Изучение основно-катализируемых реакций циклизации гидрокси- и орто-(ацил)гидроксикумаринов тема автореферата и диссертации по химии, 02.00.03 ВАК РФ

I. Введение 4 И. Основные методы получения ангелицина, псоралена и их производных (обзор литературы)

II. 1. Синтезы на основе аллилоксикумаринов

11.2. Реакция Виттига в синтезе фурокумаринов

11.3. Синтезы на основе ацилметиловых эфиров кумаринов

11.4. Синтез фурокумарин-5'-карбоновых кислот и их производных

11.5. Синтез 5'(4')-ацилфурокумаринов

11.6. Синтез фурокумаринов с электроноакцепторными заместителями в пироновом кольце

11.7. Синтез гидрокси-и алкоксифурокумаринов

11.8. Синтез аминофурокумаринов 37 III. Обсуждение результатов 46 III. 1. Новый метод синтеза эфиров фурокумарин-5 '-карбоновых кислот

III. 1.2. Синтез 5 '-карбэтоксифурокумаринов

III. 1.2. Синтез холестериловых эфиров

111.2. Синтез новых фурокумаринов 55 III.2.1. Синтез 5'-ацилфурокумаринов 55 III.2.2 Синтез арил- и алкил- псораленов

111.3. Новые реакции трансформации лактонного кольца производных кумарина в присутствии слабых оснований

111.4. Синтез гидрокси- и метоксифурокумаринов

111.5. Синтез и восстановление оксимов ацилфурокумаринов

III.6. Прикладные свойства новых фурокумаринов

IV. Экспериментальная часть 80 IV. 1. Синтез исходных гидроксикумаринов 80 IV.2. Синтез сложных эфиров гидроксикумаринов 82 IV.3. Синтез орто-ацил-7-гидроксикумаринов 83 IV.4. Синтез тозилата холестерина 84 IV.5. Синтез хлорацетата холестерина 84 IV.6. Синтез сложных эфиров 5'-фурокумаринкарбоновых кислот 84 IV.7. Синтез холестериловых эфиров 86 IV.8. Синтез этилового эфира 2-(4-метил-2-оксо-2Н-[1] бензопиранил-7-окси)бутановой кислоты

IV.9. Синтез карбоновых кислот

IV. 10. Синтез холестерил 2-(4-метил-2-оксо-2Н-[1 ] бензопиранил-7окси)бутаноата

IV.11. Синтез 8-ацил-2Н-фуро[2,3-11][1]бензоприран-2-онов и

2-ацил-7Н-фуро [3,2-g] [ 1 ] бензопиран-7-онов

IV. 12. Синтез ацилметиловых эфиров кумаринов

IV.13. Синтез производных 7Н-фуро[3,2-g][1]бензопиран-7-она

IV. 14. Синтез оксимов 5'-ацилфурокумаринов

IV. 15. Восстановление оксима

IV. 16. Восстановление 5'-ацилфурокумаринов

IV. 16.1. Синтез спиртов

IV. 16.2. Синтез простых метиловых эфиров

IV. 17. Реакции трансформации приронового цикла

V. Выводы

V. Выводы.

1. Разработан новый способ синтеза эфиров фурокумарин-5'-карбоновых кислот, основанный на конденсации орто-ацил(гидрокси)кумаринов с эфирами моногалогенуксусных кислот.

2. Указанным способом впервые получены холестериловые эфиры фурокумаринкарбоновых кислот.

3. Разработаны удобные способы получения гидрокси-, метокси-, ацил-, аминометил- и бензилфурокумаринов.

4. Обнаружены новые реакции трансформации пиронового цикла 3-карбоэтоксикумарина в присутствии слабых оснований, протекающие с сокращением и циклопропанированием лактонного кольца. Изучено влияние заместителей в бензольном кольце кумарина на направление трансформации.

5. Синтезированы и охарактеризованы методами спектроскопии ПМР и масс-спектрометрии 74 новых производных кумарина, в том числе 52 новых фурокумарина.

6. Установлено, что холестериловые эфиры карбоновых кислот фурокумаринов и кумаринов образуют устойчивые мономолекулярные слои Ленгмюра-Блоджетт, и перспективны для создания на их основе материалов молекулярной электроники (по данным НИИ физических проблем, г. Зеленоград).

7. Ряд фурокумаринов передан для изучения их взаимодействия с ДНК в Центральный научно-исследовательский рентгено-радиологической институт РАМН (г. Санкт-Петербург). Найдено высокое значение темновой константы связывания для 2-ацетил-3,5,9-триметилпсоралена.

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