Synlett
DOI: 10.1055/s-0037-1612083
cluster
© Georg Thieme Verlag Stuttgart · New York

Sodium Selenosulfate from Sodium Sulfite and Selenium Powder: An Odorless Selenylating Reagent for Alkyl Halides to Produce Dialkyl Diselenide Catalysts

Yonghong Liu
b  School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. of China
,
Hai Ling
b  School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. of China
c  Department of Chemistry, East China Normal University, Shanghai, 200062, P. R. of China   Email: xfjiang@chem.ecnu.edu.cn
,
Chao Chen
b  School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. of China
,
Qing Xu
b  School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. of China
,
Lei Yu  *
a  Guangling College, Yangzhou University, Yangzhou, Jiangsu 225000, P. R. of China   Email: yulei@yzu.edu.cn
b  School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. of China
,
c  Department of Chemistry, East China Normal University, Shanghai, 200062, P. R. of China   Email: xfjiang@chem.ecnu.edu.cn
› Author Affiliations
This work was supported by the Nature Science Foundation of Guangling College (ZKZZ18001).
Further Information

Publication History

Received: 12 November 2018

Accepted after revision: 26 December 2018

Publication Date:
07 February 2019 (eFirst)

Published as part of the Cluster Organosulfur and Organoselenium Compounds in Catalysis

Abstract

Na2SeSO3, which can be generated in situ by the reaction of Na2SO3 with Se power, was found to be an odorless reagent for the selenenylation of alkyl halides to produce dialkyl diselenides. These products have been recently shown to be good catalysts for the Baeyer–Villiger oxidation of carbonyl compounds, for the selective oxidation of alkenes, or for the oxidative deoximation of oximes. By using aqueous EtOH as the solvent and avoiding the generation of a malodourous selenol intermediate, the selenylation reaction with Na2SeSO3 is much more environmentally friendly than conventional methods. Owing to the cheap and abundant starting materials and selenium reagents, our novel synthetic method reduces the production costs of dialkyl diselenides as organoselenium catalysts, thereby advancing practical applications of organoselenium-catalysis technologies.

Supporting Information

 
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  • 15 Dialkyl Diselenides 2am; General ProcedureA glass pressure-reaction tube equipped with a magnetic stirrer bar was charged with Na2SO3 (189.0 mg, 1.5 mmol), Se powder (118.5 mg, 1.5 mmol) and H2O (2 mL). The tube was then filled with N2 and sealed. The mixture was stirred at 140 °C for 48 h, and then cooled to r.t. A solution of the appropriate alkyl halide (1 mmol) in EtOH (1 mL) was added, and the tube filled with air and sealed. The mixture was heated in air at 100 °C for 48 h. The product was then isolated by preparative TLC (silica gel, PE).Dibutyl Diselenide (2a) 17Yellow oil; yield: 100.7 mg (74%). IR (film): 2956, 2924, 2853, 1461, 1377, 1287, 1251, 1210, 1179, 720 cm–1. 1H NMR (400 MHz, CDCl3, TMS): δ = 2.95–2.87 (m, 4 H), 1.74–1.66 (m, 4 H), 1.44–1.37 (m, 4 H), 0.92 (t, J = 7.4 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 33.0, 29.9, 22.6, 13.6.
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