- Some reactions of bis(trifluoromethyl)phosphines, -phosphine oxides, and -phosphine sulfides with alcohols and mercaptans. Preparation, characterization, and NMR spectra of a homologous series of esters and thioesters
-
The esters (CF3)2POR and thioesters (CF3)2PSR (R = CH3, C2H5, CH(CH3)2, and C(CH3)3) of trivalent phosphorus have been synthesized. Previously unknown esters in the series have been characterized and NMR parameters of all the above esters recorded. Synthesis of phosphinous esters and thioesters is aided by the presence of amine which is mandatory in the case of the reaction of tert-butyl alcohol with (CF3)2PCl. In the absence of amine, (CF3)2PCl reacted with tert-butyl alcohol to give (CF3)2P(O)C(CH3)3 and HCl. Separate reactions showed that (CF3)2POC(CH3)3 reacted with HCl to yield (CF3)2POH and (CH3)3CCl and that (CF3)2POH and (CH3)3CCl reacted to form (CF3)2P(O)C(CH3)3 and HCl. These reactions provide a basis for the detailed understanding of the reaction of (CF3)2PCl and related systems with tert-butyl alcohol. The oxy- and thioesters of pentavalent phosphorus, (CF3)2P(O)OR, (CF3)2P(O)SR, (CF3)2P(S)OR, and (CF3)2P(S)SR (R = CH3, C2H5, CH(CH3)2), were prepared by reactions analogous to those used to prepare the phosphinous esters; however, the competitive reaction of salt formation with amines in the case of the tert-butyl and, to a lesser extent, methyl esters requires use of alternate synthetic routes. In the case of tert-butyl esters, isobutene was also obtained in addition to the amine salt due to the instability of the tert-butylammonium salt. The tert-butyl thioester (CF3)2P(S)SC(CH3)3 was obtained from tert-butyl iodide and the appropriate phosphorus acid salt, (CF3)2PS2-. In contrast the dioxo and oxythioesters could not be prepared in this way. NMR parameters are recorded for all esters of pentavalent phosphorus and the new esters of pentavalent phosphorus have been characterized. Separate reaction of the esters of pentavalent phosphorus with trimethylamine gave R′(CH3)3N+(CF3) 2PXY- (X, Y = O, S) salts. In the case of esters of trivalent phosphorus, only (CF3)2POCH3 formed a 1:1 adduct with trimethylamine which may be the salt (CH3)4N+(CF3)2PO - NMR parameters of the tert-butylphosphine oxide (CF3)2P(O)C4H4 are also given.
- Cavell, Ronald G.,Pinkerton, A. Alan,Sim, William,Tomlinson, Adrian J.
-
p. 2901 - 2908
(2007/10/12)
-
- Mixed-valence derivatives of phosphorus sulfides. Two new isomeric thiophosphoryl-μ-thio-phosphines containing fluorine and trifluoromethyl substituents and a discussion of their exchange properties
-
Two new mixed-valence phosphorus compounds F2P(S)SP(CF3)2 and (CF3)2P(S)SPF2 are formed by the reaction of the acids F2PS2H or (CF3)2PS2H with the aminophosphines (CF3)2PN(CH3)2 or F2PN(CH3)2, respectively. Temperature-dependent nmr spectroscopy demonstrates the presence of an exchange process which destroys P-P coupling at room temperature in (CF3)2P(S)SPF2 but not in F2P(S)SP(CF3)2. The directly bound substituents are not interchanged by the exchange process and phosphorus valence is maintained. Concentration-dependent nmr studies indicate an intermolecular process and a plausible bimolecular process is described which accounts for the exchange process in X2P(S)SPX2 (X = F, CF3) molecules. When combined, the two new mixed-valence compounds equilibrate to form the two known symmetrically substituted isomers F2P(S)SPF2 and (CF3)2P(S)SP(CF3)2 and the equilibrium mixture can also be approached from these compounds. Thermal stability trends indicate a lower stability for compounds containing the PF2 moiety. Chemical reaction with protic species occurs with cleavage at the PIII-S link to yield phosphines and the parent acid and with halogens to yield halogeno phosphines and thiophosphinates. The reactions with mercury yield dithiophosphinato complexes and diphosphines or their decomposition products. Alkaline hydrolysis of CF3 species proceeds to yield 2 mol of CF3H per CF3 phosphino group and 1 mol per thiophosphinato group.
- Doty, Leon F.,Cavell, Ronald G.
-
p. 2722 - 2729
(2007/10/14)
-