Fluoroacetate treatment

Zhou, J., Kauffman, F.C., Ballow, C.H., Thurman, R.G. (1984). Inhibition of mixed-function oxidation in perfused rat liver by fluoroacetate treatment. Biochem. Pharmacol. 33 319-23. 

If this electrostatic treatment of the substituent effect of poles is sound, the effect of a pole upon the Gibbs function of activation at a particular position should be inversely proportional to the effective dielectric constant, and the longer the methylene chain the more closely should the effective dielectric constant approach the dielectric constant of the medium. Surprisingly, competitive nitrations of phenpropyl trimethyl ammonium perchlorate and benzene in acetic anhydride and tri-fluoroacetic acid showed the relative rate not to decrease markedly with the dielectric constant of the solvent. It was suggested that the expected decrease in reactivity of the cation was obscured by the faster nitration of ion pairs. 

Benzamidomethyl-A -methylcysteine has been prepared as a crystalline derivative (H0CH2NHC0C6H 5, anhydr. CF3CO2H, 25°, 45 min, 88% yield as the tri-fluoroacetate salt) and cleaved (100% yield) by treatment with mercury(II) acetate (pH 4, 25°, 1 h) followed by hydrogen sulfide. Attempted preparation of S-acetamidomethyl-N-methylcysteine resulted in noncrystalline material, shown by TLC to be a mixture. ... 

Dimethyl dioxirane in wet acetone oxidizes isocyanates to nitro compounds (RNCO —> RN02). Oximes can be oxidized to nitro compounds with peroxytri-fluoroacetic acid, or Oxone ," sodiumperborate," among other ways. " Primary and secondary alkyl azides have been converted to nitro compounds by treatment with PhjP followed by ozone. Aromatic nitroso compounds are easily oxidized to nitro compounds by many oxidizing agents. ... 

B. Reactions.—(/) Halides. Whereas ylides are alkylated in the normal way on treatment with a-bromo- or a-iodo-esters, quite different reactions occur with a-fluoro- and a-chloro-acetates. When salt-free ylides were refluxed in benzene with ethyl fluoroacetate or trifluoroacetate normal Wittig olefin synthesis took place with the carbonyls of the ester groups to give vinyl ethers, e.g. (14). On the other hand, methyl chloroacetate with... 

Secondary Alkyl Alcohols. Treatment of secondary alkyl alcohols with tri-fluoroacetic acid and organosilicon hydrides results only in the formation of the trifluoroacetate esters no reduction is reported to occur.1,2 Reduction of secondary alkyl alcohols does take place when very strong Lewis acids such as boron trifluoride126 129 or aluminum chloride136,146 are used. For example, treatment of a dichlo-romethane solution of 2-adamantanol and triethy lsilane (1.3 equivalents) with boron trifluoride gas at room temperature for 15 minutes gives upon workup a 98% yield of the hydrocarbon adamantane along with fluorotriethylsilane (Eq. 10).129... 

Tourtellotte, W.W. and J.M. Coon. 1950. Treatment of fluoroacetate poisoning in mice and dogs. Jour. Pharmacol. Exper. Therapeut. 101 82-91. 

Namely, allyl alcohol is successively treated with diethylzinc, (R,R) dipropyl tartrate, and 4-methoxybenzohydroximinoyl chloride (163) to afford the enantiomeric isoxazoline alcohol 166, which under the Jones oxidation conditions affords the corresponding carboxylic acid derivative (167). Treatment of compound 167 with hydroxylamine-O-triflate followed by tri-fluoroacetic acid gives rise to the desired enantiomeric 165 in high excess enantiomeric yield. The synthesis of other isosteric analogues of 165 was reported in the same paper. None of the isosteric analogues exhibits LpxC inhibitory and antibacterial activities [103]. 

The formation of iminium ions of 20-epipandoline occurred only under Polo-novski-Potier conditions. Thus on treatment of the TV-oxide of 165 with tri-fluoroacetic anhydride followed by an aqueous solution of KCN, the iminium ion 329 was obtained, readily isolated as the corresponding a-amino nitrile 331 (Scheme 17). The reaction was completely regioselective and no traces of the enamine 332 could be obtained. This made the synthesis of spiroketone 333... 

The Arbuzov reaction has been applied for the synthesis of fluorinated carbohydrates. 1,2 3,4-Di-O-isopropylidene-a-D-galactopyran-ose 6-(N,N-diethyl-P-methylphosphonamidite) was treated with ethyl fluoroacetate, to afford 6-deoxy-6-fluoro-l,2 3,4-di-O-isopropylidene-a-D-galactopyranose in 19% yield.241 The corresponding 6-deoxy-6-fluoride was obtained in 60% yield by treatment of l,2 3,4-di-0-isopropylidene-a-D-galactopyranose 6-(dipropylphosphinite) with hexafluoropropene.242 The mechanism of this reaction has been discussed.243,244 In contrast, treatment of 1,2 -.3,4-di-O-isopropylidene-a-D-galactopyranose 6-(tetraethylphosphorodiamidite) with benzoyl fluoride yielded the corresponding 6-benzoate, not the 6-deoxy-6-flu-oride expected.245... 

Perfluoroalkanccarboxylic acids react with xenon difluoride to form corresponding unstable fluoroxenon esters, which decompose to give perfluoroalkyl radicals successfully trapped by various substrates. Treatment of benzene in dichloromethane with a modest excess of tri-fluoroacetic acid and xenon difluoride at room temperature gives trifluoromethylbenzene in 33-42% yield. The better yields are achieved with aromatics bearing electron-withdrawing substituents.8x86... 

Scission of the triazole ring in the triazolopyrimidine 13a occurred in tri-fluoroacetic acid or in hot glacial acetic acid alone or in the presence of acetyl chloride, yielding the 2-substituted pyrimidine derivatives 14a-c. However, 13b-d were stable to prolonged treatments with acids [71JCS (C)2156]. 

Fluoroacetate. Another metabolic inhibitor is fluoroacetic acid, a compound of high mammalian toxicity which has been widely used as a rodenticide. In 1952 Peters (99) discovered that fluoroacetic acid is converted in the body to fluorocitrate by acetyl CoA and oxaloacetate transacetase. The fluorocitrate proved by competition to be powerfully inhibiting to the metabolism of citric acid by aconitase. Thus the natural cycle is blocked and citrate accumulates in the tissues. Treatment with glycerol monoacetate has been used (24). 

Lead tetraacetate (LTA) and lead tetrakisfluoioacetate (LTFA) are common oxidants for the introduction of the hydroxy group. It has been suggested that the oxidation proceeds via electrophilic attack directly onto oxygen, but this seems unlikely in view of the fact that aryllead species are well characterized compounds,and they are known to give the corresponding acetates on treatment with tri-fluoroacetic acid or acetic acid. Some examples of the use of LTA have already been described (see Sections 2.10.2.4 and 2.10.3). 

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