Perfluoroalkyl stability

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... 

The haloform reaction of unsymmetrical perfluoroalkyl and co-hydroper-fluoroalkyl trifluororaethyl ketones gives the alkane corresponding to the longer alkyl chain [54] (equation 53) If the methyl group contains chlorine, the reaction can take different pathways, leading to loss of chlorine (equation 54), because of the variable stability of the chlorine-substituted methyl carbanions in alkali. 

Perfluocoalkyl groups thermodynamically destabilize double bonds and small rings, but they can kineiically stabilize highly stramed molecules [75]. This remarkable perfluoroalkyl effect has made possible the isolation of stmctures that are uncommon m hydrocarbon chemistry, especially valence-bond isomers of aromatics and heteroaromatics such as 1, 2, and 3 [108],... 

Cobalt trifluoride fluorination corresponds to the electron-transfer mechanism via a radical cation. RF groups attached to the ring enhance the stability of intermediate dienes and monoenes. Perfluoroalkyl pyridines, pyrazines, and pyrimidines were successfully fluorinated but pyridazines eliminated nitrogen. The lack of certain dienes was attributed to the difference in stability of FC=C and RFC=C and steric effects [81JCS(P1)2059]. 

This study relates to a continuous process for the preparation of perfluoroalkyl iodides over nanosized metal catalysts in gas phase. The water-alcohol method provided more dispersed catalysts than the impregnation method. The Cu particles of about 20 nm showed enhanced stability and higher activity than the particles larger than 40 nm. This was correlated with the distribution of copper particle sizes shown by XRD and TEM. Compared with silver and zinc, copper is better active and stable metal. 

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... 

Radical copolymerization of TFE with hydrocarbon functional monomers has also not been widely used, owing perhaps to the high activity in the reaction with the C—H bond with its high probability of chain transfer to the monomer and the polymer, which is a feature of growing perfluoroalkyl radicals, and to poor chemical stability of the copolymers. 

Spruce meal and beech blocks were modified by using a mixture of perfluoroalkyl ethanol and MDI. Improved dimensional stability and water repellency were reported (Engonga etal., 1999). In order to avoid the handling problems associated with the use of most isocyanates, the generation of isocyanates within the wood by thermal rearrangement of acyl azides has been studied (Gdrardin etal., 1995) (Figure 4.8). This is potentially a... 

Rate constants and Arrhenius parameters for the reaction of Et3Si radicals with various carbonyl compounds are available. Some data are collected in Table 5.2 [49]. The ease of addition of EtsSi radicals was found to decrease in the order 1,4-benzoquinone > cyclic diaryl ketones, benzaldehyde, benzil, perfluoro propionic anhydride > benzophenone alkyl aryl ketone, alkyl aldehyde > oxalate > benzoate, trifluoroacetate, anhydride > cyclic dialkyl ketone > acyclic dialkyl ketone > formate > acetate [49,50]. This order of reactivity was rationalized in terms of bond energy differences, stabilization of the radical formed, polar effects, and steric factors. Thus, a phenyl or acyl group adjacent to the carbonyl will stabilize the radical adduct whereas a perfluoroalkyl or acyloxy group next to the carbonyl moiety will enhance the contribution given by the canonical structure with a charge separation to the transition state (Equation 5.24). 

All the S-, Se-, and Te-(perfluoroalkyl)dibenzothiophenium, -selenophenium, and -tellurophenium salts synthesized above are stable crystalline materials at room temperature. Their melting or decomposition points (dec. p) are higher than 100°C. Nitro substituents decrease their stability [S-salt 17 mp 155°C > dinitro S-salt 39 dec. p 130-135°C]. The chalcogen stability increases in the order S < Se < Te [dec. p S-salt 39 130-135°C < Se-salt 40 198-200°C < Te-salt 41 275-280°C]. Thermolysis of S-salt 17 at 200 C gave trifluoromethyl triflate (50) and dibenzothiophene (51) in high yields (Eq. 12). Thermolysis of dinitro S-salt 39 at 140°C gave 50 and dinitrodiben-zothiophene 52 (Eq. 13). 

Ozonolysis is generally carried out in solution as part of a synthetic route. Many 1,2,4-trioxolanes are isolated because of their unusual stability. In deliberate preparations of 1,2,4-trioxolanes, reactions in solution may not always be the most efficient process. Several ozonides can be prepared by dry ozonolysis where the alkene is reacted without solvent, for example the highly stable perfluoroalkyl 1,2,4-trioxolane (139) was obtained by heating the alkene (138) to 100°C in the presence of ozone (Equation (24)) <85TL2889>. 

Transmission electron microscope ( ) images of such n-Al powders indicate the presence of a thin passivation layer of aluminum oxide (A1203) which provides stability to it in the air. Without this layer, A1 nanoparticles would be pyrophoric and also have tendency to agglomerate to form bulk A1 metal. In order to protect this n-Al powder further, some researchers have suggested its coating with self-assembled nanolayers using perfluoroalkyl carboxylic acid [90]. 

Arguments similar to those stated above can be used to explain the relative chemical inertness of fluoropolymers. Consider the reactivity of alkanes vs. perfluoroalkanes as shown in Table 4.2 (abstracted from Sheppard and Sharts Statistically, FA based materials will have many more types of bonds, in addition to C—F, than fluoropolymers. These bonds will be subject to the same chemical fate during assault by aggressive reagents as bonds in their hydrocarbon counterparts. Similar reasoning can be used to explain the relative thermal stability of FAs compared to fluoropolymers. Thus, incorporation of perfluoroalkyl groups will not make the modified material less stable than the native one. 

All of the unique properties imparted by fluorocarbons can be traced back to a single origin the nature of the C—F bond. These properties include low surface tension, excellent thermal and chemical stability, low coefficient of friction, and low dielectric constant. However, not all of these properties are possessed by the entire inventory of available fluorocarbons. The fluorocarbons can be assigned to two major categories (1) fluoropolymers, which are materials that are comprised mainly of C—F bonds and include such examples as PTFE, and (2) fluorochemicals (FA) based on the perfluoroalkyl group, which are materials that generally have fewer C—F bonds and often exist as derivatives of other classes of molecules (e.g., acrylates, alcohols, esters). In addition, the properties that dictate the uses of fluorocarbons can be classified into (1) bulk properties (e.g., thermal and chemical stability, dielectric constant) and (2) surface properties (e.g., low surface tension, low coefficient of friction). The types of materials available and properties imparted are not exclusive and overlap substantially. From this array of fluorocarbons and attributes, a large variety of unique materials can be constructed. 

Other perfluoroalkyl polymers have been produced with sufficient thermal stability to withstand the temperatures of nylon melts from which carpet fihers are spun. During the subsequent heat treatment of the fiher the perfluoroalkyl groups diffuse to the surface to form a soil-resistant coating. Although such coatings add to the initial cost of the carpet they eventually save money by increasing the time intervals between cleanings. 

The 1,3-proton shift reaction has also been applied to the synthesis of a-(perfluoroalkyl)-a-amino acids, specifically 3.3,3-trifluoroalanine.2 -26 Attempts to prepare the A-benzylimine of ethyl 3,3.3-trifluoro-2-oxopropanoate by direct condensation with benzylamine were very difficult due to the exceptionally high stability of the intermediate a-amino alcohol, which fails to dehydrate. By contrast, 1-phenylethanamine reacted with ethyl 3,3,3-trifluoro-2-oxo-propanoate to form ketimine 33 in 83 % yield.26 The 1,3-proton shift reaction of 33 is much faster than those of ketimines derived from perfluoroalkyl ketones or perfluoroaldehydes (see Table 5). Complete conversion in triethylamine required 6 hours at room temperature and afforded the isomeric Shiff base 34 in 92 % yield. Mild hydrolysis of Shifif base 34 gives a-amino ester 35, which in turn hydrolyzes to 3,3,3-trjfluoroalanine hydrochloride (36). 

The values presented in Table 2 depict the variation of C = C re-bond strength with increasing fluorination and are consistent with the differences in reactivity associated with differing degrees of fluorination.3 Fluorination also destabilizes allenes and acetylenes.20 22 Similarly, per-fluoroalkyl groups destabilize C = C bonds. Note, however, that perfluoroalkyl groups can lend kinetic stabilization to strained molecules.3... 

Fluorination has a particularly profound effect on the additions of nucleophiles to per-fluorinated alkenes where the intermediate is anionic. Such processes are dramatically assisted by the strongly stabilizing influence of perfluoroalkyl groups substituted at the incipient anionic site.66 Similar to carbocations (see Section 1.4.), the effect of fluorination in such systems is often ambiguous when monofluorination is involved. a-Halogens generally stabilize anions in the order bromine > chlorine > fluorine, which is the exact opposite to the inductive electron-withdrawing order of the substituents. This effect reflects the importance of l7t-repulsion.67... 

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