Amino radicals, from decomposition

Thermochemical data for alkyl amino radicals show for alkylhydrazines a trend in D (N-N) for these compounds in which the N-N bond was strengthened by increasing the degree of substitution by methyl in NH2 NH2 . From these values it was possible to determine values for the enthalpies of formation of the alkylamino radicals , and to confirm these by electron impact studies. The latter values were found to be in agreement with those obtained from pyrolysis studies. Hydrazine has often been used as a source of amino radicals by pyrolysis flame decomposition shock tube decomposition , electrodeless discharge and microwave discharge , viz. 

From the effect of solvent (Table 15) it is evident that the reactions discussed are nitrene reactions hydrogen-rich solvents suppress ring contraction and give rise to solvent dimer (bibenzyl) and/or a yellow nitrene dimer. The structure of the dimer is not known, but one possibility is shown in 144. A similar (colorless) dimer was obtained from 9-phenanthridylnitrene at 500 ° 7). Xhe two dimers formed from 137 and 141 in cyclohexane have nearly identical IR spectra. How could a hydrogen-rich solvent promote dimeriztion There is evidence from aryl azide decomposition in solution that amino radicals are formed first, and these dimerize and dehydrogenate as shown for 1-naphthylnitrene in [Eq. (48)] 82). 

Poly(azophenylene-o-carborane) (see 6) has been prepared from diphenyl-o-carborane by means of nitration, reduction, and acylation to initially give 1,2-bis(/ -nitroso-acetylaminophenyl)-o-carborane (NAFC). Rapid decomposition in solution affords phenylene amino phenyl carborane (PAFC) by recombination of phenylene and azophenylene radicals.40 These radicals have also been utilized to form copolymers of carborane-containing copolymers from monomers polymerizable via radical mechanisms. Thus, copolymers of polystyrene and poly(azophenylene) can be readily formed by means of emulsion copolymerization of styrene with NAFC decomposition products. 

HOCl-mediated protein oxidation accelerates under pathophysiological conditions. Thus, proteins from extracellular matrix obtained from advanced human atherosclerotic lesions contained the enhanced levels of oxidized amino acids (DOPA and dityrosine) compared to healthy arterial tissue [44], It was also found that superoxide enhanced the prooxidant effect of hypochlorite in protein oxidation supposedly by the decomposition of chloramines and chlor-amides forming nitrogen-centered free radicals and increasing protein fragmentation [45], In addition to chlorination, hypochlorite is able to oxidize proteins. The most readily oxidized amino acid residue of protein is methionine. Methionine is reversibly oxidized by many oxidants including hypochlorite to methionine sulfide and irreversibly to methionine sulfone [46] ... 

Fig. 1. a-Oxidation of amino acids. Hydroxyl radical (or other reactive radical) abstracts hydrogen atom from the a-carbon. The C-centered free radical formed may react with other amino acid residues or dimerize in the absence of oxygen, which leads to protein aggregation. In die presence of oxygen the carbon-centered radical forms peroxyl radical. Reduction of peroxyl radical leads to protein hydroperoxide. Decomposition of hydroperoxide leads to formation of carbonyl compounds via either oxidative deamination or oxidative decarboxylation. Oxidation of the new carbonyl group forms a carboxyl group. 

Protonated A-nitroso amines undergo photolytic decomposition from the excited state generating transient aminium radicals and nitric oxide. Aminium radicals, which are electrophilic radicals, initiate the addition to alkenes to give //-amino nitroso compounds or oc-amino oximes (Section 7.2.5.2), however, under an oxygen atmosphere, //-nitryloxy amines (/i-amino nitrates) are produced through peroxynitrites intermediates97-99. 

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