Difluoroamine

Oxidation of A-aminoazetidines (19), deoxygenation of A-nitrosoazetidines (20) and direct deamination of azetidines (21) with difluoroamine leads to cyclopropanes (23) by extrusion of nitrogen from a diazine intermediate (22) (63JA97). A further interesting ring contraction occurs in the Ag" catalysed solvolysis of the A-chloroazetidine (24), which appears to involve the intermediate cation (2S) (7ITLI09). 

The high reactivity of N-H bonds has also been exploited to produce N-F denvatives without significant substitution on neighbonng C-H bonds, Diethyl-phosphoramidates of ammonia, alkylammes, and a,polar solvents to produce difluoroamine [57], N,N-difluoroalkylamines, and a,to-bis(At,7V-difluoroamino)alkanes [52] Acetamide undergoes fluonnation to give modest yields of N,N difluoroacetatnide and acetyl fluonde when fluorinated... 

Reactions of benzylic a,P-aminoalcohols and a-hydroxyazindines with Olah s reagent provide a highly efficient way to a P-fluoroamines, a-fluoro-azindines, and ot,Y-difluoroamines [dS] (equations 43 and 44)... 

Acetoacetic esters react with difluoroamine to give alkyl 3,3-bis(difluoro-amino)butyrates [lOI] (equation 87). 

Caesimn fluoride, Difluoroamine See Difluoramine Benzenediazonimn tetrafluoroborate, etc. 

J.C. Oxley, J.L. Smith, J. Zhang, C Bedford, A Comparison of the Thermal Decomposition of Nitramines and Difluoroamines J. Phys. Chem. A., 105 (2001) 579-590. J. Zhang, J. Oxley, J. Smith, C. Bedford, R. Chapman Mass Spectral Fragmentation Pathways in Cyclic Difluoroamino and Nitro Compounds J. Mass Spectrometry, 35 (2000), 841-852. 

Difluoroamine (fluorimide) was discovered by Kennedy and Colburn as a by-product accompanying tetrafluorohydrazine in the reduction of NF3 by arsenic1 and arsine. It was found to be a product of hydrolysis of fluorinated urea80 and was detected in trace amounts among the products of fluorination of ammonia.8 Reactions to be considered for preparative purposes include the following (1) reduction of tetrafluorohydrazine,4 (2) hydrolysis of difluorourea, (3) protonation of trityldifluoroamine, (4) hydrolysis of difluorosulfamide,7 and (5) hydrolysis of isopropyl difluorocarbamate.8... 

Trityldifluoroamine and isopropyl difluorocarbamate are reported to be stable reagents which permit the generation of difluoroamine directly with a minimum of preliminary effort. Tetrafluorohydrazine also can be converted to difluoroamine with ordinary laboratory equipment. If these difluoroamino compounds are not available or if expense is a factor to be considered, the straightforward fluorination of urea or sulfamide in water followed by hydrolysis in situ permits the preparation of usable quantities of difluoroamine in a simple manner. 

---