Donetsk National Technical University
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https://ea.donntu.edu.ua/jspui/handle/123456789/26005| Title: | Применение инверсионного трансфазного катализа для реакций фосфорилирования фенолов |
| Other Titles: | APPLICATION OF INVERSE PHASE TRANSFER CATALYSIS FOR THE PHOSPHORYLATION OF PHENOL |
| Authors: | Анищенко, В.Н. Рыбаченко, В.И. Чотий, К.Ю. Редько, А.Н. |
| Keywords: | фосфорилирование пиридин-1-оксид DFT phosphorylation pyridine-1-oxide |
| Issue Date: | 2014 |
| Publisher: | Наукові праці ДонНТУ. Серія: Хімія і хімічна технологія. - 2014. - Вип. 2(23). - С. 97-104 |
| Abstract: | Исследован инверсионный трансфазный катализ (ИТК) реакции фосфорилирования фенолов в двухфазной системе вода/дихлорметан. В качестве катализаторов использовали производные пиридин-1-оксида. С помощью квантово-химических расчетов изучена реакция хлордифенилфосфата с пара-замещенными пиридин-1-оксидами в среде дихлорметана. |
| Description: | Inverse phase transfer catalysis of phosphorylation of phenol was studied. Para- substituted (4-methyl, 4-methoxy-, 4-morpholino- and 4-dimethylamino-) pyridine-1-oxides were used as IPT catalysts. The reaction proceeds via the formation of an ionic intermediate in the organic phase – 1-(diphenoxyphosphoryl)oxypyridinium chloride. Effect of catalyst structure on activation energy and product yield was investigated on the phosphorylation of 4-nitrophenol. With increasing basicity of the catalyst a lower activation energy and higher product yield were reached. Moreover, decreasing of reaction temperature leads to increasing of product yield due to retarding of hydrolysis of ionic intermediate. The first stage of IPTC process was the reaction between diphenyl chlorophosphate and para-substituted pyridine-1-oxide and it was theoretically studied using quantum chemistry at the DFT level of theory. Influence of solvent was taken into account by adding one molecule of dichloromethane and COSMO model. It was shown that diphenyl chlorophosphate, transitional states and -(diphenoxyphosphoryl)oxypyridinium chloride could exist in several conformational forms. Spatial orientation of phenyl rings significantly influence reactivity of chlorophosphate. Good correlation between experimental activation energy and calculated free activation energy was obtained. |
| URI: | http://ea.donntu.edu.ua/handle/123456789/26005 |
| Appears in Collections: | Випуск 2(23), 2014 |
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