THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ
Chlorine-containing condensing agents (PCl3, TiCl4, SiCl4) are widely used in the synthesis of carboxylic acid arylamides by the reaction of arylamines with carboxylic acids in stoichiometric amounts, and often in excess (40–150 mol % relative to the latter). To find the optimal amount of the conden...
Збережено в:
| Дата: | 2023 |
|---|---|
| Автор: | |
| Формат: | Стаття |
| Мова: | English |
| Опубліковано: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2023
|
| Онлайн доступ: | https://ucj.org.ua/index.php/journal/article/view/553 |
| Теги: |
Додати тег
Немає тегів, Будьте першим, хто поставить тег для цього запису!
|
| Назва журналу: | Ukrainian Chemistry Journal |
Репозитарії
Ukrainian Chemistry Journal| id |
oai:ojs2.1444248.nisspano.web.hosting-test.net:article-553 |
|---|---|
| record_format |
ojs |
| spelling |
oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5532023-08-10T12:23:11Z THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ Shteinberg, Leon trichloride phosphorus, phosphorous acid, 3-hydroxy-2-naphthoic acid, anilide of 3-hydroxy-2-naphthoic acid, aniline, benzoic acid, titanium tetrachloride, silicon tetrachloride, catalysis, salicylic acid. Chlorine-containing condensing agents (PCl3, TiCl4, SiCl4) are widely used in the synthesis of carboxylic acid arylamides by the reaction of arylamines with carboxylic acids in stoichiometric amounts, and often in excess (40–150 mol % relative to the latter). To find the optimal amount of the condensing agent used, the acylation of aniline with 3-hydroxy-2-naphthoic acid in boiling ortho-xylene was studied in the PCl3 concentration range of 0–10 mol % from 3-hydroxy-2-naphthoic acid. It has been established that phosphorus tri-chlorochloride plays the role of a condensing agent and a catalyst, while 3-hydroxy-2-naphthoic acid anilide is formed along two routes with different rates, which can be separated kinetically. The first route includes the rapid synthesis of acid chloride, its interaction with aniline to obtain the target product. The second route is implemented due to phosphorous acid, which is formed from phosphorus trichloride and is a true acylation catalyst. The maximum yield of anilide 3-hydroxy-2-naphthoic acid decreases with increasing catalyst concentration, approximately propor-tional to the amount of aniline phosphite formed from it in the mass, which, apparently, is not reactive when interacting with the starting acid. Similar patterns were also found in the acylation of aniline with benzoic and salicylic acids in the presence of phosphorus trichloride; benzoic acid in the presence of titanium tetrachloride; 3-hydroxy-2-naphthoic acid in the presence of silicon tetrachloride. They allow a new look at the role of these products (PCl3, TiCl4, SiCl4) as condensing agents and/or catalysts in the synthesis of amides of carboxylic acids. Taking into account the obtained results, in practice it is better to use PCl3 as a catalyst in an amount not exceeding 2–2.5%, or even to replace it with phosphorous acid. This allows to completely get rid of the release of hydrogen chloride, significantly reduce the consumption rates for raw materials, simplify the entire technological process, reduce the amount of waste, ensure the yield of 3-hydroxy-2-naphthoic acid anilide close to quantitative, create a direct catalytic amidation technology that fully meets the criteria «green» chemistry processes. V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-06-26 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/553 10.33609/2708-129X.89.05.2023.37-52 Ukrainian Chemistry Journal; Vol. 89 No. 5 (2023): Ukrainian Chemistry Journal; 37-52 Украинский химический журнал; Том 89 № 5 (2023): Ukrainian Chemistry Journal; 37-52 Український хімічний журнал; Том 89 № 5 (2023): Ukrainian Chemistry Journal; 37-52 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/553/283 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
|
| datestamp_date |
2023-08-10T12:23:11Z |
| collection |
OJS |
| language |
English |
| topic_facet |
trichloride phosphorus phosphorous acid 3-hydroxy-2-naphthoic acid anilide of 3-hydroxy-2-naphthoic acid aniline benzoic acid titanium tetrachloride silicon tetrachloride catalysis salicylic acid. |
| format |
Article |
| author |
Shteinberg, Leon |
| spellingShingle |
Shteinberg, Leon THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ |
| author_facet |
Shteinberg, Leon |
| author_sort |
Shteinberg, Leon |
| title |
THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ |
| title_short |
THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ |
| title_full |
THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ |
| title_fullStr |
THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ |
| title_full_unstemmed |
THE INFLUENCE OF THE CONCENTRATION OF CHLORINE-CONTAINING CONDENSING AGENTS IN THE SYNTHESIS OF CARBOXYLIC ACID ANILIDESТ |
| title_sort |
influence of the concentration of chlorine-containing condensing agents in the synthesis of carboxylic acid anilidesт |
| description |
Chlorine-containing condensing agents (PCl3, TiCl4, SiCl4) are widely used in the synthesis of carboxylic acid arylamides by the reaction of arylamines with carboxylic acids in stoichiometric amounts, and often in excess (40–150 mol % relative to the latter). To find the optimal amount of the condensing agent used, the acylation of aniline with 3-hydroxy-2-naphthoic acid in boiling ortho-xylene was studied in the PCl3 concentration range of 0–10 mol % from 3-hydroxy-2-naphthoic acid. It has been established that phosphorus tri-chlorochloride plays the role of a condensing agent and a catalyst, while 3-hydroxy-2-naphthoic acid anilide is formed along two routes with different rates, which can be separated kinetically. The first route includes the rapid synthesis of acid chloride, its interaction with aniline to obtain the target product. The second route is implemented due to phosphorous acid, which is formed from phosphorus trichloride and is a true acylation catalyst.
The maximum yield of anilide 3-hydroxy-2-naphthoic acid decreases with increasing catalyst concentration, approximately propor-tional to the amount of aniline phosphite formed from it in the mass, which, apparently, is not reactive when interacting with the starting acid.
Similar patterns were also found in the acylation of aniline with benzoic and salicylic acids in the presence of phosphorus trichloride; benzoic acid in the presence of titanium tetrachloride; 3-hydroxy-2-naphthoic acid in the presence of silicon tetrachloride. They allow a new look at the role of these products (PCl3, TiCl4, SiCl4) as condensing agents and/or catalysts in the synthesis of amides of carboxylic acids.
Taking into account the obtained results, in practice it is better to use PCl3 as a catalyst in an amount not exceeding 2–2.5%, or even to replace it with phosphorous acid. This allows to completely get rid of the release of hydrogen chloride, significantly reduce the consumption rates for raw materials, simplify the entire technological process, reduce the amount of waste, ensure the yield of 3-hydroxy-2-naphthoic acid anilide close to quantitative, create a direct catalytic amidation technology that fully meets the criteria «green» chemistry processes. |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2023 |
| url |
https://ucj.org.ua/index.php/journal/article/view/553 |
| work_keys_str_mv |
AT shteinbergleon theinfluenceoftheconcentrationofchlorinecontainingcondensingagentsinthesynthesisofcarboxylicacidanilidest AT shteinbergleon influenceoftheconcentrationofchlorinecontainingcondensingagentsinthesynthesisofcarboxylicacidanilidest |
| first_indexed |
2025-09-24T17:43:51Z |
| last_indexed |
2025-09-24T17:43:51Z |
| _version_ |
1849658128012935168 |