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Amination, Acetamidation, and Amidation of Substituted Aromatic Carbamates in Polyphosphoric Acid

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Abstract

Electrophilic amination of methyl N-(hydroxyphenyl)carbamates and methyl N-(4-methoxyphenyl)carbamate with sodium azide in 86% polyphosphoric acid (PPA) at 55–60°C regioselectively afforded methyl N-(3-amino-2-hydroxyphenyl)-, N-(4-amino-3-hydroxyphenyl)-, N-(3-amino-4-hydroxyphenyl)-, and N-(3-amino-4-methoxyphenyl)carbamates, i.e., the amino group entered the ortho position with respect to the hydroxy or methoxy group. The reactions of methyl N-(4-methoxyphenyl)carbamate with nitromethane and nitroethane in 80% PPA at 95–110°C gave methyl N-(3-carbamoyl-4-methoxyphenyl)carbamate and methyl N-(3-acetamido-4-methoxyphenyl)carbamate, respectively. Methyl N-[4-(N′-hydroxyethanimidamido)phenyl]carbamate was obtained by reaction of 4-[(methoxycarbonyl)amino]benzoic acid with excess nitroethane in 86% PPA at 125°C.

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Authors and Affiliations

  1. Astrakhan State University, 414000, Astrakhan, Russia

    A. V. Velikorodov & N. N. Stepkina

  2. Astrakhan State Medical University, Ministry of Health of the Russian Federation, 414000, Astrakhan, Russia

    A. V. Velikorodov, E. N. Kutlalieva & E. A. Shustova

  3. Armavir State Pedagogical University, 352901, Armavir, Russia

    O. Yu. Poddubny

Authors
  1. A. V. Velikorodov
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  2. E. N. Kutlalieva
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  3. N. N. Stepkina
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  4. E. A. Shustova
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  5. O. Yu. Poddubny
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Correspondence to A. V. Velikorodov.

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Velikorodov, A.V., Kutlalieva, E.N., Stepkina, N.N. et al. Amination, Acetamidation, and Amidation of Substituted Aromatic Carbamates in Polyphosphoric Acid. Russ J Org Chem 56, 1570–1575 (2020). https://doi.org/10.1134/S1070428020090110

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  • DOI: https://doi.org/10.1134/S1070428020090110

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