Difluoroamino radical

Difluoroamino radical acetylene addition reactions, 33 185-189 addition reactions, 33 183-189 hydrogen abstraction reactions, 33 182-183 reactions with olefins, 33 183-185 reactions with other radicals, 33 181... 

The difluoroamino radical is able in some instances to abstract hydrogen from an organic substrate, producing a radical which can then itself react with NF2. The best known examples of this type are the reactions of N2F4 with some aldehydes (234), the following reaction being typical ... 

The difluoroamino radical may also react with a radical produced by a reaction with a third reactant in the system. Thus, for example, N2F4 will react with ethers when irradiated with light of wavelength 3000 A in the presence of benzophenone (80). There is no reaction between N2F4 and benzophenone, and it is thought that the latter abstracts hydrogen from the ether and so initiates reactions. 

In theory it should be possible to prepare tetrakis(difluoroamines) by the addition of difluoroamino radicals to an acetylene. It is found,... 

Difluoroamino radicals are readily generated from the equOibrium dissociation of tetrafluorohydrazine [360—364]... 

ADDITION OF DIFLUOROAMINO RADICALS TO DOUBLE AND TRIPLE BONDS... 

The difluoroamino radical is the only radical with the free electron situated on the nitrogen atom other than atomic nitrogen for which kinetic data for olefin addition have been accumulated. The only studies are those of Trotman-Dickenson and his co-workers [156—158]. 

Relative reactivity at 373 K of various olefins towards difluoroamino radicals [156, 158]... 

N2F4 dissociates readily into difluoroamino radicals, and these add to olefinic bonds slowly and reversibly... 

The absolute rate studies are summarized in Table 45. From these data relative rates can, of course, be calculated, and these are presented in Table 46. These relative rates indicate that the difluoroamino radical is rather electrophilic, with considerable discriminatory powers in reaction with olefins. The reactivity of vinyl fluoride seems much too low, but the investigators acknowledge experimental difficulty in measuring the rate with this compound. 

The photo-oxidation of CD3N2CD3,° the photolysis of azocyclohexane alone and in the presence of O2,10° and the photolysis of 1,1,1-trifluoromethylazo-methane as a source of CFS and CH3 radicals101 have been reported. Other studies of interest are concerned with the flash photolysis of hydrazine,102 the photolysis of H202-p-nitrosodimethylaniline-02 mixtures,103 temperature-dependent relaxation processes in electronically excited nitrosamide,104 the flash photolysis of difluoramine105 and the difluoroamino radical,100 and the lifetime of the state of PN.107... 

Gas-phase Kinetics of the Difluoroamino-radical , by A. J. White, Chem. 

Other names Difluoroamino radical, difluoroamidogen CAS Registry Number [3744-07-6]... 

The commonly used name, difluoroamino radical, is used in this text. 

A. F. Trotman-Dickenson, P. Cadman, A. J. White, The Kinetics of the Organic Reactions of the Difluoroamino Radical, Anales Asoc. Quim. Arg. 59 [1971] 163/8. 

J. P. Freeman, Chemical Characteristics of the Difluoroamino Radical, Inorg. Chim. Acta Rev. 1 [1967] 65/8. 

Tetrafluorohydrazine first synthesized in the late 1950s is a toxic, colorless gas of musty odor which liquefies at -73°C and solidifies at -163°C. The most characteristic chemical property of N2F4 is its easy dissociation into two difluoroamino radicals. At 300°C, N2F4 is almost completely dissociated. Many reactions of the very reactive N2F4 can be explained by its facile cleavage into NF2 radicals and their relative stability. 

NF2 + O. There is considerable disagreement on products, reaction stoichiometry, and rate constants for the reaction of the difluoroamino radical with oxygen atoms. A bright, green luminescence was ascribed to the (0,0) and (0,1) bands of the NF( 2 X 2") system. Additional weaker NF( A X 2 ) emission was observed when 0( P) atoms reacted with excess NF2 (both in Ar) [13]. A yellow-green luminescence from O + NO- NOJ was observed when oxygen atoms were in excess. The proposed reaction mechanism included three steps ... 

---