Difluoro -amine

Chlorodifluoroamine has been prepared by reaction of difluoro-amine with boron trichloride,1 phosgene (carbonyl chloride),2 or hydrogen chloride 2 treating a mixture of sodium azide and sodium chloride with fluorine 3 reaction of chlorine trifluoride with ammonium fluoride 4 reaction of chlorine with diflu oro-amine in the presence of potassium fluoride 5 and photolysis of tetrafluorohydrazine and sulfinyl chloride (thionyl chloride).6... 

DIFLUOROUREA SOLUTIONS AND DIFLUORO-AMINE—EXTRA-HAZARDOUS MATERIALS... 

The unstable difluoroammonium ion can be made from the explosive difluoro-amine, NHF2 (see below), by the reaction... 

Fluorinations of other functionalities containing C = N bonds, such as 2//-azirines and imines, are included in this section. Certain 2Ff-azirines and imines yield a-fluoro ketones. With other 2Ff-azirines, /i,/(-difluoro amines are the main reaction products. In a strict sense, these reactions cannot be considered as examples of substitution of nitrogen-containing functional groups no substitution takes place when /S. -difluoro amines are the reaction products. However, these methods have been included. 

The reaction of 2//-azirines (e.g.. 1) with hydrogen fluoride in pyridine [pyridinium poly(hy-drogen fluoride). Olah s reagent] gives /f,/f-difluoro amines (e.g., 7) or a-fluoro ketones (e.g., 5) (Table 10). In some cases, pyrazines (e.g.. 9) are the main reaction products (Table IQj 31-35 2//-Azirines arc more reactive than aziridines towards pyridinium poly(hydrogcn... 

In the mechanism proposed to explain the formation of /l,y difluoro amines and a-fluoro ketones, two main, competing pathways are possible, after protonation of the 2//-azirine 1. One pathway leads to the / ,/ -difluoro amine 7 via the intermediates 2 and 6. A second possibility, via 2, 3 and 4, gives the observed a-fluoro ketone 5. Pyrazines are formed by the intermoleciilar reaction of the intermediates corresponding to 3, lo give diprotonated intermediates, e.g. 8. 

Difluoro Amines and a-Fluoro Ketones by the Reaction of 2//-Azirines with Pyridinium Poly(hydrogen fluoride) General Procedure ... 

Depending on the fluorinating reagent used, the reaction of imines leads to different fluorination products. Treatment of Schiff bases with trifluoromethyl hypofluorite gives A,A-difluoro amines under mild reaction conditions however, if the reaction is carried out using A-fluoro-bis(trifluoromethanesulfonyl)amine (TfjNF), a-monofluoro 2 and/or a,a-difluoro ketones 3 are obtained (Table 11). ... 

The ring-opening of aziridines by fluorinating agents yields a,j3-difluoro-amines. The stereochemistry of opening can be controlled by the correct choice of reagent, e.g. anhydrous HF, Olah s reagent, or EtaN wHF n = 2,... 

N,N-Difluoroamines. Primary amines can be converted into N,N-difluoro-amines in 50-75% yield by conversion into the Schiff base with benzaldehyde or, preferably, the sodium salt of 4-carboxybenzaldehyde, followed by reaction with fluoroxytrifluoromethane in methanol-methylene chloride. In the absence of methanol the alkyl fluoride is formed preferentially. ... 

Attempts to synthesize JV -difluoroamides via the action of a difluoro-amine-potassium fluoride adduct (7) on perfluoroalkanoyl fluorides (see p. 208) have led to the isolation and detailed spectral characterization of several perfluorinated aliphatic esters. Thus, treatment of trifluoroacetyl fluoride with adduct (7) at — 78 C gave the ester (8) as well as the amide CFg CO-NFg at -105°C, however, pentafluoroethyl trifluoroacetate was obtained at the expense of the bis(difluoroamino)>ester (8). It seems logical to assume that the HNFg,KF adduct acted as a source of fluoride ion and thereby initiated the dimerization of the acid fluoride (see Scheme 9). Acti vated [i.e. obtained via thermal decomposition of (CF3)gCF OK] potassium fluoride alone, vacuum-dried potassitim bifluoride, or a (CFglgN-OH-KF... 

A mixture of the imines jy -CFO NF (39%), a r/-CFO NF (52%), CFj NF (9%), and Ca, NF (trace) is product when A /V -difluorodichloro-fluoromethylamine is heated (100 Q with mercury and the iViV-difluoro-amines CF,CI-NF CFC1, NF and COj-NF, can be dechlorofluorinated with pentacarbonyliron in carbon tetrachloride at -30 to -t-20 Ctogivethe corresponding A -fluorodihalogenoimines, a procedure that apparently fails to convert the tetrafluoro-compound CHFj NF, into CHF NF but has been adapted to dehalogenate the tetrafluorohydrazine-fluoro-olefin adducts F,N CF, CXF NF, (X = F, Cl, or H) to provide cyanogen, the imine FN CF-CN, and a compound believed to be the nitrile FjN-CFj-CN. ... 

Fluoroamines s. Difluoro-amines, N-(Trifluoro-methyl) amines Fluoroazomethines... 

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