Synthesis of Hierarchical Porous Aromatic Frameworks for Immobilization of Thiourea Catalyst

doi:10.7503/cjcu20220171

Abstract

Abstract:

A hierarchical porous aromatic framework（PAF-70） was synthesized via a new synthetic strategy. Nitrogen adsorption-desorption isotherms showed that PAF-70 had mesoporous structure with narrowly distributed pore size. The pore width of PAF-70 was 3.8 nm， which agreed well with the simulation value（ca. 3.7 nm）. Thermogravimetric analysis displayed good thermal stability of PAF-70. Furthermore， PAF-70 could not be dissolved or decomposed in almost all common solvents， which demonstrated its high chemical stability. Noteworthily， the amine group in the monomer had no negative influence on the synthetic strategy， and the amine-tagged PAF with mesopores could be obtained by the same synthetic strategy. Then using a post-synthesis modification strategy， the thiourea unit was easily introduced into the pores of PAF-70 to synthesize PAF-70-thiourea. The catalytic performance of PAF-70- thiourea was further tested using a series of alcohols in the catalysis of N-bromosuccinimide（NBS）-mediated oxidation of alcohols. In the current catalyst system PAF-70-thiourea showed high catalytic activity， high stability as well as broad substrate suitability. In comparison with the thiourea-containing MOF（IRMOF-3-thiourea） in the same catalyst system， the experimental results further demonstrated that PAFs are more suitable platforms for immobilization of catalyst for organocatalysis.

Key words: Porous aromatic framework, Thiourea, Organocatalysis, Highly stable catalyst, Oxidation of alcohols

CLC Number:

O643

TrendMD:

SUN Jinshi, CHEN Peng, JING Liping, SUN Fuxing, LIU Jia. Synthesis of Hierarchical Porous Aromatic Frameworks for Immobilization of Thiourea Catalyst[J]. Chem. J. Chinese Universities, 2022, 43(10): 20220171.

Figures/Tables 4

References 36

1	Das S.， Heasman P.， Ben T.， Qiu S.， Chem. Rev.， 2017， 117（3）， 1515—1563
2	Dhakshinamoorthy A.， Garcia H.， ChemSusChem， 2014， 7（9）， 2392—2410
3	Slater A. G.， Cooper A. I.， Science， 2015， 348（6238）， aaa8075
4	Xu Y.， Jin S.， Xu H.， Nagai A.， Jiang D.， Chem. Soc. Rev.， 2013， 42（20）， 8012—8031
5	Jiao L.， Wang Y.， Jiang H. L.， Xu Q.， Adv. Mater.， 2018， 30（37）， 1703663
6	Liu K. G.， Sharifzadeh Z.， Rouhani F.， Ghorbanloo M.， Morsali A.， Coordin. Chem. Rev.， 2021， 436， 213827
7	Wang C.， An B.， Lin W.， ACS Catal.， 2019， 9（1）， 130—146
8	Wei Y. S.， Zhang M.， Zou R.， Xu Q.， Chem. Rev.， 2020， 120（21）， 12089—12174
9	Li H.， Feng X.， Shao P.， Chen J.， Li C.， Jayakumar S.， Yang Q.， J. Mater. Chem. A， 2019， 7（10）， 5482—5492
10	Mullangi D.， Chakraborty D.， Pradeep A.， Koshti V.， Vinod C. P.， Panja S.， Nair S.， Vaidhyanathan R.， Small， 2018， 14（37）， 1801233
11	Yusran Y.， Li H.， Guan X.， Fang Q.， Qiu S.， EnergyChem， 2020， 2（3）， 100035
12	Debruyne M.， Van Speybroeck V.， Van Der Voort P.， Stevens C. V.， Green Chem.， 2021， 23（19）， 7361—7434
13	Li Z.， Yang Y. W.， Adv. Mater.， 2022， 34（6）， 2107401
14	Zhang P.， Wang S.， Ma S.， Xiao F. S.， Sun Q.， Chem. Commun.， 2020， 56（73）， 10631—10641
15	Ben T.， Ren H.， Ma S.， Cao D.， Lan J.， Jing X.， Wang W.， Xu J.， Deng F.， Simmons J. M.， Qiu S.， Zhu G.， Angew. Chem. Int. Ed.， 2009， 48（50）， 9457—9460
16	Chen P.， Zhang L.， Sun J. S.， Xiao E. K.， Wu X. T.， Zhu G.， ChemPlusChem， 2020， 85（5）， 943—947
17	Tian Y.， Zhu G.， Chem. Rev.， 2020， 120（16）， 8934—8986
18	Yuan Y.， Sun F.， Ren H.， Jing X.， Wang W.， Ma H.， Zhao H.， Zhu G.， J. Mater. Chem.， 2011， 21（35）， 13498—13502
19	Zhang L.， Sun J. S.， Sun F.， Chen P.， Liu J.， Zhu G.， Chem. Eur. J.， 2019， 25（15）， 3903—3908
20	Chen P.， Sun J. S.， Zhang L.， Ma W. Y.， Sun F.， Zhu G.， Sci. China Mater.， 2019， 62（2）， 194—202
21	Jing L. P.， Sun J. S.， Sun F.， Chen P.， Zhu G.， Chem. Sci.， 2018， 9（14）， 3523—3530
22	Merino E.， Verde⁃Sesto E.， Maya E. M.， Iglesias M.， Sanchez F.， Corma A.， Chem. Mater.， 2013， 25（6）， 981—988
23	Sun J. S.， Jing L. P.， Tian Y.， Sun F.， Chen P.， Zhu G.， Chem. Commun.， 2018， 54（13）， 1603—1606
24	Zhang Y.， Li B.， Ma S.， Chem. Commun.， 2014， 50（62）， 8507—8510
25	Ghosh A.， Biju A. T.， Angew. Chem. Int. Editon.， 2021， 60（25）， 13712—13724
26	Guo H.， Fan Y. C.， Sun Z.， Wu Y.， Kwon O.， Chem. Rev.， 2018， 118（20）， 10049—10293
27	Hegedus L. S.， J. Am. Chem. Soc.， 2009， 131（50）， 17995—17997
28	Silvi M.， Melchiorre P.， Nature， 2018， 554（7690）， 40—48
29	Chen P.， Bao X.， Zhang L. F.， Liu G. J.， Jiang Y. J.， Eur. J. Org. Chem.， 2016， 2016（4）， 704—715
30	Luan Y.， Zheng N.， Qi Y.， Tang J.， Wang G.， Catal. Sci. Technol.， 2014， 4（4）， 925—929
31	Serdyuk O. V.， Heckel C. M.， Tsogoeva S. B.， Org. Biomol. Chem.， 2013， 11（41）， 7051—7071
32	Zhang Z.， Bao Z.， Xing H.， Org. Biomol. Chem.， 2014， 12（20）， 3151—3162
33	Lan J.， Cao D.， Wang W.， Ben T.， Zhu G.， J. Phys. Chem. Lett.， 2010， 1（6）， 978—981
34	Lukose B.， Wahiduzzaman M.， Kuc A.， Heine T.， J. Phys. Chem. C， 2012， 116（43）， 22878—22884
35	Stuckwisch C. G.， Hammer G. G.， Blau N. F.， J. Org. Chem.， 1957， 22（12）， 1678—1680
36	Tripathi C. B.， Mukherjee S.， J. Org. Chem.， 2012， 77（3）， 1592—1598

Entry	Alcohol	Product	t/℃	Time	Yield ^a	Entry	Alcohol	Product	t/℃	Time	Yield ^a
1^［23］			-35	3 d	78%	6^［23］			-35	7 d	62%
	1a	1b					6a	6b
2			-20	8 h	77%	7^［23］			-20	20 h	90%
	2a	2b					7a	7b
3			-20	4 d	72%	8			-35	7 d	75%
	3a	3b					8a	8b
4			-20	2 d	65%	9			-20	15 h	76%
	4a	4b					9a	9b
5			-20	4 d	67%	10			-20	6 d	76% ^b
	5a	5b					10a	10b

Entry	Alcohol	Product	t/℃	Time	Yield ^a	Entry	Alcohol	Product	t/℃	Time	Yield ^a
1^［23］			-35	3 d	78%	6^［23］			-35	7 d	62%
	1a	1b					6a	6b
2			-20	8 h	77%	7^［23］			-20	20 h	90%
	2a	2b					7a	7b
3			-20	4 d	72%	8			-35	7 d	75%
	3a	3b					8a	8b
4			-20	2 d	65%	9			-20	15 h	76%
	4a	4b					9a	9b
5			-20	4 d	67%	10			-20	6 d	76% ^b
	5a	5b					10a	10b

[1]	HUANG Qiuhong, LI Wenjun, LI Xin. Organocatalytic Enantioselective Mannich-type Addition of 5H-Oxazol-4-ones to Isatin Derived Ketimines [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220131.
[2]	LIU Chang, ZHANG Pengfei, LI Pengfei. Asymmetric Organocatalytic Enantioselective ［1+4］-Annulation of Morita-Baylis-Hillman Carbonates with Thiazolyl Enones for Assembling of Dihydrofurans Featuring Thiazole Skeleton [J]. Chem. J. Chinese Universities, 2020, 41(10): 2272.
[3]	Lixin XIA,Hongcui ZHANG,Bin FENG,Dongqi YANG,Naishun BU,Yunbo ZHAO,Zhuojun YAN,Zhangnan LI,Ye YUAN,Xiaojun ZHAO. Facile Strategy to Prepare Fluorescent Porous Aromatic Frameworks for Sensitive Detection of Nitroaromatic Explosives ^† [J]. Chem. J. Chinese Universities, 2019, 40(12): 2456.
[4]	DONG Xu, FENG Boxu, CHEN Li, LI Xin. Asymmetric [3+2] Annulations of 1,4-Di-thiane-2,5-diol and N-Boc Aldimines Catalyzed by Tertiary-amine Thiourea^† [J]. Chem. J. Chinese Universities, 2018, 39(8): 1707.
[5]	YAN Tingting,XING Guolong,BEN Teng,QIU Shilun. Influence of Building Blocks on Gas Adsorption Performance of Porous Aromatic Frameworks^† [J]. Chem. J. Chinese Universities, 2018, 39(5): 1072.
[6]	GAO Xu, LU Ping, MA Yuguang. Ultrasound-assisted Synthesis and Characterization of Silicon Centered Porous Aromatic Frameworks^† [J]. Chem. J. Chinese Universities, 2014, 35(8): 1795.
[7]	CHEN Zhanguo, WANG Yingjie, LIU De’e, LIU Yali, LI Ya’nan, WANG Dan, GE Miao. α,β-Vicinal Bromoamine Compounds Converted into α,β-Dehydroamino Derivatives Promoted by Combination of Potassium Carbonate and Thiouea in Water^† [J]. Chem. J. Chinese Universities, 2014, 35(7): 1458.
[8]	LIU Hanwen, PEI Wenchou, TANG Zilong, ZHAO Yunhui. Synthesis of Thioureas Containing Thiadiazole^† [J]. Chem. J. Chinese Universities, 2014, 35(3): 511.
[9]	LIAN Zhao-Bin¹, TIAN Xiao-Hong¹, CAO Ling-Hua^1,2*. Synthesis and Biological Activities of Novel Guanidinoglucosides [J]. Chem. J. Chinese Universities, 2007, 28(7): 1297.
[10]	CHEN Guo-Liang^1,2, ZHOU Jian-Zhang¹, LIN Zhong-Hua¹, LU Jiang-Hong², LIN Jin-Mei². EQCM Study of Effect of Allyl Thiourea on Anodic Dissolution and Cathodic Deposition of Cu in Acidic Media [J]. Chem. J. Chinese Universities, 2006, 27(9): 1699.
[11]	ZHANG Jing, ZHU Qin-Lei, HUANG Ru-Dan, FU Yin-Xia, HU Chang-Wen. Synthesis and Crystal Structure of a Three-dimensional Supramolecular Network [Cu₂(ETU)₆]SO₄ Based on Hydrogen Bonds [J]. Chem. J. Chinese Universities, 2006, 27(11): 2039.
[12]	XU Yan, WANG Fei, FU Yong, ZHANG Qiao-Hong, YE Bao-Xian, SONG Mao-Ping, WU Yang-Jie. Synthesis, Crystal Structure and Electrochemical Properties of Two Novel Diferrocenyl Thiourea Derivatives FcL₁ And FcL₂ [J]. Chem. J. Chinese Universities, 2005, 26(6): 1081.
[13]	XU Yun-Gen, HUA Wei-Yi, ZHU Dong-Ya, SHI Yu, FENG Xiao-Qin . Synthesis and iNOS Inhibitory Activity of S-Alkyl(or aralkyl)-1-alkyl (or aryl)-3-[4-(benzimidazole-2-mercapto)phenyl] Isothioureas [J]. Chem. J. Chinese Universities, 2003, 24(12): 2208.
[14]	CHENG Shao-Ling, HUANG Wen-Qiang. Synthesis of 2-Polystyrylsulfonylethanol and Its Application in Solid-phase Organic Synthesis of Hydantoins and Ureas [J]. Chem. J. Chinese Universities, 2002, 23(9): 1809.
[15]	ZHAO Di-Shun, ZHANG Xing-Chen, ZHOU Qing-Ze, LI Hui-Yong, ZHANG Yue, XIONG Pei-Wen . A Study of New Solid Electrolytes Based on Urea and Thiourea [J]. Chem. J. Chinese Universities, 1999, 20(5): 768.