Chlorination of Conjugated Nitroalkenes with PhICl2 and SO2Cl2 for the Synthesis of α-Chloronitroalkenes

Anastasia A. Fadeeva; Sema L. Ioffe; Andrey A. Tabolin

doi:10.1055/s-0040-1707396

Synthesis, Table of Contents

Synthesis 2020; 52(18): 2679-2688
DOI: 10.1055/s-0040-1707396

paper

Chlorination of Conjugated Nitroalkenes with PhICl₂ and SO₂Cl₂ for the Synthesis of α-Chloronitroalkenes

Anastasia A. Fadeeva

^aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, Moscow 119991, Russian Federation Email: atabolin@ioc.ac.ru Email: tabolin87@mail.ru

^bHigher Chemical College, D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow 125047, Russian Federation

,

Sema L. Ioffe

^aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, Moscow 119991, Russian Federation Email: atabolin@ioc.ac.ru Email: tabolin87@mail.ru

,

Andrey A. Tabolin ∗

^aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, Moscow 119991, Russian Federation Email: atabolin@ioc.ac.ru Email: tabolin87@mail.ru

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Abstract

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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.

Key words

nitroalkenes - halogenation - chlorination - nitro compounds - chemoselectivity

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References

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