Tetraethylenepentamine Functionalized Phenolic Resin as Highly Active Acid-Base Bifunctional Catalyst for Knoevenagel Condensation Reaction

doi:10.6023/cjoc202109031

Abstract

The tetraethylenepentamine functionalized phenolic resin (TEPA-PR) for Knoevenagel condensation reaction has been prepared by aminating a commercially available phenolic resin (PR) and tetraethylenepentamine. The TEPA-PR was characterized by Fourier-transfer infrared spectroscopy (FTIR), X-ray diffraction spectra (XRD) and elemental analysis (EA). The TEPA-PR can efficiently catalyze Knoevenagel condensation reaction of aromatic aldehydes with high yields of a wide range of products. Furthermore, the reaction can be easily carried out in different solvents of different polarity. The novel developed resin catalyst shows good reusability (5 times) without significant decrease of catalytic activity.

Key words: phenolic resin, acid-base catalysis, heterogeneous catalysis, Knoevenagel condensation reaction, water phase catalysis

Cite this article

JIan Xiao, Zhiying Wu, Ziyi Chen, Pengfei Zhao. Tetraethylenepentamine Functionalized Phenolic Resin as Highly Active Acid-Base Bifunctional Catalyst for Knoevenagel Condensation Reaction[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1179-1187.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 12

References 29

[1]	(a) Varga G.; Kukovecz Á.; Kónya Z.; Sipos P.; Pálinkó I. J. Catal. 2020, 381, 308. pmid: 27196438
	(b) Moteki T.; Koga Y.; Ogura M. J. Catal. 2019, 378, 131. pmid: 27196438
	(c) Zacuto M. J. J. Org. Chem. 2019, 84, 6465. doi: 10.1021/acs.joc.9b00450 pmid: 27196438
	(d) Li J. P. H.; Kennedy E. M.; Adesina A. A.; Stockenhuber M. J. Catal. 2019, 369, 157. pmid: 27196438
	(e) Jia Y.; Fang Y.; Zhang Y.; Miras H. N.; Song Y. Chem.-Eur. J. 2015, 21, 14862. pmid: 27196438
	(f) Garrabou X.; Wicky B. I. M.; Hilvert D. J. Am. Chem. Soc. 2016, 138, 6972. doi: 10.1021/jacs.6b00816 pmid: 27196438
	(g) Franconetti A.; Domínguez-Rodríguez P.; Lara-García D.; Prado-Gotor R.; Cabrera-Escribano F. Appl. Catal. A: Gen. 2016, 517, 176. doi: 10.1016/j.apcata.2016.03.012 pmid: 27196438
	(h) Ezugwu C. I.; Mousavi B.; Asraf M. A.; Luo Z.; Verpoort F. J. Catal. 2016, 344, 445. pmid: 27196438
[2]	(a) Kumar N. S.; Reddy M. S.; S. Kumar T. S.; Bheeram V. R.; Mukkamala S. B.; Rao L. C. ChemistrySelect 2019, 4, 1188. doi: 10.1002/slct.201803302
	(b) Gu X.; Tang Y.; Zhang X.; Luo Z.; Lu H. New J. Chem. 2016, 40, 6580. doi: 10.1039/C6NJ00613B
	(c) Pandey R.; Singh D.; Thakur N.; Raj K. K. ACS Omega 2021, 6, 13240. doi: 10.1021/acsomega.1c01155
	(d) Grass J.; Klühspies K.; Reiprich B.; Schwieger W.; Inayat A. Catalysts 2021, 11, 474. doi: 10.3390/catal11040474
	(e) Das A.; Anbu N.; SK M. Dalton Trans. 2019, 4, 17371.
	(f) Zhang X.; Zhang R.; Jin Y.; Li T. J. Solid State Chem. 2019, 278, 120927.
	(g) Guo C. Y.; Zhang Y. H.; Zhang L.; Zhang Y.; Wang J. D. CrystEngComm 2018, 20, 5327. doi: 10.1039/C8CE00954F
[3]	(a) Das A.; Anbu N.; Dhakshinamoorthy A.; Biswas S. Microporous Mesoporous Mater. 2019, 284, 459. doi: 10.1016/j.micromeso.2019.04.057
	(b) Gao M.; Qi M.; Liu L.; Han Z. Chem. Commun. 2019, 55, 6377. doi: 10.1039/C9CC02174D
[4]	(a) Zhang X. Y.; He X. Y.; Zhao S. H. Green Chem Lett. Rev. 2021, 14, 85. doi: 10.1080/17518253.2020.1862312
	(b) Jiang Y.; Jiang F.; Liao X.; Lai S.; Wang S.; Xiong X.; Zheng J.; Liu Y. J. Porous Mater. 2020, 27, 779. doi: 10.1007/s10934-020-00859-3
[5]	(a) Appaturi J. N.; Pulingam T.; Rajabathar J. R.; Khoerunnisa F.; Ling T. C.; Tan S. H.; Ng E. Microporous Mesoporous Mater. 2021, 320, 111091. doi: 10.1016/j.micromeso.2021.111091
	(b) Li R. J.; Chen C.; Hu L. Y.; ChemistrySelect 2020, 5, 14578. doi: 10.1002/slct.202004048
[6]	(a) Jaenicke S.; Chuah G. K.; Lin X. H.; Hu X. C. Micro¬porous Mesoporous Mater. 2000, 35-36, 143.
[7]	(a) Qian B.; Wang F.; Li D.; Li Y. Zhang B.; Zhu J. New J. Chem. 2020, 44, 5995. doi: 10.1039/C9NJ06097A
	(b) Zhu J.; Wang F.; Li D.; Zhai J.; Liu P.; Zhang W.; Li Y.; Catal. Lett. 2020, 150, 1909. doi: 10.1007/s10562-020-03103-4
	(c) Xue B.; Liu X.; Liu N.; Li Y. Res. Chem. Intermed. 2018, 44, 1523. doi: 10.1007/s11164-017-3182-2
[8]	(a) Hajizadeh F.; Maleki B.; Zonoz F. M.; Amiri A. J. Iran. Chem. Soc. 2021, 18, 793. doi: 10.1007/s13738-020-02071-1
	(b) Hu Y.; Zhang J.; Wang Z.; Huo H.; Jiang Y.; Xu X.; Lin K. ACS Appl. Mater. Inter. 2020, 12, 36159. doi: 10.1021/acsami.0c09544
[9]	(a) Zhang X.; He X.; Zhao S. Green Chem. Lett. Rev. 2021, 14, 85. doi: 10.1080/17518253.2020.1862312
	(b) Gilanizadeh M.; Zeynizadeh B. Can. J. Chem. 2021, 99, 531. doi: 10.1139/cjc-2020-0421
[10]	(a) Yao C.; Zhou S.; Kang X.; Zhao Y.; Yan R.; Zhang Y.; Wen L. Inorg. Chem. 2018, 57, 11157. doi: 10.1021/acs.inorgchem.8b01713
	(b) Sarmah B.; Srivastava R. Mol. Catal. 2017, 427, 62.
	(c) Zhang L.; Wang H.; Shen W.; Qin Z.; Wang J.; Fan W. J. Catal. 2016, 344, 293.
[11]	Xiao J.; Wang L.; Ran J.; Zhao J.; Ma N.; Tao M.; Zhang W. J. Cleaner Prod. 2020, 274, 122473. doi: 10.1016/j.jclepro.2020.122473
[12]	Laha B.; Khullar S.; Gogia A.; Mandal S. K. Dalton Trans. 2020, 49, 12298. doi: 10.1039/D0DT02153A
[13]	Sadjadi S.; Akbari M.; Kahangi F. G.; Heravi M. M. Polyhedron 2020, 179, 114375. doi: 10.1016/j.poly.2020.114375
[14]	Tian H.; Liu S.; Zhang Z.; Dang T.; Lu Y.; Liu S. ACS Sustainable Chem. Eng. 2021, 9, 4660. doi: 10.1021/acssuschemeng.1c00389
[15]	Zabihzadeh M.; Omidi A.; Shirini F.; Tajik H.; Langarudi M. S. N. J. Mol. Struct. 2020, 1206, 127730. doi: 10.1016/j.molstruc.2020.127730
[16]	Wen H.; Xie J.; Zhou Y.; Zhou Y.; Wang J. Catal. Sci. Technol. 2019, 9, 5725. doi: 10.1039/C9CY01329F
[17]	Xu Q.; Niu Y.; Wang G.; Li Y.; Zhao Y.; Singh V.; Niu J.; Wang J. Mol. Catal. 2018, 453, 93.
[18]	Taher A.; Lee D.; Lee B.; Lee I. Synlett. 2016, 27, 1433. doi: 10.1055/s-0035-1561356
[19]	Modak A.; Mondal J.; Bhaumik A. Appl. Catal. A: Gen. 2013, 459, 41. doi: 10.1016/j.apcata.2013.03.036
[20]	Rong N.; Qiu T.; Qian R.; Lu L.; Huang X.; Ma Z.; Cui C. Inorg. Chem. Commun. 2017, 86, 98. doi: 10.1016/j.inoche.2017.09.017
[21]	Blanco-Ania D.; Valderas-Cortina C.; Hermkens P. H. H.; Sliedregt L. A. J. M.; Scheeren H. W.; Rutjes F. P. J. T. Molecules 2010, 15, 2269. doi: 10.3390/molecules15042269 pmid: 20428042
[22]	Balalaie S.; Bararjanian M.; Hekmat S.; Salehi P. Synth. Commun. 2006, 36, 3703. doi: 10.1080/10916460600946113
[23]	Xu H.; Pan L.; Fang X.; Liu B.; Zhang W.; Lu M.; Chang H. Tetrahedron Lett. 2017, 58, 2360. doi: 10.1016/j.tetlet.2017.05.006
[24]	Li J.; Lear M. J.; Hayashi Y. Chem.-Eur. J. 2021, 27, 5901.
[25]	Shi D. Q.; Chen J.; Zhuang Q. Y.; Wang X. S.; Hu H. W. Chin. Chem. Lett. 2003, 14, 1242.
[26]	Tukhtaev H. B.; Ivanov K. L.; Bezzubov S. I.; Cheshkov D. A.; Melnikov M. Y.; Budynina E. M. Org. Lett. 2019, 21, 1087. doi: 10.1021/acs.orglett.8b04135
[27]	Ren Y. M.; Cai C. Catal. Lett. 2007, 118, 134. doi: 10.1007/s10562-007-9169-7
[28]	Wiles C.; Watts P. Haswell S. J. Lab Chip 2007, 7, 322. doi: 10.1039/B615069A
[29]	Yadav J. S.; Reddy B. V. S.; Basak A. K.; Visali B.; Narsaiah A. V.; Nagaiah K. Eur. J. Org. Chem. 2004, 2004, 546. doi: 10.1002/ejoc.200300513

Entry	Resin	Amino content/ (mmol•g^–1)	TEPA content/ (mmol•g^–1)
1	TEPA-PR	4.875	0.975
2	TEPA-PR-1	3.085	0.617
3	TEPA-PR-2	1.625	0.325

Entry	Resin	Amino content/ (mmol•g^–1)	TEPA content/ (mmol•g^–1)
1	TEPA-PR	4.875	0.975
2	TEPA-PR-1	3.085	0.617
3	TEPA-PR-2	1.625	0.325

Entry	Resin	Elemental analysis
Entry	Resin	N	C	H
1	Br-PR	1.728	55.713	5.114
2	TEPA-PR	5.647	60.506	5.264

Entry	Resin	Elemental analysis
Entry	Resin	N	C	H
1	Br-PR	1.728	55.713	5.114
2	TEPA-PR	5.647	60.506	5.264

Entry	Solvent	Catalyst loading/mol%	Dosage of methyl cyanoacetate/equiv.	Temp./℃	Time/h	Yield^b/%
1	H₂O	—	1.5	30	5	N.R.
2^c	H₂O	0.1 g	1.5	30	15	44
3^d	H₂O	2.5	1.5	30	5	56
4	Cyclohexane	2.5	1.5	30	5	41
5	CH₃CN	2.5	1.5	30	5	75
6	EtOH	2.5	1.5	30	5	80
7	H₂O	2.5	1.5	30	5	97
8	H₂O	2.5	1.2	30	5	92
9	H₂O	2.5	1.5	30	1	80
10	H₂O	2.5	1.5	30	3	87
11	H₂O	2.5	1.5	30	4	96
12	H₂O	2.5	1.5	25	7	97
13^e	H₂O	2.5	1.5	30	5	96
14^f	H₂O	2.5	1.5	30	5	84
15^g	H₂O	2.5	1.5	30	1	97
16	H₂O	1	1.5	30	5	44
17	H₂O	5	1.5	30	5	96
18	H₂O	10	1.5	30	5	95

四乙烯五胺功能化酚醛树脂作为Knoevenagel缩合反应的高活性酸碱双功能催化剂