Лящук С.Н., Дорошенко Т.Ф. Направления реакции циклоприсоединения бис(диоксидо- λ6-сульфанилиден)метана к активированным олефинам
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| Title |
Лящук С.Н., Дорошенко Т.Ф. Направления реакции циклоприсоединения бис(диоксидо- λ6-сульфанилиден)метана к активированным олефинам
CYCLOADDITION REACTION ROUTES OF BIS(DIOXIDO-λ6- SULFANILIDEN)METHANE TO ACTIVATED OLEFINES |
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| Creator |
Лящук, С.Н.
Дорошенко, Т.Ф. |
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| Subject |
гетерокумулены
тиоальдегиддиоксиды циклоприсоединение изомеры квантово-химические расчеты heterocumulenes thioaldehydedioxides cycloaddition isomers quantum- chemical calculations |
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| Description |
It is known that aliphatic sulfonyl chlorides in the presence of triethylamine react with compounds containing electron-donating substituents that activate of ethylenic bonds. These reactions may lead to formation as acyclic as heterocyclic products. In view of these facts, it is represented perspective using methanedisulfonyl chloride in similar reactions and examination of an opportunity of participation of the intermediate bis(dioxido-λ6-sulfaniliden)methane or (dioxido-λ6-sulfanylidene)-methanesulfonyl chloride in reactions with some ethenes. The possibility of realization of these reactions for synthesis of insufficiently studied sulfur-containing heterocyclic compounds was tested by the example of several processes. It was found that with diethylacetal of ketene in chloroform or methylene chloride medium with a yield of 45 % the product of double cycloaddition, i.e. spirodithiethanetetraoxide (3,3,7,7-tetra-ethoxy-1,5-dithiaspiro[3.3]heptane 1,1,5,5-tetraoxide) is formed. Formation of spiro compound can be explained both with the supposition of the bis(dioxido-λ6-sulfaniliden)methane intermediate and through formation of thietane-S,S-dioxides. The spirodithiethanetetraoxide has only restricted stability and at ageing in the ethanol solution within day give the 2-[(2,2-diethoxyethenyl)sulfonyl]-3,3-diethoxy-thietane 1,1-dioxide quantitatively with tearing up of one of rings. Similar reaction of methanedisulfonyl chloride with 1-morpholinocyclohexene in the presence of triethylamine does not result in formation of spiro- system. With a yield of 30-40 % it is formed only acyclic 4-[6-({[2-(morpholin-4-yl)cyclohex-2-ene-1-sulfonyl]methane}sulfonyl)cyclohex-1-ene-1-yl]morpholine. The fact that spiro- system in this case is not formed, apparently, it is possible to explain by presence of the considerable steric difficulties for embodying such process. Reaction of methanedisulfonyl chloride, triethylamine and 1-piperidinopropene under the same conditions result in formation of 3-(piperidin-1-yl)-2-({[1-(piperidin-1-yl)prop-1-ene-2-sulfonyl]-methane}sulfonyl)prop-2-ene-1-ylidene with a yield of 15-25%. It is probable that the mechanism of reaction in this case includes formation of spiro-system, similar that was observed at use of acetal of the ketene, however available steric difficulties lead to disclosing cycles already in the time of carrying out of reaction and to formation of an acyclic product. The results of quantum chemical calculations at PM7 semi-empirical approximation showed that the bis(dioxido-λ6-sulfaniliden)methane is a stronger electrophile than its carbon analogue (propadiene-1,3-dione) which is consistent with the peculiarities of its behavior in the reactions with compounds containing ethylenic bond . Реакции бис(диоксидо-λ6-сульфанилиден)метана, полученного из метандисульфонил-хлорида и триэтиламина, c рядом соединений, содержащих активированную электронодонорным заместителем этиленовую связь (1-морфолиноциклогексеном, 1-пиперидинопропеном и диэтилацеталем кетена) приводят к образованию продуктов замещения и спиробитиетантетроксидам в зависимости от природы заместителей в этене и условий проведения реакции. Предложен двухстадийный механизм образования бис(диоксидо-λ6-сульфанилиден)метана из соответствующего сульфохлорида. Результаты квантово-химических расчетов показали, что бис(диоксидо-λ6-сульфанилиден)метан является более сильным электрофилом по сравнению с его углеродным аналогом (пропадиен-1,3-дионом), что согласуется с особенностями его поведения в реакциях присоединения к соединениям, содержащим этиленовую связь. |
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| Date |
2014-04-15T14:42:26Z
2014-04-15T14:42:26Z 2014 |
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| Type |
Article
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| Identifier |
УДК 547.56:547.233:541.127/128
http://ea.donntu.edu.ua/handle/123456789/25982 |
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| Language |
other
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| Publisher |
Наукові праці ДонНТУ. Серія: Хімія і хімічна технологія. - 2014. - Вип. 1(22). - С. 134-141
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