CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE

CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE

The catalytic preparation of substituted benzanilides by the reaction of substituted benzoic acids with aniline is an important model process that has been intensively deve­lo­ped recently, in the field of the «green chemistry» concept, direct catalytic amidation, and its study is an urgent scientif...

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Date:2022
Main Author: Shteinberg, Leon
Format: Article
Language:English
Published: V.I.Vernadsky Institute of General and Inorganic Chemistry 2022
Online Access:https://ucj.org.ua/index.php/journal/article/view/458
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Ukrainian Chemistry Journal
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spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4582022-09-07T13:21:23Z CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE Shteinberg, Leon phosphorus trichloride, phosphorous acid, kinetics, reaction rate constant, substituted benzoic acids, substituted benzani­lides, aniline, Hammett's equation, catalysis. The catalytic preparation of substituted benzanilides by the reaction of substituted benzoic acids with aniline is an important model process that has been intensively deve­lo­ped recently, in the field of the «green chemistry» concept, direct catalytic amidation, and its study is an urgent scientific and practical task.  Within the framework of solving this problem, the catalysis of the acylation of aniline by substituted benzoic acids with trivalent phosphorus compounds P(III) was studied. It was established that P(III) in the amount of only 2% mol. from substituted benzoic acid effectively catalyze this reaction, which proceeds in boiling low-polar solvents with intensive water distillation in an air atmosphere, which leads to obtaining anilides of substituted benzoic acids with a yield close to quantitative. The new catalysts, phosphorus trichloride and tribromide, phosphorous acid, successfully complement the catalytic system tetrabutoxytitanate/polybutoxytitanate, previously used for these purposes, allowing to obtain anilides of amino­benzoic acids with greater selectivity, as well as anilides of oxybenzoic acids. The study of the kinetic regularities of the reaction catalyzed by phosphorus trichloride showed a weak effect of substituents: |ρ| ≤ 0.61. Hammett dependences are represented by curves with a maximum, straight line segments are characteristic only for certain groups of substituents, both for meta- and para-substituted and for orthosubstituted benzoic acids.  One of the possible mechanisms of acylation is the formation in situ in the first mi­nutes of the reaction of aniline phosphite, which can act as an oxygen-nucleophilic catalyst, and, upon interaction with substituted benzoic acid, forms the corresponding benzoyl phosphite, which is then attacked by a free aniline molecule to obtain substituted benzanilide.  The ortho effect for P(III) catalysis is absent or very weak, in the case of aminobenzoic acids. At the same time, anthranilic acid can form a phosphite with phosphorous acid, which directly participates in catalysis. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-07-27 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/458 10.33609/2708-129X.88.06.2022.102-120 Ukrainian Chemistry Journal; Vol. 88 No. 6 (2022): Ukrainian Chemistry Journal; 102-120 Украинский химический журнал; Том 88 № 6 (2022): Ukrainian Chemistry Journal; 102-120 Український хімічний журнал; Том 88 № 6 (2022): Український хімічний журнал; 102-120 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/458/234
institution Ukrainian Chemistry Journal
baseUrl_str
datestamp_date 2022-09-07T13:21:23Z
collection OJS
language English
topic_facet phosphorus trichloride
phosphorous acid
kinetics
reaction rate constant
substituted benzoic acids
substituted benzani­lides
aniline
Hammett's equation
catalysis.
format Article
author Shteinberg, Leon
spellingShingle Shteinberg, Leon
CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE
author_facet Shteinberg, Leon
author_sort Shteinberg, Leon
title CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE
title_short CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE
title_full CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE
title_fullStr CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE
title_full_unstemmed CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE
title_sort catalysis of trivalent phosphorus compounds of the reactions of substituted benzoic acids with aniline
description The catalytic preparation of substituted benzanilides by the reaction of substituted benzoic acids with aniline is an important model process that has been intensively deve­lo­ped recently, in the field of the «green chemistry» concept, direct catalytic amidation, and its study is an urgent scientific and practical task.  Within the framework of solving this problem, the catalysis of the acylation of aniline by substituted benzoic acids with trivalent phosphorus compounds P(III) was studied. It was established that P(III) in the amount of only 2% mol. from substituted benzoic acid effectively catalyze this reaction, which proceeds in boiling low-polar solvents with intensive water distillation in an air atmosphere, which leads to obtaining anilides of substituted benzoic acids with a yield close to quantitative. The new catalysts, phosphorus trichloride and tribromide, phosphorous acid, successfully complement the catalytic system tetrabutoxytitanate/polybutoxytitanate, previously used for these purposes, allowing to obtain anilides of amino­benzoic acids with greater selectivity, as well as anilides of oxybenzoic acids. The study of the kinetic regularities of the reaction catalyzed by phosphorus trichloride showed a weak effect of substituents: |ρ| ≤ 0.61. Hammett dependences are represented by curves with a maximum, straight line segments are characteristic only for certain groups of substituents, both for meta- and para-substituted and for orthosubstituted benzoic acids.  One of the possible mechanisms of acylation is the formation in situ in the first mi­nutes of the reaction of aniline phosphite, which can act as an oxygen-nucleophilic catalyst, and, upon interaction with substituted benzoic acid, forms the corresponding benzoyl phosphite, which is then attacked by a free aniline molecule to obtain substituted benzanilide.  The ortho effect for P(III) catalysis is absent or very weak, in the case of aminobenzoic acids. At the same time, anthranilic acid can form a phosphite with phosphorous acid, which directly participates in catalysis.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2022
url https://ucj.org.ua/index.php/journal/article/view/458
work_keys_str_mv AT shteinbergleon catalysisoftrivalentphosphoruscompoundsofthereactionsofsubstitutedbenzoicacidswithaniline
first_indexed 2025-09-24T17:43:45Z
last_indexed 2025-09-24T17:43:45Z
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