Alkyl alcohols fluorination

Optically active fluorine-containing alcohols (91-93% ee) (entries 12 and 13) and deuterio alcohols (84-94% ee) (entries 14 and 15) are synthesized, respectively, by the enantioselective alkylation of fluorine-containing aldehyde and deuterio aldehyde using DBNE. 

FTOHs are a subset of fluorinated alcohols which consist of a perfluorinated alkyl chain combined with a non-perfluorinated alkyl alcohol. Due to the non-perfluorinated character of the alkyl alcohol, these compounds can participate in condensation reactions which would not be possible if the entire alkyl chain was perfluorinated. In this manner, FTOHs are often incorporated as a side-chain to higher molecular weight, non-perfluorinated polymers. The resultant free perfluorinated alkyl side-chain imparts release properties to the finished polymer. Most commercial products consist of FTOHs with a C2 non-perfluorinated alkyl group coupled to perfluorinated alkyls of various chain lengths. The most common FTOH has a C8 perfluorinated alkyl chain coupled with a C2 non-perfluorinated alkyl alcohol (perfluorooctylethanol—8-2 FTOH, Fig. 7.2). FTOHs used in the production of perfluorinated polymers typically include mixtures of varying chain lengths, with the most prevalent FTOH species being the 8-2 and 10-2 FTOHs. 

With alcohols, mixtures of alkyl fluorides and alkyl ethers are obtained (100). Alcohols beating electron-withdrawiag groups can be converted to the corresponding fluorides ia high yield (101). Sulfur tetrafluoride replaces the carboayl oxygea with fluorine (100,102). 

Numerous fluorinated and perfluorinated alkyl hypochlorites have been synthesized and characterized, eg, CF OCl [22082-78-6] C2F OCl [22675-67-8] /-C F OCl [22675-68-9] and /-C F OCl [22082-78-6]. These nonmetal oxychlorine compounds are much more thermally stable than the corresponding parent compounds and can be prepared by reaction of GIF with the appropriate carbonyl compound or alcohol. 

In contrast to phosphorus esters, sulfur esters are usually cleaved at the carbon-oxygen bond with carbon-fluorine bond formation Cleavage of esteri nf methanesulfonic acid, p-toluenesidfonic acid, and especially trifluoromethane-sulfonic acid (tnflic acid) by fluoride ion is the most widely used method for the conversion of hydroxy compounds to fluoro derivatives Potassium fluoride, triethylamine trihydrofluoride, and tetrabutylammonium fluoride are common sources of the fluoride ion For the cleavage of a variety of alkyl mesylates and tosylates with potassium fluoride, polyethylene glycol 400 is a solvent of choice, the yields are limited by solvolysis of the leaving group by the solvent, but this phenomenon is controlled by bulky substituents, either in the sulfonic acid part or in the alcohol part of the ester [42] (equation 29)... 

The phosphazene backbone has a particularly high resistance to thermal treatment and to homolytic scission of the -P=N- bonds, possibly due to the combination of the high strength of the phosphazene bond and its remarkable ionic character [456]. As a consequence, the onset of thermal decomposition phenomena (as detected, for instance, by TGA) are observed at considerably high temperatures for poly[bis(trifluoroethoxy)phosphazene], [NP(OCH2CF3)2]n [391, 399, 457], for phosphazene copolymers substituted with fluorinated alcohols of different length [391, 399, 457], for polyspirophosphazenes substituted with 2,2 -dihydroxybiphenyl groups [458], and for poly(alkyl/aryl)-phosphazenes [332]. 

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