ИЗУЧЕНИЕ РЕАКЦИИ ФОСФОРИЛИРОВАНИЯ ФЕНОЛОВ В УСЛОВИЯХ ИНВЕРСИОННОГО ТРАНСФАЗНОГО КАТАЛИЗА
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| Title |
ИЗУЧЕНИЕ РЕАКЦИИ ФОСФОРИЛИРОВАНИЯ ФЕНОЛОВ В УСЛОВИЯХ ИНВЕРСИОННОГО ТРАНСФАЗНОГО КАТАЛИЗА
STUDY OF THE REACTION OF THE PHENOL PHOSPHORYLATION UNDER INVERSE PHASE TRANSFER CATALYSIS |
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| Creator |
Анищенко, Виктор Николаевич
Рыбаченко, Владимир Иванович Чотий, Константин Юрьевич Редько, Андрей Николаевич |
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| Subject |
DFT
IGLO фосфорилирование ИТФК пиридин-1-оксид 1H и 31P ЯМР ИК |
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| Description |
Ряд арилдифенилфосфатов синтезировано в условиях инверсионного трансфазного катализа (ИТФК). Предложена схема реакции фенолов с хлордифенилфосфатом в двухфазной системе H2O/CH2Cl2. В качестве катализаторов использовали производные пиридин-1-оксида. Реакция протекает через стадию образования ионного интермедиата (хлорида 1-(дифеноксифосфорил)оксипиридиния) в органической фазе, что установлено с помощью ИК и 1Н ЯМР спектроскопии. Строение полученных арилдифенилфосфатов подтверждено методами ИК, 1H и 31P ЯМР и элементного анализа.
Various organic phosphates were synthesized using inverse phase transfer catalysis (IPTC). This method was effectively used for phosphorylation of para- substituted phenols (4-methyl-, 4-methoxy-, 4-chloro-, 4-hydro- and 4-nitro-) by diphenyl chlorophosphates. Para- substituted (4-chloro, 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, that confirmed by 1H NMR and IR spectroscopy. The 1H NMR spectrum shows shift of β-pyridine-1-oxide protons to the weak field. The IR spectrum shows shift to the high-frequency region of strong band of νP=O (1320 cm 1). Extended reaction scheme of reaction between diphenyl chlorophosphate and phenols in two-phase system H2O/CH2Cl2 was proposed. Effect of catalyst structure on reaction rate and product yield was investigated on the phosphorylation of 4-nitrophenol. With increasing basicity of the catalyst a higher reaction rate and product yield were reached. Initial concentration of catalyst in the aqueous phase strongly influences the reaction rate but not the yield. Initial rates of reaction were measured for characterization of reaction kinetic due to the complexity of process mechanism. The structure of obtained aryl diphenyl phosphates were confirmed by IR, 1H and 31P NMR. The experimental 31P chemical shifts of the synthesized organic phosphates were compared with calculated and good correlations were achieved. Lowest energy structures of phosphates were calculated using ORCA 2.9.0 at the DFT level of theory PBE0/6-31G(2df,p). 31P chemical shifts were predicted using IGLO method and specifically designed IGLO-II and IGLO-III basis sets. |
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| Date |
2013-04-11T15:18:37Z
2013-04-11T15:18:37Z 2013 |
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| Type |
Article
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| Identifier |
2074-6652
УДК 547.57 http://ea.donntu.edu.ua/handle/123456789/18401 |
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| Relation |
Наукові праці ДонНТУ;Серія: Хімія і хімічна технологія, 2013. - Вип.1(20). - С.90-96
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| Publisher |
Донецк, ДонНТУ
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