RING-CHAIN TAUTOMERISM IN THE PRODUCTS OF THE REACTION BETWEEN 5-SUBSTITUTED FURFURYLAMINES AND ANHYDRIDES OF α,β-UNSATURATED CARBOXYLIC ACIDS

Authors

  • Фёдор И. Зубков People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198
  • Виктор Д. Голубев People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198
  • Владимир П. Зайцев People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198
  • Ольга В. Баханович People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198
  • Евгения В. Никитина People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198
  • Виктор Н. Хрусталёв People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198
  • Ринат Р. Айсин A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St., Moscow 119991
  • Татьяна В. Тимофеева Department of Chemistry & Biology, New Mexico Highlands University, 803 University Ave., Las-Vegas, NM 87701
  • Роман А. Новиков V. A. Engel'gardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilova St., Moscow 119991
  • Алексей Васильевич Варламов People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

DOI:

https://doi.org/10.1007/2818

Keywords:

furan, isoindole, [4 2] cycloaddition, dynamic stereochemistry, intramolecular Diels–Alder reaction, ring-chain tautomerism

Abstract

The reactions of 5-substituted furfurylamines with anhydrides of α,β-unsaturated carboxylic acids (acryloyl chloride and maleic anhydride) were studied. The first step of the reaction mechanism involved acylation of furfurylamine nitrogen atom, followed by a stereospecific, spontaneous intramolecular Diels–Alder reaction at the furan ring of the N-furfurylamide intermediates. When the starting materials were 5-alkyl-substituted furfurylamines, the expected 1-oxo-2,3,7,7a-hexahydro-1Н-3а,6-epoxyisoindoles or the corresponding 7carboxylic acids were obtained in up to 98% yields. The acylation of 5-aryl-substituted furfurylamines with maleic anhydride led to N-furfurylmaleic amides, which formed a dynamic equilibrium in solutions with adducts formed by intramolecular [4+2] cycloaddition, 3а,6-epoxyisoindole-7-carboxylic acids, as proved by NMR spectroscopy. X-ray structural analysis results show that these mixtures crystallized in the form of the cyclic tautomer.

Authors: Fedor I. Zubkov*, Victor D. Golubev, Vladimir P. Zaytsev, Olga V. Bakhanovich, Evgeniya V. Nikitina, Victor N. Khrustalev, Rinat R. Aysin, Tatiana V. Timofeeva, Roman A. Novikov, Aleksey V. Varlamov

Author Biographies

Фёдор И. Зубков, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Фёдор Иванович Зубков

доцент кафедры органической химии, Российского университета дружбы народов

Виктор Д. Голубев, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Аспирант кафедры органической химии, факультета физико-математических и естественных наук

Владимир П. Зайцев, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Владимир Петрович Зайцев

доцент кафедры органической химии, факультета физико-математических и естественных наук

Ольга В. Баханович, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Магистр кафедры органической химии, факультета физико-математических и естественных наук

Евгения В. Никитина, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Евгения Валентиновна Никитина

Заместитель декана по научной работе факультета физико-математических и естественных наук

Виктор Н. Хрусталёв, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Виктор Николаевич Хрусталёв

Заведующй кафедрой неорганической химии факультета физико-математических и естественных наук

Татьяна В. Тимофеева, Department of Chemistry & Biology, New Mexico Highlands University, 803 University Ave., Las-Vegas, NM 87701

Department of Chemistry Biology

Роман А. Новиков, V. A. Engel'gardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilova St., Moscow 119991

Лаборатория ЯМР

Алексей Васильевич Варламов, People’s Friendship University of Russia, 6 Miklukho-Maklaya St., Moscow 117198

Алексей Васильевич Варламов

Заведующих кафедрой органической химии

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Published

2016-04-11

Issue

Vol. 52 No. 4 (2016)

Section

Original Papers