dong . Recent process in developing advanced heterogeneous diatomic-site metal catalysts for electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(7): 109139-. doi: 10.1016/j.cclet.2023.109139
16. [16]
  Weichen Zhu , Wei Zuo , Pu Wang , Wei Zhan , Jun Zhang , Lipin Li , Yu Tian , Hong Qi , Rui Huang . Fe-N-C heterogeneous Fenton-like catalyst for the degradation of tetracycline: Fe-N coordination and mechanism studies. Chinese Chemical Letters, 2024, 35(9): 109341-. doi: 10.1016/j.cclet.2023.109341
17. [17]
  Jia-Cheng Hou , Hong-Tao Ji , Yu-Han Lu , Jia-Sheng Wang , Yao-Dan Xu , Yan-Yan Zeng , Wei-Min He . Sustainable and practical semi-heterogeneous photosynthesis of 5-amino-1,2,4-thiadiazoles over WS₂/TEMPO. Chinese Chemical Letters, 2024, 35(8): 109514-. doi: 10.1016/j.cclet.2024.109514
18. [18]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
19. [19]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147
20. [20]
  Ling-Hao Zhao , Hai-Wei Yan , Jian-Shuang Jiang , Xu Zhang , Xiang Yuan , Ya-Nan Yang , Pei-Cheng Zhang . Effective assignment of positional isomers in dimeric shikonin and its analogs by ¹H NMR spectroscopy. Chinese Chemical Letters, 2024, 35(5): 108863-. doi: 10.1016/j.cclet.2023.108863

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(524)
HTML views(14)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142