ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ

ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ

The polybutoxytitanates catalysis of aniline acylation by orthosubstituted benzoic acids leads to the production of substituted benzanilides. Catalytic rate constants of the second order reaction (the first with respect to aniline and ortho-substituted benzoic acid; boiling ortho=xylene, 145°C) corr...

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Дата:2021
Автор: Shteinberg, Leon
Формат: Стаття
Мова:English
Опубліковано: V.I.Vernadsky Institute of General and Inorganic Chemistry 2021
Онлайн доступ:https://ucj.org.ua/index.php/journal/article/view/287
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Назва журналу:Ukrainian Chemistry Journal

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Ukrainian Chemistry Journal
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spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2872021-05-13T15:07:38Z INFLUENCE OF SUBSTITUTES ON THE RATE OF THE REACTION OF ORTHOSUBSTITUTED BENZOIC ACIDS WTH ANILINE, CATALYZED BY POLYBUTOXYTITANATES ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ Shteinberg, Leon polybutoxytitanates, kinetics, reaction rate constant, ortho-substituted benzoic acids, aniline, substituted benzanilides, Hammett’s equation, catalysis. The polybutoxytitanates catalysis of aniline acylation by orthosubstituted benzoic acids leads to the production of substituted benzanilides. Catalytic rate constants of the second order reaction (the first with respect to aniline and ortho-substituted benzoic acid; boiling ortho=xylene, 145°C) correlate well according to the Hammett and Bronsted equations with straight line segments with ρ=1.93 and α=0.66, in contrast to the reaction of aniline with meta- and parasubstituted benzoic acids and substituted anilines with benzoic acid. This dependence drops out 2=nitrobenzoic and 1=naphthoic acids, which have relatively low reactivity and the greatest steric hindrances both for nucleophilic attack by aniline and for possible coordination with catalytically active centers of the corresponding ortho-substituted titanium polybutoxybenzoates formed in situ. Based on these data, the previously proposed mechanism of bifunctional catalysis due to titanium polybutoxybenzoates and their complexes with meta- and parasubstitutedbenzanilides was supplemented by the possibility of the steric inhibition of reaction by the most bulky substituents and chelate structures formation of orthosubstituted benzoic acids and their anilides with individual titanium atoms of the catalyst, as well as the simulta­neous H-bonding of the amino group hydrogen atoms of aniline, which leads to its activation to a nucleophilic attack, with a carbonyl group and an orthopositioned substituent of the orthobenzoate ligand in the coordination sphere of titanium. Taking into account such chelation and steric barriers, as well as inhibition of acid catalysis due to the formation of the imide form of anilides, containing electron-withdrawing substituents, the equations for the rate constants of the catalytic reaction of ortho-substituted benzoic acids with aniline are derived, corresponding to the experimentally obtained Hammett dependence. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-04-23 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/287 10.33609/2708-129X.87.03.2021.18-40 Ukrainian Chemistry Journal; Vol. 87 No. 3 (2021): Ukrainian Chemistry Journal; 18-40 Украинский химический журнал; Том 87 № 3 (2021): Ukrainian Chemistry Journal; 18-40 Український хімічний журнал; Том 87 № 3 (2021): Український хімічний журнал; 18-40 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/287/159
institution Ukrainian Chemistry Journal
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datestamp_date 2021-05-13T15:07:38Z
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language English
topic_facet polybutoxytitanates
kinetics
reaction rate constant
ortho-substituted benzoic acids
aniline
substituted benzanilides
Hammett’s equation
catalysis.
format Article
author Shteinberg, Leon
spellingShingle Shteinberg, Leon
ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ
author_facet Shteinberg, Leon
author_sort Shteinberg, Leon
title ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ
title_short ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ
title_full ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ
title_fullStr ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ
title_full_unstemmed ВПЛИВ ЗАМІСНИКІВ НА ШВИДКІСТЬ РЕАКЦІЇ ОРТОЗАМІЩЕНИХ БЕНЗОЙНИХ КИСЛОТ З АНІЛІНОМ, ЩО КАТАЛІЗУЄТЬСЯ ПОЛІБУТОКСИТИТАНАТАМИ
title_sort вплив замісників на швидкість реакції ортозаміщених бензойних кислот з аніліном, що каталізується полібутоксититанатами
title_alt INFLUENCE OF SUBSTITUTES ON THE RATE OF THE REACTION OF ORTHOSUBSTITUTED BENZOIC ACIDS WTH ANILINE, CATALYZED BY POLYBUTOXYTITANATES
description The polybutoxytitanates catalysis of aniline acylation by orthosubstituted benzoic acids leads to the production of substituted benzanilides. Catalytic rate constants of the second order reaction (the first with respect to aniline and ortho-substituted benzoic acid; boiling ortho=xylene, 145°C) correlate well according to the Hammett and Bronsted equations with straight line segments with ρ=1.93 and α=0.66, in contrast to the reaction of aniline with meta- and parasubstituted benzoic acids and substituted anilines with benzoic acid. This dependence drops out 2=nitrobenzoic and 1=naphthoic acids, which have relatively low reactivity and the greatest steric hindrances both for nucleophilic attack by aniline and for possible coordination with catalytically active centers of the corresponding ortho-substituted titanium polybutoxybenzoates formed in situ. Based on these data, the previously proposed mechanism of bifunctional catalysis due to titanium polybutoxybenzoates and their complexes with meta- and parasubstitutedbenzanilides was supplemented by the possibility of the steric inhibition of reaction by the most bulky substituents and chelate structures formation of orthosubstituted benzoic acids and their anilides with individual titanium atoms of the catalyst, as well as the simulta­neous H-bonding of the amino group hydrogen atoms of aniline, which leads to its activation to a nucleophilic attack, with a carbonyl group and an orthopositioned substituent of the orthobenzoate ligand in the coordination sphere of titanium. Taking into account such chelation and steric barriers, as well as inhibition of acid catalysis due to the formation of the imide form of anilides, containing electron-withdrawing substituents, the equations for the rate constants of the catalytic reaction of ortho-substituted benzoic acids with aniline are derived, corresponding to the experimentally obtained Hammett dependence.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2021
url https://ucj.org.ua/index.php/journal/article/view/287
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