CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES

CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES

Catalysis of the acylation of aniline with 3-­hydroxy-2-naphthoic, 1-hydroxy-2-naphthoic, 2-hydroxy-1-naphthoic and 1-hydroxy-4-naphthoic acids by phosphorus P(III) and silicon Si(IV) compounds leads to the formation anilides of the corresponding hydroxy­naphthoic acids under mild conditions (ortho-...

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Date:2023
Main Author: Shteinberg, Leon
Format: Article
Language:English
Published: V.I.Vernadsky Institute of General and Inorganic Chemistry 2023
Online Access:https://ucj.org.ua/index.php/journal/article/view/517
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Journal Title:Ukrainian Chemistry Journal

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Ukrainian Chemistry Journal
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spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5172023-04-18T13:56:30Z CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES Shteinberg, Leon phosphorus trichloride, phosphorous acid, silicon tetrachloride, hyd­roxy-naphthoic acids, hydroxynaphthoic acid anilides, aniline, catalysis Catalysis of the acylation of aniline with 3-­hydroxy-2-naphthoic, 1-hydroxy-2-naphthoic, 2-hydroxy-1-naphthoic and 1-hydroxy-4-naphthoic acids by phosphorus P(III) and silicon Si(IV) compounds leads to the formation anilides of the corresponding hydroxy­naphthoic acids under mild conditions (ortho-xylene, 146.5–147 °C) in almost quantitative yield. Among P(III) phosphorus trichloride and tribromide; phosphorous, 1-hydroxyethyli­de­ne-di­phos­phonic, pyrophosphorous and me­ta­phos­phorous acids; trimethyl-, dimethyl- and diethylphosphites; phosph(III)azan proved to be active catalysts; among Si(IV) – tri­chloro-(methyl)silane, dichloro(ethyl)silane, dichloro­(dimethyl)silane, tetrachlorosilane and tet­ra­ethoxysilane are active. The catalysts were used in an amount of only 2% mole. from hydroxynaphthoic acid, which is 15–35 times less than the conventional use of the same compounds as condensing agents in the synthesis of carboxylic acid arylamides. P(V) compounds, thionyl chloride, and sulfuryl chloride practically do not exhibit catalytic activity. The presence of catalytic activity only in P(III) compounds, capable of forming phosphorous acid in the reaction mass, does not contradict to the previously proposed mechanism of P = O-nucleophilic catalysis for the reaction of substituted benzoic acids with aniline catalyzed by PCl3. In general, the use of P(III) and Si(IV) compounds as catalysts in the preparation of hydroxybenzoic and hydroxynaphthoic acid anilides successfully complements the range of catalysts, based on Ti(IV) compounds, previously used in the formation of substituted benzoic and naphthoic acid anilides (containing no aromatically bonded hydroxy group), allowing to create a universal method for their synthesis. V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-02-24 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/517 10.33609/2708-129X.89.01.2023.46-59 Ukrainian Chemistry Journal; Vol. 89 No. 1 (2023): Ukrainian Chemistry Journal; 46-59 Украинский химический журнал; Том 89 № 1 (2023): Ukrainian Chemistry Journal; 46-59 Український хімічний журнал; Том 89 № 1 (2023): Український хімічний журнал; 46-59 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/517/264
institution Ukrainian Chemistry Journal
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datestamp_date 2023-04-18T13:56:30Z
collection OJS
language English
topic_facet phosphorus trichloride
phosphorous acid
silicon tetrachloride
hyd­roxy-naphthoic acids
hydroxynaphthoic acid anilides
aniline
catalysis
format Article
author Shteinberg, Leon
spellingShingle Shteinberg, Leon
CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES
author_facet Shteinberg, Leon
author_sort Shteinberg, Leon
title CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES
title_short CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES
title_full CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES
title_fullStr CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES
title_full_unstemmed CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES
title_sort catalysis by phosphorus and silicon compounds in the synthesis of oxynaphtoic acid anilides
description Catalysis of the acylation of aniline with 3-­hydroxy-2-naphthoic, 1-hydroxy-2-naphthoic, 2-hydroxy-1-naphthoic and 1-hydroxy-4-naphthoic acids by phosphorus P(III) and silicon Si(IV) compounds leads to the formation anilides of the corresponding hydroxy­naphthoic acids under mild conditions (ortho-xylene, 146.5–147 °C) in almost quantitative yield. Among P(III) phosphorus trichloride and tribromide; phosphorous, 1-hydroxyethyli­de­ne-di­phos­phonic, pyrophosphorous and me­ta­phos­phorous acids; trimethyl-, dimethyl- and diethylphosphites; phosph(III)azan proved to be active catalysts; among Si(IV) – tri­chloro-(methyl)silane, dichloro(ethyl)silane, dichloro­(dimethyl)silane, tetrachlorosilane and tet­ra­ethoxysilane are active. The catalysts were used in an amount of only 2% mole. from hydroxynaphthoic acid, which is 15–35 times less than the conventional use of the same compounds as condensing agents in the synthesis of carboxylic acid arylamides. P(V) compounds, thionyl chloride, and sulfuryl chloride practically do not exhibit catalytic activity. The presence of catalytic activity only in P(III) compounds, capable of forming phosphorous acid in the reaction mass, does not contradict to the previously proposed mechanism of P = O-nucleophilic catalysis for the reaction of substituted benzoic acids with aniline catalyzed by PCl3. In general, the use of P(III) and Si(IV) compounds as catalysts in the preparation of hydroxybenzoic and hydroxynaphthoic acid anilides successfully complements the range of catalysts, based on Ti(IV) compounds, previously used in the formation of substituted benzoic and naphthoic acid anilides (containing no aromatically bonded hydroxy group), allowing to create a universal method for their synthesis.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2023
url https://ucj.org.ua/index.php/journal/article/view/517
work_keys_str_mv AT shteinbergleon catalysisbyphosphorusandsiliconcompoundsinthesynthesisofoxynaphtoicacidanilides
first_indexed 2025-09-24T17:43:49Z
last_indexed 2025-09-24T17:43:49Z
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