Perfluoro-alcohols

Water, alcohols Perfluoro-tert-butanol (CFalaCOH 85.1 [133]... 

Drying agent A fluid used to displace fluids that have potential residue materials and that will vaporize quickly from the surface. Examples Anhydrous alcohol perfluoro-N-methyl morpholine plus 0.2% surfactant (3M PF-5052 DS spot-free drying agent). 

The properties of ester oils and complex esters are improved by additives, such as viscosity-index improvers of the methacrylate type. On the other hand, these ester oils are also used as base stock and additive for lithium greases (- lubricating greases). Perfluorinated alcohols (->perfluoro alkyl compounds) are sometimes built in ester oils to increase thermal stability. 

In general, the reactions of the perfluoro acids are similar to those of the hydrocarbon acids. Salts are formed with the ease expected of strong acids. The metal salts are all water soluble and much more soluble in organic solvents than the salts of the corresponding hydrocarbon acids. Esterification takes place readily with primary and secondary alcohols. Acid anhydrides can be prepared by distillation of the acids from phosphoms pentoxide. The amides are readily prepared by the ammonolysis of the acid haUdes, anhydrides, or esters and can be dehydrated to the corresponding nitriles (31). 

Rase-catalyzed reaction of alcohol favors addition, whereas increasing amounts of alkoxide favor addition-elimination reactions. Perfluoro-2-methyl-2-pentene and methanol form the saturated ether, whereas two equivalents of sodium methoxide form the vinylic ether [S] (equation 4). 

Miller et al. [9] hypothesized rules on the regioselectivity of addition from the study of the base-catalyzed addition of alcohols to chlorotnfluoroethylene. Attack occurs at the vinylic carbon with most fluorines. Thus, isomers of dichloro-hexafl uorobutene react with methanol and phenol to give the corresponding saturated and vinylic ethers The nucleophiles exclusively attack position 3 of 1,1-dichloro-l,2,3,4,4,4-hexafluoro-2-butene and position I of 4,4-dichloro-l,l,2,3,3,4-hexafluoro-1-butene [10]. In I, l-dichloro-2,3,3,4,4,4-hexafluoro-l-butene, attack on position 2 is favored [J/] (equation 5) Terminal fluoroolefms are almost invariably attacked at tbe difluoromethylene group, as illustrated by the reaction of sodium methoxide with perfluoro-1-heptene in methanol [/2J (equation 6). 

In a related process, a-halo ethers can be prepared by treatment of aldehydes and ketones with an alcohol and HX. The reaction is applicable to aliphatic aldehydes and ketones and to primary and secondary alcohols. The addition of HX to an aldehyde or ketone gives tx-halo alcohols, which are usually unstable, though exceptions are known, especially with perfluoro and perchloro species. °... 

The trend of discovering the analytical field of environmental analysis of surfactants by LC-MS is described in detail in Chapters 2.6-2.13 and also reflected by the method collection in Chapter 3.1 (Table 3.1.1), which gives an overview on analytical determinations of surfactants in aqueous matrices. Most methods have focused on high volume surfactants and their metabolites, such as the alkylphenol ethoxylates (APEO, Chapter 2.6), linear alkylbenzene sulfonates (LAS, Chapter 2.10) and alcohol ethoxylates (AE, Chapter 2.9). Surfactants with lower consumption rates such as the cationics (Chapter 2.12) and esterquats (Chapter 2.13) or the fluorinated surfactants perfluoro alkane sulfonates (PFAS) and perfluoro alkane carboxylates (PFAC) used in fire fighting foams (Chapter 2.11) are also covered in this book, but have received less attention. 

Cocaine and its ethyl homolog, cocoethylene, have been assayed simultaneously using GC-NPD (Hime et al., 1991). These compounds can be derivatized by reducing the ester groups to alcohols, which can then be derivatized with a perfluoro acylating reagent to provide sensitivity for GC-ECD (Blake et al.,... 

The sulfenyl carboxylate is, on complete exclusion of moisture, a stable, colorless liquid, which on irradiation with UV light decomposes to FC(0)SCFs and CO2. The sulfane is a good starting material for the synthesis of additional perfluoro compounds By means of fluorine-chlorine substitution with BCI3 (20°C, 2 days), it is possible to obtain C1C(0)SCF3, whose existence previously could be shown only by mass spectrometric study of the products of irradiation of a mixture of CFsSCl and CO (237). As an acid chloride, ClC(0)SCFs can be esterified with alcohols, but hydrolysis to the free acid fails. 

Using a similar approach, Chechik and Crooks (73), modified the PAMAM dendrimer-encapsulated palladium nanoparticles with perfluoropolyether tails utilizing non-covalent ion-pair interactions. The catalytic hydrogenation of six substrates under biphasic conditions (toluene/ perfluoro-2-butyltetrahydrofuran FC-75) was investigated. Allyl alcohol, methyl acrylate, vinyl isopropenyl ether, and... 

There have been efforts to enhance stereoselectivity in radical polymerization by using fluoroalcohols or Lewis acids that complex with monomers such as MMA and vinyl acetate [Isobe et al., 2000, 2001a Okamoto et al., 2002], In almost all instances the effects are nil or very small. For example, the use of perfluoro-t-butyl alcohol as solvent instead of toluene changes (rr) from 0.89 to 0.91 in the polymerization of MMA at —78°C. An exception is in the polymerization of acrylamide in the presence of some rare-earth Lewis acids such as ytterbium triflate. The polymer is atactic at 0°C, (m) = 0.46, in the absence of the Lewis acid, but significantly isotactic, (m) — 0.80, in the presence of the Lewis acid. The reason for this effect is unclear. More highly isoselective polymerization occurs in some radical polymerizations of MMA (Sec. 8-14b). 

Perfluoroalcoholates, 16 126 Perfluoro alcohols, 16 124 Perfluoroalkanes, 16 124 Perfluoroalkane sulfonic acids, 2 140-142, 3 421 24... 

The reaction of perfluoroalkyl iodides with alkenes affords the perfluoro-aikyiated alkyl iodides 931. a.a-Difluoro-functionalized phosphonates are prepared by the addition of the iododifluoromethylphosphonate (932) at room temperature[778], A one-electron transfer-initiated radical mechanism has been proposed for the addition reaction. Addition to alkynes affords 1-perfluoro-alkyl-2-iodoalkenes (933)[779—781 ]. The fluorine-containing oxirane 934 is obtained by the reaction of allyl alcohol[782]. Under a CO atmosphere, the carbocarbonylation of the alkenol 935 and the alkynol 937 takes place with perfluoroalkyl iodides to give the fluorine-containing lactones 936 and 938[783],... 

Addition of allyl alcohol to perfluoro(2-mcthy1propene) in the absence of a catalyst gave ally ether 2 and rearranged ester 4, presumably formed by alcoholysis of the intermediate acyl fluoride 3. 

Krespan also found that allyl alcohol added to 1-mcthoxy-2-(trifluoromethyl)tetrafluoro-propcnc, derived from perfluoro(2-mclhylpropene). to give the rearranged ester 5. a presage of the Johnson Claiscn rearrangement. Reactions of allylic alcohols with vinyl ethers derived from perfluoro(2-methylpropene) were subsequently studied by Andreev and co-workers11 and are discussed below. 

Propargy] alcohol reacts with hcxafluoropropene (14, X = F) and perfluoro(2-methyl-propene) (14, X = CF,) to give the 3,4-dienoates 18.11... 

In polyfluorinated and especially perfluorinated aromatics, fluorine is hydrolyzed relatively easily. Perfluorochlorobenzene gives perfluoro-4-chlorophenol (2) on treatment with potassium hydroxide in tert-butyl alcohol.33... 

Perfluoronaphthalene when treated with potassium hydroxide in tm-butyl alcohol produces perfluoro-2-naphthol (16).49... 

The substitution of geminal difluoride groups with hydroxylamines or hydrazines leads to the corresponding oximes31 or hydrazones.3,32 Diamines, amino alcohols or amino thiols give rise to N,N, N,0- or /V.A-acetals, respectively.33 Yields are especially good when perfluoro-O-silyl enol ethers (e.g., 5) are used instead of the corresponding ketones.2,33... 

Perfluoro tertiary alcohols are known, e.g. (CF3)3COH,139,140 (C6F5)3COH141 and (C2F5)3COH,142 and these will react by alcohol exchange to give metal tertiary perfluoroalkoxides, but these do not appear to have been systematically studied. 

The photolysis of aromatic species with tetranitromethane in perfluoro alcohol solvent has been studied, in which the radical cations were observed by EPR spectroscopy.284 Photo-stimulated reaction of 1- and 2-haloadamantanes and 1,2- and 1,3-dihaloadamantanes with various carbanionic nucleophiles afforded products rationalized through an SrnI mechanism.285 286 Photolysis of the cycloadduct formed between a functionalized derivative of C6o and diazomethane has been shown to afford a pah of ling-opened structures (125) and (126) via a proposed biradical intermediate (127) (Scheme 19). The UV-photolytic fragments of /-butyl iodide (T and /-Bu ) have been ionized by resonance-enhanced multiphoton ionization for TOF mass spectro-metric analysis.287 A two-dimensional position-sensitive detector provided angular distribution and translational energy data. 

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