4- fluorophenol amines

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

The cerium(IV) oxidation of lactyllactic acid49 and of 4-oxopentanoic acid50 in aqueous nitric acid solutions shows first-order dependence of the reaction on both cerium(IV) and substrate. A 1 1 complex formation between manganese(III) and amine, which later decomposes in the rate-limiting step, best explains the kinetics of oxidation of aliphatic amines by cerium(IV) in nitric acid medium in the presence of manganese(II).51 The kinetics of oxidation of naphthalene, 2-methyhiaphthalene, and a-naphthol with cerium(IV) in perchloric acid solutions have been studied.52 Use of a 50-fold molar excess of cerium(IV) perchlorate results in complete oxidation of fluorophenols to CO2, HCO2H, and HF in 48 h at 50 °C.53... 

Caddick [19] has reported the use of a novel polymer-supported tetra-fluorophenol-Unked acrylate as an activated acceptor for intermolecular radical reactions. Treatment of immobiUzed acrylate 132 with a variety of alkyl iodides in the presence of tributyltin hydride and AIBN gave the corresponding esters 133 (Scheme 29). NucleophiUc cleavage using amines gave amides 134 in good overall yield whilst regenerating phenol resin 131. 

Difunctional compounds, including certain halogenated ethers, aldehydes, ketones, phenols, amines, and nitro compounds, have been prepared by the Sandmeyer reaction. However, fluorophenols and fluoro acids are best obtained from the corresponding ethers and esters, respectively, which have been fluorinated by the Schiemann reaction. ... 

Copper mandelates react with pho ene and then pyridine to give 1,3-dioxoIan-2,4-diones, and application of this reaction to the pentafluoroKxnnpound [CeFe -C(0H)Me-C08]2Cu yields the substituted dioxolan (127) (62%). Compounds of this type give derivatives of the parent acid when they are treated with amines or alcohols, and may be polymerized to polyesters details of these reactions are awaited. Pentafluorobenzoic acid is converted into pentafluoroiodobenzene by treatment with iodine in the presence of a peroxide initiator, and certain penta-fluorobenzamido-derivatives of 4-fluorophenol, e.g. (128), prepared by conventional multistage syntheses from the parent phenol, are claimed to be useful as colour-formers in photographic emulsions. i... 

Figure 1.6 Family-dependent transformation of 4-fluorophenol basicities in CH2CI2 to 4-fluorophenol basicities in the standard solvent CO4. Different lines are found for sulfonyls 1118], carbonyls [119], pyridines [119] and amines [120].

Table 4.4 Equilibrium constants KM (I moM) and hydrogen-bond basicity scales, pKsnx and AC° (kj mol ), for the complexes of 4-fluorophenol with ammonia and primary amines, in C2Cl4 at 25 °C.

Figure 4.8 Limited linear enthalpy relationship for formation of hydrogen-bonded complexes of cyanoacetylene and 4-fluorophenol. The upper line represents n bases (benzene, mesity-lene, hexamethylbenzene), the middle line sulfur (tetrahydrothiophene), Nsp (acetonitrile) and O (ethers, CO, SO, PO) bases, and the lower line pyridine and tertiary amine bases.

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