Deep Eutectic Solvent/Benzenesulfonic Acid: An Environmental Friendly Catalyst System towards the Synthesis of Dihydropyrimidinones via Biginelli Reaction

doi:10.6023/cjoc202206002

Abstract

In a deep eutectic solvent (DES) that composed of choline chloride and ethylene glycol, 3,4-dihydropyrimidin- 2(1H)-ones were synthesized via Biginelli reaction catalyzed by p-toluenesulfonic acid (p-TSA). 3,4-Dihydropyrimidin-2(1H)- ones were synthesized under mild conditions with high yield. High purity products were obtained by direct filtration without further purification. This catalytic system can be recycled, and the catalysts, solvents and remaining reactants can be directly recycled without separation. The results showed that the catalyst can be recycled up to 8 times. A wide variety of groups such as F, Cl, OMe, NO₂, CH₃, and CH₃CONH were tolerated in this procedure, and 20 products were obtained in high yields (79%~99%).

Key words: deep eutectic solvent (DES), Biginelli reaction, dihypyrimidinone, p-toluenesulfonic acid (p-TSA)

Cite this article

Lulu Zheng, Yuqing Wang, Xiaogang Li, Wenbin Zhang. Deep Eutectic Solvent/Benzenesulfonic Acid: An Environmental Friendly Catalyst System towards the Synthesis of Dihydropyrimidinones via Biginelli Reaction[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3714-3720.

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References 37

[1]	Liu, P.; Hao, J.; Mo, L.; Zhang, Z. H. RSC Adv. 2015, 5, 48675. doi: 10.1039/C5RA05746A
[2]	Khandelwal, S.; Tailor, Y. K.; Kumar, M. J. Mol. Liq. 2016, 215, 345. doi: 10.1016/j.molliq.2015.12.015
[3]	(a) Abbot, A.; Capper, G.; Davies, D.; Munro, H.; Rasheed, R.; Tambyrajah, V. Chem. Commun. 2001, 19, 2010.
	(b) Abbot, A.; Capper, G.; Davies, D.; Rasheed, R.; Ambyrajah, V. Chem. Commun. 2003, 1, 70. doi: 10.1038/s42004-018-0071-6
	(c) Abbot, A.; Capper, G.; Davies, D.; Rasheed, R.; Tambyrajah, V. J. Am. Chem. Soc. 2004, 126, 9142. doi: 10.1021/ja048266j
[4]	Monte, D. F.; Carriazo, D.; Serrano, M.; Ferrer, M. L. ChemSusChem 2014, 7, 999. doi: 10.1002/cssc.201300864
[5]	(a) Shen, X.; Wen, J.; Mei, Q.; Chen, X.; Sun, D.; Yuan, T.; Sun, R. Green Chem. 2019, 21, 275. doi: 10.1039/C8GC03064B
	(b) Kim, K. H.; Dutta, T.; Sun, J.; Simmon, B.; Singh, S. Green Chem. 2018, 20, 809. doi: 10.1039/C7GC03029K
[6]	(a) Ge, X.; Gu, Ch.; Wang, X.; Tu, J. J. Mater. Chem. A 2017, 5, 8209. doi: 10.1039/C7TA01659J
	(b) Wahlström, R.; Hiltunen, J.; Sirkka, N.; Vuoti, S.; Kruus, K. RSC Adv. 2016, 6, 68100. doi: 10.1039/C6RA11719H
[7]	Hao, L.; Wang, M.; Shan, W.; Deng, C.; Ren, W.; Shi, Z.; Lu, H. J. Hazard. Mater. 2017, 339, 216. doi: 10.1016/j.jhazmat.2017.06.050
[8]	Panić, M.; Bubalo, M. C.; Redovniković, I. R. J. Chem. Technol. Biotechnol. 2020, 96, 14.
[9]	(a) Ullah, R.; Atilhan, M.; Anaya, B.; Khraisheh, M.; García, G.; ElKhattat, A.; Aparicio, S. Phys. Chem. Chem. Phys. 2015, 17, 20941. doi: 10.1039/c5cp03364k pmid: 26214080
	(b) Shunkla, S. K.; Mikkola, J. P. Phys. Chem. Chem. Phys. 2018, 20, 24591. doi: 10.1039/C8CP03724H pmid: 26214080
[10]	Peeters, N.; Binnemans, K.; Riaño, S. Green Chem. 2020, 22, 4210. doi: 10.1039/D0GC00940G
[11]	(a) Hillman, A. R.; Ryder, K. S.; Zaleski, C. J.; Ferreira, V.; Beasley, C. A.; Vieil, E. Electrochim. Acta 2014, 135, 42. doi: 10.1016/j.electacta.2014.04.062
	(b) Sebastian, P.; Valles, E.; Gomez, E. Electrochim. Acta 2014, 123, 285. doi: 10.1016/j.electacta.2014.01.062
[12]	Falco, G. D.; Porta, A.; Petrone, A.; Gaudio, M. P.; Hassanin, A. E.; Commodo, M.; Minutolo, P.; Squillace, A.; D'Anna, A. Environ. Sci.: Nano 2017, 4, 1095.
[13]	Wang, A. L.; Xing, P. F.; Zheng, X. L.; Cao, H. Y.; Yang, G.; Zheng, X. F. RSC Adv. 2015, 5, 59022. doi: 10.1039/C5RA08950F
[14]	Imperato, G.; Eibler, E.; Niedermaier, J. Chem. Commun. 2005, 9, 1170.
[15]	Liu, S.; Ni, Y. X.; Wei, W. J.; Qiu, F. L.; Xu, S. L.; Ying, A. G. J. Chem. Res. 2014, 38, 186. doi: 10.3184/174751914X13926483381319
[16]	Wang, P.; Ma, F. P.; Zhang, Z. H. J. Mol. Liq. 2014, 198, 259. doi: 10.1016/j.molliq.2014.07.015
[17]	(a) Zhang, M.; Liu, Y. H.; Shang, Z. R.; Hua, H. C.; Zhang, Z. H. Catal. Commun. 2017, 88, 39. doi: 10.1016/j.catcom.2016.09.028
	(b) Ma, C. T.; Liu, P.; Wu, W.; Zhang, Z. H. J. Mol. Liq. 2017, 242, 606. doi: 10.1016/j.molliq.2017.07.060
	(c) Zhang, W. H.; Chen, M. N.; Hao, Y.; Jiang, X.; Zhou, X. L.; Zhang, Z. H. J. Mol. Liq. 2019, 278, 124. doi: 10.1016/j.molliq.2019.01.065
[18]	Stefanovic, R.; Ludwig, M.; Webber, G. B.; Atkin, R.; Page, A. J. Phys. Chem. Chem. Phys. 2017, 19, 3297. doi: 10.1039/C6CP07932F
[19]	Crespo, E. A.; Silva, L. P.; Lloret, J. O.; Carvalho, P. J.; Vega, L. F.; Llovell, F.; Coutinho., J. A. P. Phys. Chem. Chem. Phys. 2019, 21, 15046. doi: 10.1039/C9CP02548K
[20]	Wang, Y.; Hou, Y.; Wu, W.; Liu, D.; Ji, Y.; Ren, S. H. Green Chem. 2016, 18, 3089. doi: 10.1039/C5GC02909K
[21]	(a) Atwal, K. S.; Swanson, B. N.; Unger, S. E. J. Med. Chem. 1991, 34, 806. pmid: 1995904
	(b) Sunna, V.; Summa, V.; Petrocchi, A; Matassa, V. G.; Gardelli, C.; Muraglia, E.; Rowley, M.; Gonzalez Paz, O.; Laufer, R.; Monteagudo, E.; Pace, P. J. Med. Chem. 2006, 49, 6646. doi: 10.1021/jm060854f pmid: 1995904
	(c) Kaan, H. Y. K.; Ulaganathan, V.; Rath, O.; Prokopcová, H.; Dallinger, D.; Kappe, O.; Kozielski, F. J. Med. Chem. 2010, 53, 5676. doi: 10.1021/jm100421n pmid: 1995904
	(d) Khaldi-Khellafi, N.; Makhloufi-Chebli, M.; Oukacha-Hikem, D.; Bouaziz, S. T.; Lamara, K. O.; Idir, T.; Benazzouz-Touami, A.; Dumas, F. J. Mol. Struct. 2019, 1181, 261. doi: 10.1016/j.molstruc.2018.12.104 pmid: 1995904
[22]	Biginelli, P. Gaza Chim. Ital. 1893, 23, 360.
[23]	More, U. B. Asian J. Chem. 2012, 24, 1906.
[24]	Hu, E. H.; Sidler, D. R.; Dolling, U. H. J. Org. Chem. 1998, 63, 3454. doi: 10.1021/jo970846u
[25]	(a) Pasunooti, K. K.; Chai, H.; Jensen, C. N.; Gorityala, B.; Wang, S.; Liu, X. W. Tetrahedron Lett. 2011, 52, 80. doi: 10.1016/j.tetlet.2010.10.150
	(b) Paraskar, A. S.; Dewkar, G. K.; Sudalai, A. Tetrahedron Lett. 2003, 44, 3305. doi: 10.1016/S0040-4039(03)00619-1
[26]	(a) Damkaci, F.; Szymaniak, A. J. Chem. Educ. 2014, 91, 943. doi: 10.1021/ed400390k
	(b) Wu, M.; Yu, J.; Zhao, W.; Wu, J.; Cao, S. J. Fluorine Chem. 2011, 132, 155. doi: 10.1016/j.jfluchem.2010.12.010
[27]	(a) Khabazzadeh, H.; Saidi, K.; Sheibani, H. Bioorg. Med. hem. Lett. 2008, 18, 278.
	(b) Ranu, B.; Hajra, A.; Jana, U. J. Org. Chem. 2000, 65, 270.
[28]	Debache, A.; Boumoud, B.; Amimour, M.; Belfaitah, A.; Rhouati, S.; Carboni, B. Tetrahedron Lett. 2006, 47, 5697. doi: 10.1016/j.tetlet.2006.06.015
[29]	Lima, C. G. S.; Silva, S.; GonÅalves, R. H.; Leite, E. R.; Schwab, R. S.; CorrÞa, G.; Paix, M. W. ChemCatChem 2014, 6, 3455. doi: 10.1002/cctc.201402689
[30]	(a) Saloutin, V. L.; Burgart, Y. V.; Kuzueva, O. G.; Kappe, C. O.; Chupakhin, O. N. J. Fluorine Chem. 2000, 103, 17. doi: 10.1016/S0022-1139(99)00216-X
	(b) Shutalev, A. D.; Kishko, E. A.; Sivova, N. V.; Yu, A. Molecules 1998, 3, 100. doi: 10.3390/30300100
[31]	Simeonova, S. P.; Afonsob, C. A. RSC Adv. 2016, 6, 5485. doi: 10.1039/C5RA24558C
[32]	Zolfagharinia, S., Koukabi, N.; Eskandar, K. RSC Adv. 2016, 6, 113844. doi: 10.1039/C6RA22791K
[33]	Ma, Y.; Qian, C. T.; Wang, L. M.; Yang, M. J. Org. Chem. 2000, 65, 3864 pmid: 10864778
[34]	Hrirati, Z. D. H.; Shirini, F.; Shojaei, A. F. RSC Adv. 2016, 6, 67072 doi: 10.1039/C6RA11201C
[35]	Wang, D. C.; Guo, H. M.; Qu, G. R. Synth. Commun. 2010, 40, 1115. doi: 10.1080/00397910903043009
[36]	Zhang, G. L.; Cai, X. H. Synth. Commun. 2005, 35, 829. doi: 10.1081/SCC-200050956
[37]	Shirini, F.; Lati, M. P. J. Iran. Chem. Soc. 2017, 14, 75. doi: 10.1007/s13738-016-0959-y

Entry^a	R¹ (1)	R² (2)	R¹/R² (3)	Yield^b/%
1	H (1a)	C₂H₅O (2a)	H/C₂H₅O (3a)	94
2	Cl (1b)	C₂H₅O (2b)	Cl/C₂H₅O (3b)	91
3	F (1c)	C₂H₅O (2c)	F/C₂H₅O (3c)	97
4	2,4-F₂ (1d)	C₂H₅O (2d)	2,4-F₂/C₂H₅O (3d)	97
5	CH₃O (1e)	C₂H₅O (2e)	CH₃O/C₂H₅O (3e)	96
6	NO₂ (1f)	C₂H₅O (2f)	NO₂/C₂H₅O (3f)	93
7	CH₃ (1g)	C₂H₅O (2g)	CH₃/C₂H₅O (3g)	97
8	CH₃CONH (1h)	C₂H₅O (2h)	CH₃CONH/C₂H₅O (3h)	90
9	CN (1i)	C₂H₅O (2i)	CN/C₂H₅O (3i)	95
10	Br (1j)	C₂H₅O (2j)	Br/C₂H₅O (3j)	97
11	H (1k)	CH₃ (2k)	H/CH₃ (3k)	86
12	Cl (1l)	CH₃ (2l)	Cl/CH₃ (3l)	94
13	F (1m)	CH₃ (2m)	F/CH₃ (3m)	89
14	2,4-F₂ (1n)	CH₃ (2n)	2,4-F₂/CH₃ (3n)	96
15	CH₃O (1o)	CH₃ (2o)	CH₃O/CH₃ (3o)	95
16	NO₂ (1p)	CH₃ (2p)	NO₂/CH₃ (3p)	79
17	CH₃ (1q)	CH₃ (2q)	CH₃/CH₃ (3q)	97
18	CH₃CONH (1r)	CH₃ (2r)	CH₃CONH/CH₃ (3r)	72
19	CN (1s)	CH₃ (2s)	CN/CH₃ (3s)	85
20	Br (1t)	CH₃ (2t)	Br/CH₃ (3t)	84

Entry^a	R¹ (1)	R² (2)	R¹/R² (3)	Yield^b/%
1	H (1a)	C₂H₅O (2a)	H/C₂H₅O (3a)	94
2	Cl (1b)	C₂H₅O (2b)	Cl/C₂H₅O (3b)	91
3	F (1c)	C₂H₅O (2c)	F/C₂H₅O (3c)	97
4	2,4-F₂ (1d)	C₂H₅O (2d)	2,4-F₂/C₂H₅O (3d)	97
5	CH₃O (1e)	C₂H₅O (2e)	CH₃O/C₂H₅O (3e)	96
6	NO₂ (1f)	C₂H₅O (2f)	NO₂/C₂H₅O (3f)	93
7	CH₃ (1g)	C₂H₅O (2g)	CH₃/C₂H₅O (3g)	97
8	CH₃CONH (1h)	C₂H₅O (2h)	CH₃CONH/C₂H₅O (3h)	90
9	CN (1i)	C₂H₅O (2i)	CN/C₂H₅O (3i)	95
10	Br (1j)	C₂H₅O (2j)	Br/C₂H₅O (3j)	97
11	H (1k)	CH₃ (2k)	H/CH₃ (3k)	86
12	Cl (1l)	CH₃ (2l)	Cl/CH₃ (3l)	94
13	F (1m)	CH₃ (2m)	F/CH₃ (3m)	89
14	2,4-F₂ (1n)	CH₃ (2n)	2,4-F₂/CH₃ (3n)	96
15	CH₃O (1o)	CH₃ (2o)	CH₃O/CH₃ (3o)	95
16	NO₂ (1p)	CH₃ (2p)	NO₂/CH₃ (3p)	79
17	CH₃ (1q)	CH₃ (2q)	CH₃/CH₃ (3q)	97
18	CH₃CONH (1r)	CH₃ (2r)	CH₃CONH/CH₃ (3r)	72
19	CN (1s)	CH₃ (2s)	CN/CH₃ (3s)	85
20	Br (1t)	CH₃ (2t)	Br/CH₃ (3t)	84

Entry^a	Yield^b/g	Total yield/%
1	4.17	98
2	5.12
3	5.25
4	5.30
5	5.31
6	5.32
7	5.28
8	5.32

Entry^a	Yield^b/g	Total yield/%
1	4.17	98
2	5.12
3	5.25
4	5.30
5	5.31
6	5.32
7	5.28
8	5.32

低共熔溶剂/苯磺酸: 通过Biginelli反应合成二氢嘧啶酮类化合物的环境友好催化体系