Imidization perfluorination

Atkins, J. R., Sides, C. R., Greager, S. E., Harris, J. L., Pennington, W. T., Thomas, B. H. and DesMarteau, D. D. 2003. Effect of equivalent weight on water sorption, PTFE-like crystallinity, and ionic conductivity in bis[(perfluoroalkyl) sulfonyl] imide perfluorinated ionomers. Journal of New Materials for Electrochemical Systems 6 9-15. 

A large variety of newer poly(ether imide)s has been described. Included among these are perfluorinated polymers (96), poly(ester ether imide)s (97), poly(ether imide)s derived from A/,Ar-diamino-l,4,5,8-naphthalenetetracarboxyHcbisimide (98), and poly(arylene ether imide ketone)s (99). In addition, many other heterocyHc groups have been introduced into polyether systems, eg, poly(pyrazole ether)s (100) and poly(aryl ether phenylquinoxaLine)s (101) poly(aryl ether oxazole)s with trifluoromethyl groups (102) and polyethers with other heterolinkages, eg, poly(arylether azine)s (103). 

New synthetic efforts generated a few structural derivatives of Lilm with longer perfluorinated alkyls such as LiBeti and a lithium salt of an asymmetric imide anion, and the stability of A1 in the electrolytes based on these salts was found to be much improved when compared with those in electrolytes based on Lilm and LiTf.i i s... 

The perfluoroacetamide catalysts, rhodium(II) trifluoroacetamidate [Rh2(tfm)4] and rhodium(II) perfluorobutyramidate [Rh2(pfbm)4], are interesting hybrid molecules that combine the features of the amidate and perfluorinated ligands. In early studies, these catalysts were shown to prefer insertion over cycloaddition [30]. They also demonstrated a preference for oxindole formation via aromatic C-H insertion [31], even over other potential reactions [86]. In still another example, rhodium(II) perfluorobutyramidate showed a preference for aromatic C-H insertion over pyridinium ylide formation, in the synthesis of an indole nucleus [32]. Despite this demonstrated propensity for aromatic insertion, the perfluorobutyramidate was shown to be an efficient catalyst for the generation of isomtinchnones [33]. The chemoselectivity of this catalyst was further demonstrated in the cycloaddition with ethyl vinyl ethers [87] and its application to diversity-oriented synthesis [88]. However, it was demonstrated that while diazo imides do form isomtinchnones under these conditions, the selectivity was completely reversed from that observed with rhodium(II) acetate [89, 90]. 

Perfluorinated tertiary amides and cyclic imides react cleanly with sulfur tetrafluoride/ hydrogen fluoride at elevated temperatures by replacing the carbonyl oxygen atom by fluorines to give good yields of tertiary perfluoroamines, e.g. formation of 13 and 14.178... 

Imides of perfluorinated succinic and glutaric acids react with xenon difluoride forming the respective yV-fluoroimides 3 in good yield.111... 

Anand and Filler123 demonstrated that pyridine reacted with xenon difluoride forming 2-fluoro-, 3-fluoro- and 2,6-difluoropyridine and 8-hydroxyquinoline was converted to 5-fluoro 8-hydroxyquinoline, while nitrogen functionalization was observed by reaction of phthalimide and saccharin in benzene124. A-Fluoroimides were formed in good yields by reactions of xenon difluoride with imides of perfluorinated succinic and glutaric acids125 (Scheme 52). 

A large variety of ILs of high purity with water content below lOOppm and halide content below lOppm are now available commercially. These include numerous iV-alkylpyridinium, 7V,7V -dialkylimidazolium, alkylammonium and alkylphosphonium salts, covalent hydrophobic ILs (e.g. l,2-dimethyl-3-propyliniidazolium bis(trifluoromethylsulfonyl)imide, task-specific ILs, Bronsted acidic ILs (e.g. 3-[triphenylphosphonio]propane-l-sulfonic acid tosylate), nitrile-fiinction sed ILs, perfluorinated ILs (e.g. tetrabutylammonium nonafluorobutane sulfonate, BASF Basionics (e.g. 1,2,3-trimethylimidazolium methyl sulfate), and TOMATS for heavy metal extraction (e.g. methyltrioctylammonium thiosalicylate)... 

Similar to cyclic anhydrides, imides of perfluorinated acids usually are prepared using derivatives of perfluorinated bis-carboxylic acids as starting material. For example, imides of F-succinic acid (46), F-glutaric (47), and F-adipic (48) " acids were synthesized through the reactions of either amido derivatives or cyclic anhydrides. 

Cyclic imides of perfluorinated disulfonic acids 74—76, reported by Koshar in 198266.67 ]jy DesMarteau group, are prepared by action of... 

Perfluorinated sulfonyl N—fluoro imides were demonstrated to be by far better fluorinating agents compared to perfluorinated A-fluoro amines, due to a combination... 

Imides of perfluorinated carboxylic acids also undergo the ring opening in the reactions with nucleophiles, giving derivatives of dicarboxylic acids. However, there are a number of processes proceeding with the preservation of heterocycle, such as reaction of silver salt of imide F-succinic acid 46 with diazomethane to produce Al-Me derivative. ... 

In a careful study of rhodium catalysts for the decomposition of a-diazo imide 450, Padwa and co-workers found that perfluorinated ligands greatly favor isomunchnone formation, whereas acetate leads to the generation of a six-membered carbonyl ylide. Thus 450 is converted to isomunchnone 451 with either rhodium perfluorobutyroamidate (Rh2(pfm)4), rhodium perfluorobutyrate (Rh2(pfb)4), or rhodium trifluoroacetate (Rh2(tfa)4) but is converted to 454 with Rh2(OAc)4 (Scheme 4.17). Neither 1,3-dipole can be isolated, but isomunchnone... 

Table III lists the properties of perfluorinated polyimides, along with those of partially fluorinated and unfluorinated polyimides. The structure of PMDA/ODA is the same as that of Dupont s Kapton. Because of the direct introduction of fluorines into the aromatic rings and the flexible structure of the lOFEDA component, the polymer decomposition temperatures and Tg s of perfluorinated polyimides are slightly lower than those of conventional poly imides. The thermal stability of these films is nonetheless high enough to withstand the manufacturing process for IC s and muitichip modules.

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