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Synthesis 2020; 52(18): 2679-2688
DOI: 10.1055/s-0040-1707396
DOI: 10.1055/s-0040-1707396
paper
Chlorination of Conjugated Nitroalkenes with PhICl2 and SO2Cl2 for the Synthesis of α-Chloronitroalkenes
This work was supported by the Russian Science Foundation (grant 19-73-00146).Further Information
Publication History
Received: 18 March 2020
Accepted after revision: 28 April 2020
Publication Date:
14 May 2020 (online)
Abstract
Chlorination of conjugated nitroalkenes with iodobenzene dichloride or sulfuryl chloride to give target α-chloronitroalkenes in good yields is described. Details of the procedure depend on the donating ability of the nitroalkene substituents. The activity of the described chlorinating agents increases in order ‘PhICl2/Py’ < ‘SO2Cl2’ < ‘SO2Cl2/HCl’ with the former producing the best yields for highly donating substrates and the latter for non-activated groups. An autocatalytic role of hydrogen chloride and the chemoselectivity of chlorination were also demonstrated.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707396.
- Supporting Information
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For the synthesis of α-fluoronitroalkenes, see:
For selected rare examples of α-iodonitroalkenes, see:
For chloronium cations, see:
For Ph3PO-promoted dichlorination of alkenes with SO2Cl2, see:
For activation of halogenating agents, see for example: