Groups perfluoroalkyl

Perfluoroalkyl derivatives have important technical uses, e.g. sulphonic acids as surfactants introduction of perfluoroalkyl groups confers useful properties on many drugs. 

Particularly alkyl halides which have a perfluoroalkyl group at the /3-position undergo smooth carbonylation. Probably the coordination of fluorine to form a five-membered chelate ring accelerates the reaction. Double carbonylation to give the a-keto amide 915 is possible in Et NH with the fluorine-bearing alkyl iodide 914[769,770]. The ester 917 is obtained by the carbonylation of the /3-perfluoroalkyl iodide 916 in ethanol. 

Although nitrosation of (l-dicarbonyl compounds becomes increasingly more facile upon successive replacement of the a alkyl groups with perfluoroalkyl groups because of the increased ionization of the perfluorinated enolate (equation 7), the stability of the nitrosodiketone tautomers decreases Thus, 1,1,1-trifluoro pentane-2,4-dione and 1,1,1,5,5,5-hexafluoropentane 2,4 dione mtrosate much faster than penta-2,4 dione but yield ketoximes, which decompose upon workup... 

Allylation of perfluoroalkyl halides with allylsilanes is catalyzed by iron or ruthenium carbonyl complexes [77S] (equation 119) Alkenyl-, allyl-, and alkynyl-stannanes react with perfluoroalkyl iodides 111 the presence ot a palladium complex to give alkenes and alkynes bearing perfluoroalkyl groups [139] (equation 120)... 

The cyanohydrin of methyl perfluoroheptyl ketone was synthesized by a two-step process addition of sodium bisulfite and subsequent treatment with sodium cyanide. When the ketone was reacted with sodium cyanide, cyclic addition products were obtained, instead of the product of cyanohydrin formation. This result was attributed to the solubility characteristic of a long perfluoroalkyl group, which makes the compound less soluble in water and polar organic solvents [54] (equation 40) (Table 14). 

Under sonication conditions, the reaction of perfluoroalkyl bromides or iodides with zinc can be used to effect a variety of functionalization reactions [39, 40, 41, 42] (equation 30) Interestingly, the ultrasound promoted asymmetric induction with the perfluoroalkyl group on the asymmetric carbon was achieved by the reaction of perfluoroalkyl halides with optically active enamines in the presence of zinc powder and a catalytic amount of dichlorobisftc-cyclopenta-dienyl)titanium [42] (equation 31)... 

Reactions of fluorinated dipolarophiles. Electron-deficient unsaturated species generally make better dipolarophiles, therefore, fluonnated alkenes become better dipolarophiles when vinylic fluonnes are replaced by perfluoroalkyl groups For example, perfluoro-2-butene is unreactive with diazomethane, but more highly substituted perfluoroalkenes, such as perfluoro-2-methyl-2-pentene, undergo cycloadditions in high yields [5] (equation 2) Note the regiospecificity that IS observed in this reaction... 

In contrast to the relative lack of Diels-Alder reactivity exhibited by fluorinated ethylenes, ethylenes substituted with perfluoroalkyl groups show greatly... 

Perfluoroalkyl groups adjacent to multiple bond systems lower the frontier molecular orbitals (FMOs) Therefore, cycloaddition reactions preferentially occur with electron-rich multiple-bond systems The preference of bis(trifluoromethyl)-substituted hetero-l,3-dienes for polar reacuons makes them excellent model compounds for developing new types of diene reactions deviating from the well documented Diels-Alder scheme (pathway 1) A systematic study of the reactions of diene (1 =2-3=4)-dienophile (5=6) combinations reveals new synthetic possibilities that have not yet been fully exploited as tools for preparative organic cherrustry (equation 25)... 

Similarly, low-temperature photolysis of 4,5,6-fluorosubstituted 1,2,3-tna zines results in the elimination of nitrogen, but the product composition depends on the substituents When the substituents are fluonne atoms, the intermediate product IS a four-membered, mtrogen-contaming ring that quickly dimenzes When all the substituents are perfluoroalkyl groups, the pyrolysis results in a mixture perfluoroalkyl acetylenes and perfluoroalkyl cyanides [79] (equations 48 and 49). 

Irradiation of cyclic ketones having perfluoroalkyl groups causes cleavage of a ring to yield acyclic products [I74 (equation 44) Similarly, perfluonnated ketones undergo decarbonylation when irradiated [775]. Gas-phase photolysis of perfluorodiazoketones, in the presence of a trapping agent, yields fluorinated furan as a major product [176] (equation 45)... 

Fluorocarbons with a hydrophilic functional group are very active surfactants [23]. Less than 1% of ionic or nonionic surfactants with perfluoroalkyl groups can reduce the surface tension of water from 72 to 15-20 dyne/cm, compared with 25-35dyne/cm for typical hydrocarbon surfactants [24] Perfluoroether surfactants are about as active as their perfluoroalkyl counterparts of similar chain length [25, 26], but fluorosurfactants with more polar alkyl end groups are considerably less active than their perfluoroalkyl analogues (Table 7)... 

A synthetic procedure to insert the perfluoroalkyl group into the dihydropyrone cycle via ethoxybutenone has been elaborated (98T2819). 6-Ethoxy-2-trifiuoro-methyl-4//-pyran-4-one (309) was synthesized by the condensation of ethyl... 

Peptide synthesis, 81 Perfluoroalkyl groups, 346 Personal protective equipment (PPE), 246... 

Perfluoroalkyl group-containing surfactants like fluoroalkylsuccinamic surfactant and fluoroalkylthio derivatives from the reaction of bis-2-hydroxyethyl-aminomethylphosphonic acid ester with maleic anhydride were especially useful for the preparation of foams for extinguishing burning hydrocarbon liquids. A surface tension of 19.8 mN/m in a 0.1% aqueous solution was observed [88. ... 

Figure 10.69 Change in critical surface energy with length of the perfluoroalkyl groups in acrylic polymers [502]...

The development of synthetic methods for the selective introduction of short-chain perfluoroalkyl groups into organic molecules is of interest in drug development [464]. Fluoromodifications often confer unique properties on a molecule, for example in terms of increased metabolic stability and lipophilicity and, as a consequence, the pharmacokinetic profiles are often improved [465]. Burger and coworkers developed a domino process consisting of a SN reaction combined with a Claisen and a Cope rearrangement which allows the transformation of simple fluorinated compounds into more complex molecules with fluoro atoms [466]. Treatment of furan 2-917 with 2-hydroxymethyl thiophene (2-918) in the presence... 

Addition of HSiMeCl2 to cyclopentadiene is catalyzed by (42) at room temperature at low catalyst loading (0.01 mol.%) to give the (S)-allylsilane in moderate ee.125 This enantioselectivity can be enhanced dramatically with incorporation of perfluoroalkyl groups into the amine functionality (Scheme 26).126... 

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