Perfluorinated amines

The perfluorinated amine 344 is cleaved by antimony pentafluoride to the inline 345... 

While aromatic amines are discussed in Section 5.2.14., various data for aliphatic amines are listed in Table 20. It is worthwhile remembering that tertiary perfluorinated amines, such as perfluorotributylamine. are completely stable, inert and nontoxic compounds, while some partially fluorinated tertiary amines tend to be unstable, eliminating hydrogen fluoride even at low temperature and are therefore toxie. Primary and secondary aliphatic fluorinated amines carrying CF,N groups have not, so far, been isolated due to their instability. 

Perfluorinated amines, ethers and ketones usually have much lower boiling points than their hydrocarbon analogues. 

Their pronounced ability to dissolve molecular oxygen in combination with their non-toxicity and complete physiological inertness makes perfluorocarbon fluids attractive for applications as respiratory fluids and as components of artificial blood substitutes [102] (Scheme 4.44). Many perfluorocarbons and perfluorinated amines can dissolve up to 40-50% v/v oxygen at 1 atm and 37 °C. It has been speculated that this unusual oxygen-dissolving capacity is related to the molecular shape and the occurrence of "cavities in perfluorocarbon fluids [103]. 

The general pattern of diaziridine synthesis is probably also followed by three-membered ring formation from perfluorinated aminals " as well as by a diaziridine synthesis from hydrazoic acid." In the course of the difluorodiazirine synthesis of Mitsch," perfluoromethylenediamine 96 is defluorinated by ferrocene. 

Diazirines fluorinated at the ring carbon were first described by Mitsch, °° and shortly afterward by Rebertus and co-workers. They are obtained from suitable perfluorinated amines by reduction with ferrocene or iodide, as well as by reduction with diphenylamine, semicarbazide hydrochloride and by electrolytic reduction. ... 

One of the successful utilizations of the difference in the relative stability between fluorinated and nonfluorinated imines is an effective transformation of perfluorinated ketones to the perfluorinated amines via imines by base-catalyzed 1,3-proton-shift methodology [9]. The driving force for the proton shift from 31 to 32 arises from the relatively lower stability of perfluoroalkyl imines compared to benzylidene imines [9]. Soloshonok developed an asymmetric version of the transformation in which DBU (l,8-diazabicyclo[5.4.0]undec-7-ene) catalyzes the asymmetric 1,3-proton shift of 31 to provide enantio-enriched (3-aminoester (33), as shown in Scheme 1.20 [10]. 

Preparation of Perfluorinated Nitrogen and Nitrogen-Oxygen Containing Heterocycles A wide range of perfluorinated amines was prepared in last 60 years. Electrochemical fluorination is the main method used for the preparation of variety saturated perfluorinated heterocycles. Despite the low yields of perfluorinated materials, the process is reliable and can be used for the preparation of perfluorinated materials. Detailed reports on the use of ECF for the preparation of fluorinated materials can be found in several reviews published in last 40 years Major types of perfluorinated N-... 

Due to the combination of lower electronegativity and the presence of unshared electron pair on nitrogen atom, perfluorinated cyclic amines are more reactive toward electrophiles, compared to ethers. As it is demonstrated by Hayashi et al., cyclic perfluorinated amines undergo selective, high-yield conversion into the corresponding lactams 41—45 upon treatment with fuming 112804 ° (Fig- 9.10). 

FIGURE 9.22 Ring opening of cyclic perfluorinated amines under the action of AICI3. 

As it was shown by Sokolov et al., perfluorinated amines are more reactive toward AICI3. The reaction of perfluorinated cyclic amines results in the ring opening and is accompanied by fluorine-chlorine exchange, leading to noncyclic isomeric imidoyl chlorides 80 (Fig. 

Petrov, V.A. Belen kii, G.G. German, L.S. Reaction of higher perfluorinated amines with antimony pentafluoride. Izv. Akad. Nauk SSSR, Ser. Khim. 1985, (8), 1934-1935. 

An early report on computational estimation of the thermodynamic properties of (difluoramino)alkanes, outside of the context of the American and Russian research programs, was by inel (Bogazi i University, Turkey), who estimated heats of formation, entropies, and bond dissociation energies of several simple difluoramines [141,142], derived from pubhshed experimental data on perfluorinated amines and thermochemical relationships. 

Fluorinated surfactants can lower the interfacial tension between a fluorocarbon, such as per perfluorodecalin, and water to as low as 1 mN/m. This suggests that fluorinated surfactants should be effective emulsifiers for biomedical fluorochemicals [42]. The first fluorinated surfactants [112-121] used in fluorochemical emulsions included potassium oleate, a perfluorinated amine oxide [115,116], a nonionic fluorinated surfactant derived from perfluoroalcohol [117], a fluorinated surfactant with two perfluoroalkyl end groups [118], and perfluo-roalkylated polyols [119]. However, the toxicity of these fluorinated surfactants has hindered their intravascular use. 

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