РЕАКЦИЯ ЭШВАЙЛЕРА-КЛАРКА В СИНТЕЗЕ ТЕТРАГИДРОБЕНЗО-ТИЕНО[2,3-С]ПИРИДИНОВ, ТЕТРАГИДРОБЕНЗОФУРО[2,3-С]ПИРИДИНОВ, ТЕТРАГИДРОБЕНЗОТИЕНО[2,3-С]АЗЕПИНОВ
Електронний архів E-archive DonNTU – (Electronic archive Donetsk National Technical University)
Переглянути архів Інформація| Поле | Співвідношення | |
| Title |
РЕАКЦИЯ ЭШВАЙЛЕРА-КЛАРКА В СИНТЕЗЕ ТЕТРАГИДРОБЕНЗО-ТИЕНО[2,3-С]ПИРИДИНОВ, ТЕТРАГИДРОБЕНЗОФУРО[2,3-С]ПИРИДИНОВ, ТЕТРАГИДРОБЕНЗОТИЕНО[2,3-С]АЗЕПИНОВ
ESCHWEILER-CLARKE REACTION IN SYNTHESIS OF TETRAHYDROBENZOTHIENO[2,3-C]PYRIDINES, TETRAHYDROBENZOFURO [2,3-C]PYRIDINES, TETRAHYDROBENZOTHIENO[2,3-C]PYRIDINES |
|
| Creator |
Ересько, Александр Борисович
Толкунов, Валерий Сергеевич Толкунов, Сергей Владимирович |
|
| Subject |
1,2,3,4-тетрагидробензофуро[2,3-с]пиридины
2,3,4,5-тетрагидро-1H-[1]бензотиено[2,3-c]азепины Реакция Эшвайлера-Кларка реакция Пикте-Шпенглера 1,2,3,4 тетрагидробензотиено[2,3-с]пиридины 2,3,4,5-tetrahydro-1H-[1]benzothieno[2,3-c]azepines Eschweiler–Clarke reaction Pictet-Spengler reaction 1,2,3,4-tetrahydrobenzothieno[2,3-c]pyridines 1,2,3,4-tetrahydrobenzofuro[2,3-c]pyridines |
|
| Description |
Синтезирована серия неизвестных ранее 1,2,3,4-тетрагидробензотиено[2,3-с]пири-динов, 1,2,3,4-тетрагидробензофуро[2,3-с]пиридинов, 2,3,4,5-тетрагидро-1H-[1]бензотиено[2,3-c]азе-пинов с использованием реакций Эшвайлера-Кларка и Пикте-Шпенглера.
The Eschweiler-Clarke reaction is commonly used for methylation of primary or secondary amines by the action of formaldehyde in the presence of formic acid. This reaction can be used for obtaining of 2-methyltetrahydropyridines as well as azepines. The 1-R-1,2,3,4-tetrahydrobenzothieno[2,3-c]pyridines and 7-methyl-1-R-1,2,3,4-tetrahydrobenzofuro[2,3-c]pyridines obtained by Pictet-Spengler reaction was used as the starting products for the synthesis of 2-methylderivatives by the Eschweiler-Clarke reaction. A different behavior of initial 2-(1-hetaryl-3)ethylamine by Pictet-Spengler reaction was found. The reaction proceeds well in the series of benzofuranes. Under similar conditions, [2-(1-benzothien-3-yl)ethyl]amine reacts with benzaldehyde to form by-products – aminoacetales. Interaction of [2-(1-benzothien-3-yl)ethyl]methylamine and benzaldehyde under Pictet-Spengler reaction occurs exclusively with the formation of aminoacetales, so this method is not applicable for the preparation of 1-aryl-2-metiltetragidrobenzotieno[2,3-c]pyridine. These pyridines were synthesized by the methylation with formaldehyde in formic acid by the reaction of Eschweiler-Clarke. Methylation of 7-methyl-1-R-1,2,3,4-tetrahydrobenzofuro[2,3-c]pyridines with formic acid and formaldehyde mixture in the Eschweiler–Clarke reaction conditions does not lead to the 2,7-dimethyl-1-R-1,2,3,4-tetrahydrobenzofuro[2,3-c]pyridine formation. Corresponding 2,7-dimethyl-1,2,3,4-tetrahydro[1]benzofuro[2,3-c]pyridine was obtained by this method. This compound is formed directly from the [2-(6-methyl-1-benzofuran-3-yl)ethyl]amine in the Eschweiler–Clarke reaction conditions. Eschweiler-Clarke reaction proceeds well in the series of benzothienyl-3-ethyl(propyl)amine. 2-Methyl-1,2,3,4-benzothieno[2,3-c]pyridines and 2-methyl-2,3,4,5-tetrahydro-1H-benzothieno[2,3-c]azepine were obtained by heating of 2-(1-benzothienyl-3)ethylamine and benzothienyl-3-propylamine in a mixture of 90% formic acid - formaldehyde in high yields. Benzothienyl-3-propylamine does not react with aromatic aldehydes under any conditions. We have shown that the Eschweiler–Clarke reaction conditions can be successfully used for obtaining of N-substituted derivatives of benzothieno[2,3-c]pyridines and benzothieno[2,3-c]azepine. |
|
| Date |
2013-04-11T15:37:44Z
2013-04-11T15:37:44Z 2013 |
|
| Type |
Article
|
|
| Identifier |
2074-6652
УДК 547.735’83+547.728.1’83+547.735’89 http://ea.donntu.edu.ua/handle/123456789/18404 |
|
| Relation |
Наукові праці ДонНТУ;Серія: Хімія і хімічна технологія, 2013. - Вип.1(20). - С.109-115
|
|
| Publisher |
Донецк, ДонНТУ
|
|