Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2
White phosphorus has been catalytically oxidized by oxygen in alcoholic solutions of copper (II) acetylacetonate, halides or carboxylates to yield dialkyl phosphites and trialkyl phosphates under mild reaction conditions. Trialkyl phosphite has been observed as unstable organophosphorus intermediate...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
al-Farabi Kazakh National University
2010-11-01
|
| Series: | Eurasian Chemico-Technological Journal |
| Online Access: | http://ect-journal.kz/index.php/ectj/article/view/509 |
| _version_ | 1818526882878980096 |
|---|---|
| author | R. R. Abdreimova F. Kh. Faizova A. A. Karimova |
| author_facet | R. R. Abdreimova F. Kh. Faizova A. A. Karimova |
| author_sort | R. R. Abdreimova |
| collection | DOAJ |
| description | White phosphorus has been catalytically oxidized by oxygen in alcoholic solutions of copper (II) acetylacetonate, halides or carboxylates to yield dialkyl phosphites and trialkyl phosphates under mild reaction conditions. Trialkyl phosphite has been observed as unstable organophosphorus intermediate, which is being converted into the main reaction products. In the case of methanolic solutions, the derivatives of two step acidolysis of dimethyl phosphite, monomethyl phosphite and phosphorous acid, have been additionally detected among the reaction products. The influence of the copper (II) catalysts on the kinetics of accumulation and transmutation of organophosphorus products has been explored. It has been found that the Cu(II) compounds take a role of catalysts-electron-carriers from white phosphorus to oxygen. The indispensable molar ratio between catalyst and white phosphorus and the order of catalytic activity for the copper (II) compounds have been established. The major steps of the catalytic reaction including (i) the coordination of white phosphorus and alcohol to metal ion, (ii) the redox decomposition of this intermediate complex accompanied by reducing elimination of elementary copper and formation of organophosphorus product and (iii) the oxidation of the reduced form of catalyst by oxygen have been also suggested. |
| first_indexed | 2024-12-11T06:28:59Z |
| format | Article |
| id | doaj.art-93ba7d8c73834505937f6e9a4f12a043 |
| institution | Directory Open Access Journal |
| issn | 1562-3920 2522-4867 |
| language | English |
| last_indexed | 2024-12-11T06:28:59Z |
| publishDate | 2010-11-01 |
| publisher | al-Farabi Kazakh National University |
| record_format | Article |
| series | Eurasian Chemico-Technological Journal |
| spelling | doaj.art-93ba7d8c73834505937f6e9a4f12a0432022-12-22T01:17:35Zengal-Farabi Kazakh National UniversityEurasian Chemico-Technological Journal1562-39202522-48672010-11-01123-426727210.18321/ectj54509Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2R. R. Abdreimova0F. Kh. Faizova1A. A. Karimova2D. V. Sokolsky Institute of Organic Catalysis and Electrochemistry, 142 Kunaev St., 050010 Almaty, KazakhstanD. V. Sokolsky Institute of Organic Catalysis and Electrochemistry, 142 Kunaev St., 050010 Almaty, KazakhstanD. V. Sokolsky Institute of Organic Catalysis and Electrochemistry, 142 Kunaev St., 050010 Almaty, KazakhstanWhite phosphorus has been catalytically oxidized by oxygen in alcoholic solutions of copper (II) acetylacetonate, halides or carboxylates to yield dialkyl phosphites and trialkyl phosphates under mild reaction conditions. Trialkyl phosphite has been observed as unstable organophosphorus intermediate, which is being converted into the main reaction products. In the case of methanolic solutions, the derivatives of two step acidolysis of dimethyl phosphite, monomethyl phosphite and phosphorous acid, have been additionally detected among the reaction products. The influence of the copper (II) catalysts on the kinetics of accumulation and transmutation of organophosphorus products has been explored. It has been found that the Cu(II) compounds take a role of catalysts-electron-carriers from white phosphorus to oxygen. The indispensable molar ratio between catalyst and white phosphorus and the order of catalytic activity for the copper (II) compounds have been established. The major steps of the catalytic reaction including (i) the coordination of white phosphorus and alcohol to metal ion, (ii) the redox decomposition of this intermediate complex accompanied by reducing elimination of elementary copper and formation of organophosphorus product and (iii) the oxidation of the reduced form of catalyst by oxygen have been also suggested.http://ect-journal.kz/index.php/ectj/article/view/509 |
| spellingShingle | R. R. Abdreimova F. Kh. Faizova A. A. Karimova Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2 Eurasian Chemico-Technological Journal |
| title | Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2 |
| title_full | Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2 |
| title_fullStr | Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2 |
| title_full_unstemmed | Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2 |
| title_short | Copper (II) Catalyzed Oxidative Alkoxylation of White Phosphorus. Communication 2 |
| title_sort | copper ii catalyzed oxidative alkoxylation of white phosphorus communication 2 |
| url | http://ect-journal.kz/index.php/ectj/article/view/509 |
| work_keys_str_mv | AT rrabdreimova copperiicatalyzedoxidativealkoxylationofwhitephosphoruscommunication2 AT fkhfaizova copperiicatalyzedoxidativealkoxylationofwhitephosphoruscommunication2 AT aakarimova copperiicatalyzedoxidativealkoxylationofwhitephosphoruscommunication2 |