Fluorinated phosphonic acid derivative

Fluorinated phosphinic and phosphonic acid derivatives Perfluoro derivatives of alkyl phosphonic acid CnF2n+1-P(0)(0H)2 and alkyl phosphinic acid CnF2n+i(CmF2m+1)-P(0)0H (n = m or n m) shown with their general structural formulae in Fig. 2.11.29(1) and (II) were examined by negative ESI- and APCI-FIA-MS. These anionic surfactant compounds contained perfluoro alkyl chains [2,22,25]. By analogy with their behaviour in the TSI-FIA-MS(—) process [25], the phosphonic acid formed [M — H] ions at m/z 399 and 499... 

Halogenoalkyl and halogenocycloalkyl acids. a-Trifluoromethylphospho-nate (140) is a newly prepared synthon for making fluorinated a-hydroxy and a-amino phosphonic acid derivatives (141) and (142) (Scheme 50). ... 

An improved route to fluorinated 4-hydroxycoumarins has been reported, based on a facile decarboxylation-deacetylation of their 3-(3-oxopropanoic acid) derivatives <96TL15S1>. The reaction of methyl salicylates with triphenylphosphoranylidene ketene, Ph3P=C=C=0, affords 4-methoxycoumarins <96JCS(P1)2799> and the formation of coumarin 3-phosphonates from salicylaldehydes and phosphonoacetates, Et02CCH2P(0)(0R)2, has been investigated <96T12597>. 

The kinetics of deuterium isotope exchange between diphenyl phosphine and t-butylthiol have been studied by H n.m.r. spectroscopy.274 A negative temperature coefficient was observed for the reaction of a perf1uoroalky1 phosphite with a fluorinated aldehyde.275 The kinetics for the reaction of alcohols with phosphoryl trichloride bore strong similarities to those of carboxylic acid derivatives.276 An interesting report desribed the solvolysis of ary 1 hydroxymethyl-phosphonates. It was shown that a phosphoryl group does not prevent carbocation formation on an immediately adjacent carbon atom.277... 

C-6,209,214 anhydro sugars,branched monosaccharides, fluori-nated amino sugars,difluorinated monosaccharides, and fluorinated monosaccharide phosphates,and phosphonates have been described. Further progress has been achieved in the synthesis and n.m.r.-spectral analysis of fluorinated avermectin Bu, tylono-lide, and neuraminic acid derivatives. " ... 

Protein-tyrosine (PTP) inhibitors are potentially valuable pharmacological tools for studying cellular signal transduction and for therapeutic intervention. Derivatives of 1,1-difluoromethylphosphonic acid are known to be potent PTP inhibitors. An important method for synthesis of these compounds is fluorina-tion of acyl phosphonates by diethylaminosulfur trifluoride (DAST). This method allows synthesis of fcrf-butyl-protected difluoro(aryl)- or (naphthal-enyl)methylphosphonates, which under mildly acidic deprotection conditions afford desirable phosphonic acids [16, 39]. Acyl phosphonate fluorination by DAST has also been utilized for synthesis of a,a-(difluoroprop-2-ynyl)phos-phonates [14]. 

Tessier, J., Demoute, J.-P, and Truong, V.T., Process for preparing fluorinated derivatives of phosphonic acid, and products obtained using this process, Roussel Uclaf, Eur. Patent Appl. EP 224417, 1987 Chem. Abstr., 107, 96889y, 1987. 

Enolphosphate phosphonates derived from perfluoroalkanoylphosphonates have a number of synthetic uses. Reactions of such compounds with nucleophiles such as amines or alcohols in the presence of catalytic amounts of tetrabutylammonium fluoride (tbaf) gave a,j5-unsaturated perfluorocarboxylic acid derivatives, presumably via a ketene type intermediate (equation 94) When a primary amine was employed as the nucleophile a,j -unsaturated amides were formed, which could be converted into fluorinated pyrimidi-nones by treatment with urea. On the other hand, butylcopper(I) reagent reduces such... 

Various strategies for the syntheses of either aliphatic or aromatic functional fluorinated monomers have been proposed in the hterature. Because of their costs, they have been involved in copolymerization with fluoroalkenes, and although a lack of basic research is noted (e.g., no assessment of the reactivity ratios), many apphed investigations have been developed. In fact, most companies producing fluorinated monomers and derivatives have solved the challenge to prepare fluorocopolymers bearing sulfonic acid side groups. Nevertheless, quite a few studies concern phosphonic acid function. Compared with direct copolymerization, the alternative to prepare fluorofunctional copolymers by chemical modification of polymers is often employed. 

Osipov, S. N., Artyushin, O. I., Kolomiets, A. F., et al. (2001) Synthesis of racemic cyclic amino acids Synthesis of fluorine-containing cyclic a-amino acid and a-amino phosphonate derivatives by alkene metathesis. Fur. J. Org. Chem., 3891-3897. 

Scheme 11 indicates the usefulness of salts derived from Wittig ylide reagents and anhydrides of perfluorocarboxylic acids in the synthesis of fluorinated alkenylphosphonic diesters (127), often together with (epoxyalkyl)phosphonic diesters (128)(Rf = CF3 or... 

Some 4, S -unsaturated-S -fluoroadenosine nucleosides are described in Chapter 20 as well as some purine nucleosides containing the 2 -deoxy-2 fluoro- -D-arabinofuransoyl moiety. A number of dideoxymonofluoro- and dideo difluoro-a-D-glucopyranosyl phosphates have been prepared in order to study their relative rates of acid hydrolysis. The synthesis of a fluorinated 3-deoj -D-glyceric add phosphonate is discussed in Chapter 17 and the conversion of a l,3-anhydro-2-deojty- 2,2-difluoro-D-hexose derivative into a hydrolytically stable thromboxane A2 mimic is covered in Chapter 24. 

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