Page 9 of 10
Catalysis Science & Technology
Please do not adjust margins
Journal Name
ARTICLE
General experimental procedure for one-pot synthesis of imines
2
3
4
82-90.
DOI: 10.1039/D0CY00974A
Catal, 2019, 377, 145-152.
M. Holmes, L. A. Schwartz, M. J. Krische, Chem. Rev., 2018, 118,
6026–6052.
Y. Qin, L. H. Zhu, S. Z. Luo, Chem. Rev., 2017, 117, 9433-9520.
A. Kumar, N. A. Espinosa-Jalapa, G. Leitus, Y. Diskin-Posner, L.
Avram, D. Milstein, Angew. Chem. Int. Ed., 2017, 56, 14992–
14996.
S. P. Midya, J. Pitchaimani, V. G. Landge, V. Madhu, E.
Balaraman, Catal. Sci. Technol., 2018, 8, 469-3473.
K. Z. Demmans, C. S. G. Seo, A. J. Lough, R. H. Morris, Chem. Sci.,
2017, 8, 6531-6541.
In a typical procedure for one-pot synthesis of imines, a mixture of
amine (0.5 mmol), benzyl alcohol (0.625 mmol), KOtBu (0.10 mmol)
and catalyst (10 mg) was refluxed with 5 mL of toluene at 100 °C for
24 h in open system under an argon atm. After cooling, ethyl
acetate was added to dilute the reaction mixture and the catalyst
was centrifuged from the solution. Then, solution filtered through a
short pad of SiO2 column. The filtrate was analyzed by GC–MS and
NMR.
5
6
7
8
9
Reusability experiments
S. Ichikawa, M. Tada, Y. Iwasawab, T. Ikariya, Chem. Commun.,
2005, 924–926.
The dehydrogenative coupling of benzyl alcohol and p-toluidine was
also chosen as a model reaction for reusability tests. After the
completion of the first reaction, the catalyst was separated by
centrifugation, washed with ethanol, ethyl acetate and deionized
water, dried at 70ꢀ°C for 12ꢀh under vacuum, and was used for the
further runs.
10 H. Naeimi, F. Salimi, K. Rabiei, J. Mol. Catal. A-Chem., 2006, 260,
100–104.
11 B. Chen, L. Wang, S. Gao, ACS Catal., 2015, 5, 5851−5876.
12 T. Higuchi, R. Tagawa, A. Iimuro, S. Akiyama, H. Nagae, K.
Mashima, Chem. Eur. J., 2017, 23, 12795 – 12804.
13 T. Song, J. E. Park, Y. K. Chung, J. Org. Chem., 2018, 83,
4197−4203.
Conclusions
14 Y. Y. Zhang, J. X. Li, L.L. Ding, L. Liu, S. M. Wang, Z. B. Han, Inorg.
Chem., 2018, 57, 13586−13593.
In this study, we designed a novel, efficient and sustainable Ag-
based heterogeneous catalytic system for the one-pot synthesis of
imines from alcohols and amines. The Ag@MIL-101 catalyst is
prepared using the liquid phase impregnation method and
characterized by ICP-OES, P-XRD, FT-IR, TEM, HRTEM, and XPS
spectroscopies. The average particle size of the silver (0)
nanoparticles in the obtained Ag@MIL-101 catalyst was calculated
as 2.43 ± 0.22 nm. The catalyst showed high activity and selectivity
in the one-pot synthesis of imines from alcohols and amines and
can easily be recycled five times without loss of activity and
selectivity. Furthermore, on the basis of the mentioned
experimental results and previous reports, we examined a possible
reaction pathway. High catalytic performance of the Ag@MIL-101
catalyst used in the one-pot synthesis of imines is achieved by
synergistic cooperation between the silver (0) nanoparticles and
MIL-101(Cr).
15 Y. Shiraishi, M. Ikeda, D. Tsukamoto, S. Tanaka, T. Hirai, Chem.
Commun., 2011, 47, 4811–4813.
16 G. Jaiswal, V. G. Landge, D. Jagadeesan, E. Balaraman, Green
Chem., 2016, 18, 3232-3238.
17 G. J. Chen, H.C. Ma, W. L. Xin, X. B. Li, F.Z. Jin, J.S. Wang, M.Y.
Liu, Y. B. Dong, Inorg. Chem., 2017, 56, 654−660.
18 Y. Long, Z. Gao,J. Qin, P. Wang, W. Wu, L. Zhang, Z. Dong, J. Ma,
J. Colloid Interf. Sci., 2019, 538, 709–719.
19 B. Saha, S. M. W. Rahaman, P. Daw, G. Sengupta, J. K. Bera,
Chem. Eur. J., 2014, 20, 6542.
20 X. Xie, H. V. Huynh, ACS Catal., 2015, 5, 4143-4151.
21 K. Kim, B. Kang, S. H. Hong, Tetrahedron, 2015, 71, 4565.
22 T. T. Nguyen, K. L. Hull, ACS Catal., 2016, 6, 8214.
23 S. C. Ghosh, S. Muthaiah, Y. Zhang, X. Xu, S. H. Hong, Adv. Synth.
Catal., 2009, 351, 2643.
24 G. Zhang, S. K. Hanson, Org. Lett., 2013, 15, 650.
25 A. Mukherjee, A. Nerush, G. Leitus, L. J. W. Shimon, Y. Ben-
David, N. A. E. Jalapa, D. Milstein, J. Am. Chem. Soc., 2016, 138,
4298.
26 S. Wu, W. Sun, J. Chen, J. Zhao, Q. Cao, W. Fang, Q. Zhao, J.
Catal., 2019, 377, 110–121.
27 H. Liu, G. K. Chuah, S. Jaenicke, J. Catal., 2012, 292, 130–137.
28 A. Kumar, A. M. Sadanandhan, S. L. Jain, New J. Chem., 2019, 43,
9116-9122.
29 T. Mitsudome, Y. Mikami, H. Funai, T. Mizugaki, K. Jitsukawa, K.
Kaneda, Angew. Chem. Int. Ed., 2008, 47, 138 –141.
30 K. Shimizu, K. Sugino, K. Sawabe, A. Satsuma, Chem. Eur. J.,
2009, 15, 2341 – 2351.
31 W. Liu, J. Sun, X. Zhang, M. Wei, Ind. Eng. Chem. Res., 2018, 57,
15606−15612.
Conflicts of interest
There are no conflicts to declare.
Acknowledgement
We would like to thank Van Yüzüncü Yıl University Research Fund
for their financial contributions.
32 D. P. Sahoo, S. Patnaik, D. Rath, P. Mohapatra, A. Mohanty, K.
Parida, Catal. Sci. Technol., 2019, 9, 2493-2513.
33 X. Liu, B. Tang, J. Long, W. Zhang, X. Liu, Z. Mirza, Sci. Bull., 2018,
63, 502−524.
References
34 X. Gonga, W. W. Wang, X. P. Fu, S. Wei, W. Z. Yu B.. Liu, C. J. Ji, J.
Zhang, Fuel, 2018, 229, 217−226.
1
V. N. G. Lindsay, A. B. Charette, In Comprehensive Organic
Synthesis, 2nd ed.; Eds. P. Knochel, G. A. Molander, Academic
Press, Oxford, 2014, 365394.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins