Continuous Flow Microreactor Promoted the Catalytic N-Oxidation Reaction of Pyridine Derivatives

Siyuan Chen; Shanxiu Yang; Hao Wang; Yanning Niu; Zhang Zhang; Bo Qian

doi:10.1055/s-0041-1737490

Synthesis, Table of Contents

Synthesis 2022; 54(18): 3999-4004
DOI: 10.1055/s-0041-1737490

paper

Continuous Flow Microreactor Promoted the Catalytic N-Oxidation Reaction of Pyridine Derivatives

Authors

Siyuan Chen

^aKey Laboratory of Eco-Environment-Related Polymer Materials Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. China
Shanxiu Yang

^bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
Hao Wang

^bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
Yanning Niu

^cDepartment of Teaching and Research, Nanjing Forestry University, Huaian, 223003, P. R. China
Zhang Zhang∗

^aKey Laboratory of Eco-Environment-Related Polymer Materials Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. China
Bo Qian ∗

^bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China

Abstract

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Abstract

A simple continuous flow microreactor was successfully constructed for the N-oxidation of pyridine. The continuous flow microreactor used titanium silicalite (TS-1) in a packed-bed microreactor and H₂O₂ (in methanol as solvent) as the catalytic oxidation system for the formation of various pyridine N-oxides in up to 99% yields. This process is a safer, greener, and more highly efficiency process than using a batch reactor. The device was used for over 800 hours of continuous operation with the catalyst maintaining great activity thus providing great potential for large-scale production.

Key words

continuous flow microreactor - hydrogen peroxide - N-oxidation - pyridine - green synthesis - titanium silicalite

Full Text

References

References
1 Li D, Wu P, Sun N, Lu Y.-J, Wong W.-L, Fang Z, Zhang K. Curr. Org. Chem. 2019; 23: 616

The application of pyridine N-oxides in organic intermediates:

2a Tan Y, Barrios-Landeros F, Hartwig JF. J. Am. Chem. Soc. 2012; 134: 3683
2b Talbot EP. A, Richardson M, McKenna JM, Toste FD. Adv. Synth. Catal. 2014; 356: 687
2c Jones DH, Kay ST, McLellan JA, Kennedy AR, Tomkinson NC. O. Org. Lett. 2017; 19: 3512
2d Zhong J, Long Y, Yan X, He S, Ye R, Xiang H, Zhou X. Org. Lett. 2019; 21: 9790
2e Jiao L.-Y, Yin X.-M, Liu S, Zhang Z, Sun M, Ma X.-X. Catal. Commun. 2020; 135: 105889

The application of pyridine N-oxides in oxidants:

3a Wang K.-B, Ran R.-Q, Xiu S.-D, Li C.-Y. Org. Lett. 2013; 15: 2374
3b Harris RJ, Widenhoefer RA. Angew. Chem. Int. Ed. 2014; 53: 9369
3c Okugawa Y, Hirano K, Miura M. Angew. Chem. Int. Ed. 2016; 55: 13558
3d Beatty JW, Douglas JJ, Miller R, McAtee RC, Cole KP, Stephenson CR. J. Chem 2016; 1: 456

The application of pyridine N-oxides in ligands:

4a Beyeh NK, Puttreddy R. Dalton Trans. 2015; 44: 9881
4b Ouizem S, Rosario-Amorin D, Dickie DA, Hay BP, Paine RT. Polyhedron 2015; 101: 37
4c Ishihara K, Lu Y. Chem. Sci. 2016; 7: 1276
4d Lynch W, Lynch G, Sheriff K, Padgett C. Acta Crystallogr., Sect. E 2018; 74: 1405

The application of pyridine N-oxides in catalysts:

5a Zhou L, Zhang M, Li W, Zhang J. Angew. Chem. Int. Ed. 2014; 53: 6542
5b Yoshida K, Takao K.-i. Tetrahedron Lett. 2014; 55: 6861
5c Fukumoto Y, Okazaki N, Chatani N. Org. Lett. 2019; 21: 1760

The application of pyridine N-oxides in drugs:

6a Balzarini J, Stevens M, De Clercq E, Schols D, Pannecouque C. J. Antimicrob. Chemother. 2005; 55: 135
6b Stevens M, Pannecouque C, De Clercq E, Balzarini J. Biochem. Pharmacol. 2006; 71: 1122
6c Gerisch M, Hafner F.-T, Lang D, Radtke M, Diefenbach K, Cleton A, Lettieri J. Cancer Chemother. Pharmacol. 2018; 81: 195
6d Kaieda A, Takahashi M, Takai T, Goto M, Miyazaki T, Hori Y, Unno S, Kawamoto T, Tanaka T, Itono S, Takagi T, Hamada T, Shirasaki M, Okada K, Snell G, Bragstad K, Sang B.-C. Bioorg. Med. Chem. 2018; 26: 647

The application of pyridine N-oxides in materials:

7a Raja V, Sharma AK, Narasimha Rao VV. R. Mater. Lett. 2004; 58: 3242
7b Chen M, Han S, Jiang L, Zhou S, Jiang F, Xu Z, Liang J, Zhang S. Chem. Commun. 2010; 46: 3932
7c Chi X, Zhang H, Vargas-Zúñiga GI, Peters GM, Sessler JL. J. Am. Chem. Soc. 2016; 138: 5829
7d Stross AE, Iadevaia G, Hunter CA. Chem. Sci. 2016; 7: 5686
7e Hu L, Lin X.-M, Mo J.-T, Gan H.-L, Yang X.-L, Cai Y.-P. Inorg. Chem. 2017; 56: 4289

The preparation of pyridine N-oxides with strong oxidants:

8a Kress T. J. Org. Chem. 1985; 50: 3073
8b Brougham P, Cooper MS, Cummerson DA, Heaney H, Thomson N. Synthesis 1987; 1015
8c Zhang H, Huang C.-H. Environ. Sci. Technol. 2005; 39: 593
8d Zhu X, Kreutter KD, Hu H, Player MR, Gaul MD. Tetrahedron Lett. 2008; 49: 832

The preparation of pyridine N-oxides with H₂O₂ in acetic acid:

9a Mosher HS, Turner L, Carlsmith A. Org. Synth. 1953; 33: 79
9b Bockelhe V, Linn WJ. J. Am. Chem. Soc. 1954; 76: 1286
9c Ritter H, Licht HH. J. Heterocycl. Chem. 1995; 32: 585
9d Hollins RA, Merwin LH, Nissan RA, Wilson WS. J. Heterocycl. Chem. 1996; 33: 895

Catalytic methods for the N-oxidation reaction of pyridine:

10a Copéret C, Adolfsson H, Khuong TV, Yudin AK, Sharpless KB. J. Org. Chem. 1998; 63: 1740
10b Neimann K, Neumann R. Chem. Commun. 2001; 487
10c Robinson DJ, McMorn P, Bethell D, Bulman-Page PC, Sly C, King F, Hancock FE, Hutchings GJ. Catal. Lett. 2001; 72: 233
10d Rout L, Punniyamurthy T. Adv. Synth. Catal. 2005; 347: 1958
10e Xie W, Zheng Y, Zhao S, Yang J, Liu Y, Wu P. Catal. Today 2010; 157: 114
10f Zhao W, Yang C. New J. Chem. 2013; 37: 1867
10g Yang F, Zhang X, Li F, Wang Z, Wang L. Green Chem. 2016; 18: 3518

The risk for the utilization of H₂O₂ in batch reaction:

11a Chen KY, Lin CM, Shu CM, Kao CS. J. Therm. Anal. Calorim. 2006; 85: 87
11b Kertalli E, van Rijnsoever LS, Paunovic V, Neira d’Angelo MF, Schouten JC, Nijhuis TA. Chem. Eng. Sci. 2016; 165: 36
11c Fukuzumi S, Lee Y.-M, Nam W. Chin. J. Catal. 2021; 42: 1241
11d Targhan H, Evans P, Bahrami K. J. Ind. Eng. Chem. 2021; 104: 295

Selected reviews for continuous flow microreaction:

12a Jähnisch K, Hessel V, Löwe H, Baerns M. Angew. Chem. Int. Ed. 2004; 43: 406
12b Kiwi-Minsker L, Renken A. Catal. Today 2005; 110: 2
12c Gascon J, van Ommen JR, Moulijn JA, Kapteijn F. Catal. Sci. Technol. 2015; 5: 807
12d Ötvös SB, Kappe OC. Green Chem. 2021; 23: 6117
12e Fu WC, MacQueen PM, Jamison TF. Chem. Soc. Rev. 2021; 50: 7378

13 Klassen NV, Marchlngton D, McGowan HC. E. Anal. Chem. 1994; 66: 2921
14 Wang Y, Li H, Liu W, Lin Y, Han X, Wang Z. Trans. Tianjin Univ. 2018; 24: 25

Supplementary Material

Supporting Information (PDF)