Facile Synthesis of Fluorinated Phosphonates via Photochemical and Thermal Reactions
| Autor: | Donald J. Burton, Haridasan K. Nair |
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| Rok vydání: | 1997 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 119:9137-9143 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Under UV irradiation (254 nm) at ambient temperature, a degassed mixture of (EtO)2POP(OEt)2 and RfI {Rf = CF3, C2F5, C4F9, C6F13, (CF3)2CF, CF2CFCF2, ClCF2CF2, BrCF2CF2, C6F5, ClCF2CFClCF2CF2, I(CF2)3, I(CF2)4, FO2S(CF2)4, FO2S(CF2)2O(CF2)2} affords the fluorinated phosphonite, [RfP(OEt)2]. Oxidation of the phosphonites, [RfP(OEt)2], with Me3COOH gave the corresponding fluorinated phosphonates, (EtO)2P(O)Rf (1−14), in 35−80% isolated yields. CF3CCl2I reacts with (EtO)2POP(OEt)2 at room tempearture in the absence of UV irradiation to afford [CF3CCl2P(OEt)2] which upon oxidation gave a 52% yield of CF3CCl2P(O)(OEt)2 (15). The reaction of (EtO)2POP(OEt)2 and RfI (Rf = ClCF2CF2, BrCF2CF2, C2F5) at 125 °C in the presence of Me3COOCMe3 and subsequent oxidation of the resultant phosphonites afforded phosphonates (2, 7, and 8) albeit in lower yields (49−62%) compared to those of the photochemical reaction (58−80%). (RO)2P(O)CF2CF2I (R = Et, i-Pr) (16 and 17) was obtained (42−48%) when a degassed mixture of (RO)3P... |
| Databáze: | OpenAIRE |
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