Nitro-anion free radicals

Figure 12. ESR spectra of nitro-anion free radicals from the microsomal reduction of nitro compounds, a. Radicals from the anaerobic incubation of 2 mM nitrobenzene with an NADPH-generating system and 1.5 mg/ml hepatic microsomes b, radicals from the anaerobic incubation of 1 mM nitrofurantoin with an NADPH-generating system and 1 mg/ml hepatic microsomes. From [88,169], with permission.

Mechanism of Richter reaction Nucleophilic substitution in gas phase Reactions of radical ions Radical anions of nitro compounds Free radical reactions... 

The ability of a nltro group in the substrate to bring about electron-transfer free radical chain nucleophilic subsdnidon fSpj li at a saniratedcarbon atom is well documented. Such electron transfer reacdons are one of the characterisdc feanires of nltro compounds. Komblum and Russell have established ihe Spj l reaction independently the details of the early history have been well reviewed by them. The reacdon of -nitrobenzyl chloride v/ith a salt of nitro ilkane is in sharp contrast to the general behavior of the ilkyladon of the carbanions derived from nitro ilkanes here, carbon ilkyladon is predominant. The carbon ilkyladon process proceeds via a chain reacdon involving anion radicals and free radicals, as shovmin Eq. 5.24 and Scheme 5.4 fSpj l reacdoni. 

Nifurtimox (Lampit) is a nitrofuran derivative whose likely mechanism of action for kUhng of trypanosomes is through the production of activated forms of oxygen. Nifurtimox is reduced to the nitro anion radical, which reacts with oxygen to produce superoxide and hydrogen peroxide. The free radical metabolites, an absence of parasite catalase, and a peroxide dehciency lead to hpid peroxidation and cell damage. This production of activated oxygen results in toxicity to the protozoal cells. 

Radical anions of geminal nitro compounds in DMF cleave rapidly to nitrite and a radical which initiate a free radical chain in which a v/c-dinitro compound is formed [43]. Radical anions of other a-substituted nitroalkanes may cleave either the nitro group or the other substituent 1-cyano-l-nitrocyclohexane thus splits off nitrite whereas 1-nitrocyclo-hexyl p-tolyl sulfone loses p-tolylsulfinate [44]. 

Nitro compounds can react with carbanion through the nucleophilic mechan-I, ( arbanions (as well as radical anions and free radicals) can be formed by the Itlon of strong bases on nitrocompounds. Russell and co-workers [66 pre-lied it in scheme (8) ... 

This chapter, far from being exhaustive, is aimed at outlining the properties of the radical ions and of the free radicals derived from photochromic compounds independently of whether or not these paramagnetic species are involved in the photochromic process itself. In particular, it will deal with the EPR of dihydro-and dialkyldipyridyl radical cations (viologens) and of the radical anions of a variety of nitro-substituted spirofmdoline-benzopyrans], spiro[indoline-naphtho-pyrans], and spiro[indoline-naphthoxazines] as well as their triphenylgermyloxy nitroxides and with the triplet spectra observed upon irradiation of 2,2,4,4-tetrachloro-1 -keto-1,4-dihydronaphthalene. 

The trypanocidal action of nifurtimox derives from its ability to undergo activation by partial reduction to nitro radical anions. Transfer of electrons from the activated drug then forms superoxide radical anions and other reactive oxygen species. Reaction of free radicals results in lipid peroxidation and membrane injury, enzyme inactivation, and DNA damage. Benznidazole also requires a one-electron transfer that generates nitro anion radicals, leading to cellular damage that kills the parasites. 

A number of papers have been dedicated to homolytic degradation of TN under the action of ultraviolet or 7-rays. The reaction of TNM with bases (e. benzidine) beings with the formation of CT complexes [183] yielding radical anions which in turn are split into radicals (NO ) and anions (e.g. nitroformanion Irradiation with 7-rays at 77K yielded radicals N02 and C(N02)3 (184). As most nifro compounds TNT inhibits polymerization induced by radiati-[185, 186] and free radical polymerization [I8O- 191]. This is rationalized f the fact that TNM is a radicals acceptor. The higher the number of nitro groui in nitro alkanes the stronger the inhibition of polymerization (189). 

Unlike most free radicals, 02 has little tendency to add to carbon-carbon double bonds it has been shown to be inert with most simple olefins as well as many aromatic hydrocarbons. It reacts with electron-poor aromatic compounds such as quinones and nitro derivatives to produce radical anions (Wilshire and Sawyer,... 

Nitro Compounds. The electrochemical method has proved most fruitful for the production of free radicals from nitro compounds more than half (about 250) of all the radicals which have been obtained by the method are radical nitro anions. This is largely explained by advances made in the polarographic investigation of nitro compounds, which provides the theoretical basis for the electrochemical generation method [156], and also by the fact that these radicals frequently possess high stability even in aqueous media. 

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