STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS
The reactions of phenolysis of cyclophosphazenes, leading to the formation of monoaryl oxide derivatives with an excess of the substrate, were studied. The interest in this reaction is dictated by the practical value of the reaction products, which are easily formed under the conditions of transph...
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| Date: | 2022 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3982022-02-22T11:29:19Z STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS Shumeiko, Aleksandr cyclophosphazenes, transphase catalysis, phenolysis, stereoselectivity. The reactions of phenolysis of cyclophosphazenes, leading to the formation of monoaryl oxide derivatives with an excess of the substrate, were studied. The interest in this reaction is dictated by the practical value of the reaction products, which are easily formed under the conditions of transphase catalysis, and also by the fact that the studied regularities of phenolysis can extend to a significant spectrum of transphase nucleophilic substitution reactions. The general regularities of the transphase reaction of phosphazenes phenolysis were established by the example of the interaction of 4-nitrophenol with a phosphornitrile chloride trimer in a two-phase system. It was shown that the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of the transphase reagent, one can purposefully change the place of its interaction with the substrate. It was shown that the phenolysis of cyclotriphosphazenes occurs in the bulk of the organic phase or, alternatively, in the organic sublayer adjacent to the phase separation boundary. The presented data suggested that the transphase reaction can be described in terms of a single mechanism, in contrast to the generally accepted division into extraction and phase transfer. Thus, the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of transphase reagents, one can purposefully change the zone of their interaction with the substrate. In this case, the rate of the homogeneous response and the hydrophilicity of the ionic agent must be taken into account. The features of the transphase reaction described here can be extended to other catalysts, such as betaines, the analogs of which have been used in various reactions of a similar type. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-02-16 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/398 10.33609/2708-129X.88.01.2022.23-34 Ukrainian Chemistry Journal; Vol. 88 No. 1 (2022): Ukrainian Chemistry Journal; 23-34 Украинский химический журнал; Том 88 № 1 (2022): Ukrainian Chemistry Journal; 23-34 Український хімічний журнал; Том 88 № 1 (2022): Український хімічний журнал; 23-34 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/398/209 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
|
| datestamp_date |
2022-02-22T11:29:19Z |
| collection |
OJS |
| language |
English |
| topic_facet |
cyclophosphazenes transphase catalysis phenolysis stereoselectivity. |
| format |
Article |
| author |
Shumeiko, Aleksandr |
| spellingShingle |
Shumeiko, Aleksandr STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS |
| author_facet |
Shumeiko, Aleksandr |
| author_sort |
Shumeiko, Aleksandr |
| title |
STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS |
| title_short |
STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS |
| title_full |
STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS |
| title_fullStr |
STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS |
| title_full_unstemmed |
STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS |
| title_sort |
stereoselectivity in the reactions of phenolysis of cyclic phosphasenes under conditions of transphase catalysis |
| description |
The reactions of phenolysis of cyclophosphazenes, leading to the formation of monoaryl oxide derivatives with an excess of the substrate, were studied. The interest in this reaction is dictated by the practical value of the reaction products, which are easily formed under the conditions of transphase catalysis, and also by the fact that the studied regularities of phenolysis can extend to a significant spectrum of transphase nucleophilic substitution reactions. The general regularities of the transphase reaction of phosphazenes phenolysis were established by the example of the interaction of 4-nitrophenol with a phosphornitrile chloride trimer in a two-phase system. It was shown that the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of the transphase reagent, one can purposefully change the place of its interaction with the substrate. It was shown that the phenolysis of cyclotriphosphazenes occurs in the bulk of the organic phase or, alternatively, in the organic sublayer adjacent to the phase separation boundary. The presented data suggested that the transphase reaction can be described in terms of a single mechanism, in contrast to the generally accepted division into extraction and phase transfer. Thus, the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of transphase reagents, one can purposefully change the zone of their interaction with the substrate. In this case, the rate of the homogeneous response and the hydrophilicity of the ionic agent must be taken into account. The features of the transphase reaction described here can be extended to other catalysts, such as betaines, the analogs of which have been used in various reactions of a similar type. |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2022 |
| url |
https://ucj.org.ua/index.php/journal/article/view/398 |
| work_keys_str_mv |
AT shumeikoaleksandr stereoselectivityinthereactionsofphenolysisofcyclicphosphasenesunderconditionsoftransphasecatalysis |
| first_indexed |
2025-09-24T17:43:43Z |
| last_indexed |
2025-09-24T17:43:43Z |
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1849658103888347136 |