Citation: Zhi-Lei Zhou, Peng-Cheng Wang, Ming Lu. Bronsted acidic ionic liquid [C₃SO₃HDoim]HSO₄ catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study[J]. Chinese Chemical Letters, ;2016, 27(02): 226-230. doi: 10.1016/j.cclet.2015.10.010 shu

Bronsted acidic ionic liquid [C₃SO₃HDoim]HSO₄ catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study

1.
School of Chemical Engineer, Nanjing University of Science & Technology, Nanjing 210094, China

Corresponding author: Ming Lu,
Received Date: 6 September 2015
Available Online: 26 September 2015

A series of Bronsted acidic ionic liquids (ILs) were prepared and used for Biginelli-type condensation reaction among aromatic aldehydes, urea or thiourea and cyclopentanone. Through this reaction, the synthesis of various pyrimidinones could be achieved. Of interest, it was found that the reaction was efficiently catalyzed by a novel, eco-friendly functionalized IL [C₃SO₃HDoim]HSO₄, which could be reused for at least 7 times without significantly loss of catalytic activity. The reaction proceeded efficiently at 80℃ to afford the desired products in good yield (up to 96%). In addition, a possible mechanism that accounted for the IL [C₃SO₃HDoim]HSO₄-catalyzed reaction was proposed.
- Bronsted acidic ionic liquids,
- Catalysis,
- Biginelli-type reaction,
- Pyrimidinone,
- Organic synthesis,
- Applied chemistry
1. [1]
  [1] K.S. Atwal, G.C. Rovnyak, B.C. O'Reilly, J. Schwartz, Substituted 1,4-dihydropyrimidines. 3. Synthesis of selectively functionalized 2-hetero-1,4-dihydropyrimidines, J. Org. Chem. 54 (1989) 5898-5907.
2. [2]
  [2] C.O. Kappe, W.M.F. Fabian, M.A. Semones, Conformational analysis of 4-aryldihydropyrimidine calcium channel modulators. A comparison of ab initio, semiempirical and X-ray crystallographic studies, Tetrahedron 53 (1997) 2803-2816.
3. [3]
  [3] A.D. Patil, N.V. Kumar, W.C. Kokke, et al., Novel alkaloids from the sponge Batzella sp.: inhibitors of HIV gp120-human CD₄ binding, J. Org. Chem. 60 (1995) 1182-1188.
4. [4]
  [4] H.I. EI-Subbagh, S.M. Abu-Zaid, M.A. Mahran, et al., Synthesis and biological evaluation of certain α,β-unsaturated ketones and their corresponding fused pyridines as antiviral and cytotoxic agents, J. Med. Chem. 43 (2000) 2915-2921.
5. [5]
  [5] P. Biginelli, Aldureides of ethylic acetoacetate and ethylic oxalacetate, Gazz. Chim. Ital. 23 (1893) 360-416.
6. [6]
  [6] Y.L. Zhu, S.L. Huang, Y.J. Pan, Highly chemoselective multicomponent Biginellitype condensations of cycloalkanones, urea or thiourea and aldehydes, Eur. J. Org. Chem. 11 (2005) 2354-2367.
7. [7]
  [7] (a) E.H. Hu, D.R. Sidler, U.H. Dolling, Unprecedented catalytic three component one-pot condensation reaction: an efficient synthesis of 5-alkoxycarbonyl-4-aryl-3,4-dihydropyrimidin-2(1H)-ones, J. Org. Chem. 63 (1998) 3454-3457;
8. [8]
  (b) P.P. Warekar, G.B. Kolekar, M.B. Deshmukh, P.V. Anbhule, An efficient and modified Biginelli-type synthesis of 3,4-dihydro-1H-indeno[1,2-d] pyrimidine-2,5-dione using phosphorous pentoxide, Synth. Commun. 44 (2014) 3594-3601.
9. [9]
  [8] (a) J. Lu, H. Ma, Iron(Ⅲ)-catalyzed synthesis of dihydropyrimidinones. Improved conditions for the Biginelli reaction, Synlett 207 (2000) 63-64;
10. [10]
  (b) J. Lu, Y. Bai, Z. Wang, B. Yang, H. Ma, One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using lanthanum chloride as a catalyst, Tetrahedron Lett. 41 (2000) 9075-9078;
11. [11]
  (c) E. Pair, V. Levacher, J.F. Briere, Organocatalyzed multicomponent synthesis of pyrazolidinones: meldrum's acid approach, RSC Adv. 46 (2015) 46267-46271.
12. [12]
  [9] 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.
13. [13]
  [10] 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]
  [11] (a) P. Wipf, CunninghamF A., A solid phase protocol of the Biginelli dihydropyrimidine synthesis suitable for combinatorial chemistry, Tetrahedron Lett. 36 (1995) 7819-7822;
15. [15]
  (b) A. Studer, P. Jeger, P. Wipf, P. Curran, Fluorous synthesis: fluorous protocols for the Ugi and Biginelli multicomponent condensations, J. Org. Chem. 62 (1997) 2917-2924.
16. [16]
  [12] (a) H.A. Stefani, P.M. Gatti, 3,4-Dihydropyrimidin-2(1H)-ones: fast synthesis under microwave irradiation in solvent free conditions, Synth. Commun. 30 (2000) 2165-2173;
17. [17]
  (b) C.O. Kappe, D. Kumar, R.S. Varma, Microwave-assited high-speed parallel synthesis of 4-aryl-3,4-dihydropyrimidin-2(1H)-ones using a solventless Biginelli condensation protocol, Synthesis 10 (1999) 1799-1803.
18. [18]
  [13] (a) 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;
19. [19]
  (b) A.V. RamaRao, M.K. Gujar, J. Vasudevan, An enantiospecific synthesis of the tricyclic guanidine segment of the anti-HIV marine alkaloid batzelladine A, J. Chem. Soc., Chem. Commun. 26 (1995) 1369-1370;
20. [20]
  (c) Z. Wang, L. Xu, C. Xia, H. Wang, Novel Biginelli-like three-component cyclocondensation reaction: efficient synthesis of 5-unsubstituted 3,4-dihydropyrimidin-2(1H)-ones, Tetrahedron Lett. 45 (2004) 7951-7953;
21. [21]
  (d) B. Liang, X. Wang, J.X. Wang, Z. Du, New three-component cyclocondensation reaction: microwave-assisted one-pot synthesis of 5-unsubstituted-3,4-dihydropyrimidin-2(1H)-ones under solvent-free conditions, Tetrahedron 63 (2007) 1981-1986.
22. [22]
  [14] D.M. D'Souza, T.J.J. Muller, Multicomponent syntheses of heterocycles by transition-metal catalysis, Chem. Soc. Rev. 36 (2007) 1095-1108.
23. [23]
  [15] (a) S. Kobayashi, M. Sugiura, H. Kitagawa, W.W.L. Lam, Chem inform abstract: rare-earth metal triflates in organic synthesis, Chem. Rev. 102 (2002) 2227-2302;
24. [24]
  (b) M. Shibasaki, S. Matsunaga, Design and application of linked-BINOL chiral ligands in bifunctional asymmetric catalysis, Chem. Soc. Rev. 35 (2006) 269-279.
25. [25]
  [16] H. Zhang, Z. Zhou, Z. Yao, F. Xu, Q. Shen, Efficient synthesis of pyrimidinone derivatives by ytterbium chloride catalyzed Biginelli-type reaction under solventfree conditions, Tetrahedron Lett. 50 (2009) 1622-1624.
26. [26]
  [17] K.R. Seddon, Ionic liquids for clean technology, J. Chem. Technol. Biotechnol. 68 (1997) 351-356.
27. [27]
  [18] (a) T. Welton, Room-temperature ionic liquids. Solvents for synthesis and catalysis, Chem. Rev. 99 (1999) 2071-2084;
28. [28]
  (b) P. Wasserscheid, W. Keim, Ionic liquids-new "solutions" for transition metal catalysis, Angew. Chem. Int. Ed. 39 (2000) 3772-3789;
29. [29]
  (c) J.S. Wilkes, A short history of ionic liquids-from molten salts to neoteric solvents, Green Chem. 4 (2002) 73-80;
30. [30]
  (d) V.I. Parvulescu, C. Hardacre, Catalysis in ionic liquids, Chem. Rev. 107 (2007) 2615-2665.
31. [31]
  [19] C. Chiappe, E. Leandri, M. Tebano, [Hmim] [NO₃] —an efficient solvent and promoter in the oxidative aromatic chlorination, Green Chem. 8 (2006) 742-745.
32. [32]
  [20] D. Fang, J. Luo, X.L. Zhou, Z.L. Liu, One-pot green procedure for Biginelli reaction catalyzed by novel task-specific room-temperature ionic liquids, J. Mol. Catal., A: Chem. 274 (2007) 208-211.
33. [33]
  [21] S.F. Chai, L.S. Wang, G.Q. Yan, Y. Li, Solubilities of 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate in selected solvents, J. Chem. Eng. Chin. 18 (2010) 1008-1012.
34. [34]
  [22] H.Z. Zhi, C.X. Lv, Q. Zhang, et al., A new PEG-1000-based dicationic ionic liquid exhibiting temperature-dependent phase behavior with toluene and its application in one-pot synthesis of benzopyrans, Chem. Commun. 20 (2009) 2878-2880.
35. [35]
  [23] A.C. Cole, J.L. Jensen, I. Ntai, et al., Novel bronsted acidic ionic liquids and their use as dual solvent-catalysts, J. Am. Chem. Soe. 124 (2002) 5962-5963.
36. [36]
  [24] A. Yoshimura, A. Nomoto, A. Ogawa, Rhodium-catalyzed hydrothiolation of alkynes with thiols for construction of sulfur-containing π-conjugated systems, Res. Chem. Intermediat. 40 (2014) 2381-2389.
37. [37]
  [25] (a) C.O. Kappe, A reexamination of the mechanism of the Biginelli dihydropyrimidine synthesis. Support for an N-acyliminium ion intermediate, J. Org. Chem. 62 (1997) 7201-7204;
38. [38]
  (b) C.O. Kappe, Recent advances in the Biginelli dihydropyrimidine synthesis. New tricks from an old dog, Acc. Chem. Res. 33 (2000) 879-888.
39. [39]
  [26] D. Saha, A. Saha, B.C. Ranu, Remarkable influence of substituent in ionic liquid in control of reaction: simple, efficient and hazardous organic solvent free procedure for the synthesis of 2-aryl benzimidazoles promoted by ionic liquid, [pmim] BF₄, Green Chem. 11 (2009) 733-737.
40. [40]
  [27] (a) M.J. Earle, S.P. Katdare, K.R. Seddon, Paradigm confirmed: the first use of ionic liquids to dramatically influence the outcome of chemical reactions, Org. Lett. 6 (2004) 707-710;
41. [41]
  (b) B.C. Ranu, S. Banerjee, The dramatic influence of a task-specific ionic liquid, [bmIm] OH, in michael addition of active methylene compounds to conjugated ketones, carboxylic esters, and nitriles, Org. Lett. 7 (2005) 3049-3052.
42. [42]
  [28] L. Wang, J. Sheng, H. Tian, et al., A convenient synthesis of α,α'-bis(substituted benzylidene)cycloalkanones catalyzed by Yb(OTf)3 under solvent-free conditions, Synthesis 18 (2004) 3060-3064.
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沈阳化工大学材料科学与工程学院沈阳 110142

Bronsted acidic ionic liquid [C3SO3HDoim]HSO4 catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study

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通讯作者: 陈斌, bchen63@163.com

Bronsted acidic ionic liquid [C₃SO₃HDoim]HSO₄ catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study