Perfluoroalkyl iodides, hydrolysis

Polyfunctional fluoronitro alcohois are provided by tlie SRNl reaction of a perfluoroalkyl iodide or alkylene diiodides with the anhydrous lithium salt of 2-nitropropane l,3-diol acetonide. Hydrolysis of the resulting perfluoroalkyl-... 

The N-pyrrolylzinc chloride 53 undergoes Pd-catalyzed coupling with perfluoroalkyl iodides to afford the 2-substituted pyrroles 54 in good yield [52], Smaller amounts (15-20%) of 2-perfluoroalkanoyl pyrroles, which presumably arise by hydrolysis of the benzylic difluoromethylene group, are also formed. This reaction, which is performed in one pot, also affords 2-phenylpyrrole (75%) and 3-phenylpyrrole (5%) with iodobenzene. Some biphenyl (15%) is also formed. 

Perfluoroalkyl iodides reacted with trialkylsilyl chloride in DMF in the presence of zinc followed by hydrolysis with acid to give perfluoroaldehydes in good yields [55]. Recently, Hu reported a new preparation of perfluoroalkyl aldehydes via reaction of perfluoroalkyl halides and DMF, initiated by redox... 

Other functional polyfluorinated compounds are available by addition of perhaloalkyl halides to enol derivatives, e.g. formation of 1 and 2 (see also Table 4). The adducts formed from enol acetates or enol ethers are not very stable and their hydrolysis to give a-perhaloalkyl aldehydes or ketones is often rapid. However, the enol derivatives can be transformed either to give ketals using alcohols or to give various products by oxidation and reduction reactions. The peculiar perfluoroalkyl iodide addition to enamines is spontaneous at room temperature, e.g. formation of 3. ... 

Perfluoroalkyl)ethanols Hydrolysis of Iodides General Procedure 5... 

The resultants, 1,1,2,2-tetrahydroperfluoroalkyl iodides, can be easily converted, e.g., into alcohols, thiols, carboxylic acids and ethoxylated products. Thus, direct hydrolysis of 2-perfluoroalkyl iodides leads to perfIuoroalkyl-2-ethanols which show surface activity in non-aqueous solvents. Such approaches to fluorosurfactant synthesis have been put on stream by Du Pont, Ciba-Geigy, Hoechst, Asahi Glass and Daikin Kogyo. 

The preparation of perfluoroalkanecarboxylic adds and their alkali-metal salts via reaction of perfluoroalkylmagnesium bromides (generated from perfluoroalkyl iodides and phenylmagnesium bromide) with diethyl carbonate followed by hydrolysis, has been described in the patent literature. ... 

Perfluoroalkylethanols, readily available by hydrolysis of perfluoroalkyl iodides, can be oxidized to fluorinated carboxylic acids. As an example, oxidation of H(CF2CF2) CH20H with nitrogen oxides gave w-hydroperfluorocarboxylic acids [118] ... 

Pd(PPh3)4-Catalysed reaction of perfluoroalkyl and polyfluoroalkyl iodides, e.g. CF3(CF2)2CF2l and Cl(CF2)5CF2l, respectively, with R2NH (R = Et, Pr, Bu) gave 40-50% of enamines, e.g. CF3(CF2)3CH=CHNR2 and CKCFjieQMel CHNRj, which on hydrolysis with 2 M HCl afforded 95% of enaminones. ... 

Rf = CF3 or C2F5, but the compound -C3F7HgI is not appreciably soluble. The perfluoroalkyl groups can be removed by hydrolysis, but the compounds CF3HgX (X = F, Cl, Br and NO 3) have been prepared by treating perfluoromethylmercury iodide with moist silver oxide followed by the appropriate aqueous acid. 

Perfluoroalkyl-2-ethanethiols are prepared by reaction of a perfluoroalkyl-2-ethyl iodide with thiourea and subsequent alkaline hydrolysis of the thiouro-nium salt formed [90,94]. A reaction of the perfluoroalkyl-2-ethanethiol... 

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