Amines nitro and nitroso compounds

Radiation chemistry of amines, nitro and nitroso compounds... 

C. L. Greenstock, Radiation chemistry of amines, nitro and nitroso compounds in Supplement F The Chemistry of Amino, Nitroso and Nitro Compounds and their Derivatives, Part 1 (Ed. S. Patai), Wiley, Chichester, 1982, p. 291. 

Reductive alkylations have been carried out successfully with compounds that are not carbonyls or amines, but which are transformed during the hydrogenation to suitable functions. Azides, azo, hydrazo, nitro and nitroso compounds, oximes, pyridines, and hydroxylamines serve as amines phenols, acetals, ketals, or hydrazones serve as carbonyls 6,7,8,9,12,17,24,41,42,58). Alkylations using masked functions have been successful at times when use of unmasked functions have failed (2). In a synthesis leading to methoxatin, a key... 

Nitro- and nitroso-compounds,170171 amines, and thiols induce the decomposition of diacyl peroxides in what may be written as an overall redox reaction. Certain monomers have been reported to cause induced decomposition of BPO. These include AN,172 A -vinylcarbazole,17,177 Ar-vinylimidazole178 and NVP.177... 

Aromatic nitro and nitroso compounds are easily reduced at carbon and mercury electrodes. Other nitro compounds such as nitrate esters, nitramines, and nitrosamines are also typically easily reduced. The complete reduction of a nitro compound consists of three two-electron steps (nitro-nitroso-hydroxylamine-amine). Since most organic oxidations are only two-electron processes, higher sensitivity is typically found for nitro compounds. Several LCEC based determination of nitro compounds have been reported... 

FIGURE 1. Number of publications (per year) relating to force fields and dealing with amines, nitro or nitroso compounds, during the years 1968-1994. Most of the works, prior to 1975, are connected with vibrational force fields... 

In this section the electrode reactions of amines and nitro and nitroso compounds will be discussed. The presence of an amino group usually makes the reduction of a molecule more difficult, but the amino group is, in most cases, not directly involved in the reduction. Three types of exception have been found. 

Disposal methods for some of the more common classes of organic compounds may be found in Chemical Safety Matters (hydrocarbons halogenated hydrocarbons alcohols and phenols ethers, thiols, and organosnlfnr componnds carboxylic acids and derivatives aldehydes ketones amines nitro and nitroso componnds and peroxides). 

Common colored compounds include nitro and nitroso compounds (yellow), a-diketones (yellow), quinones (yellow to red), azo compounds (yellow to red), and polyconjugated olefins and ketones (yellow to red). Phenols and amines are often brown to dark-purple because of traces of air oxidation products. 

The formation of a dinitrone - in contrast to the ozonation of DOPPD - is inhibited most probably just by the stabilizing effect of the N-phenyl group. The same structural moiety stabilizes aromatic nitro and nitroso compounds formed via the amine oxide pathway no Bandrowski bases were detected in the ozonation product of HPPD. The authors (40) favor the N-alkyl side reactivity in HPPD also in the interpretation of the formation of N-phenyl-N -acyl-l,4-PD, i.e. in the condensation with aliphatic aldehydes. 

The following paragraphs describe the methods of forming azo compounds in which an N-N bond is created (for preparation by coupling see the Section on Preparation of the C-N bond by replacement .) These methods can be classified as (a) oxidative junction of amines (b) oxidation of hydrazo compounds (c) disproportionation of hydrazo compounds (d) action of hypochlorite on iV,jV -diarylsulfamides (e) condensation of nitroso compounds with amines (f) reaction of nitro compounds with amines (g) reduction of nitro and nitroso compounds and (h) reaction of JV-arylhydroxylamines with sulfinylimines. 

The primary antioxidants are normally broken down further into the classes of chain-breaking donor (CB-D) and chain-breaking acceptor (CB-A). CB-D additives interact with peroxy radicals, and are by far the commonest class of antioxidant in general use. They are represented by such additives types as hindered phenols and secondary aromatic amines. CB-A additives interact with alkyl radicals but, due to the rapid oxidation of such radicals, these additives are really useful only under low oxygen availability. CB-A types are represented by aromatic nitro and nitroso compounds, and a few speciality stable free radicals. Some transformation products of CB-D antioxidants can also act as CB-A species. 

A wide range of ar. nitro and nitroso compounds are rapidly and smoothly reduced to the corresponding amines by NaBH4 in the presence of palladized charcoal.—E A little 10 -Pd-on-charcoal suspended in water, 2 moles of NaBH4 in water added, a slow Ng-stream bubbled through the mixture while a soln. of o-nitrophenol in 2 N NaOH-soln. is added dropwise during 5 min., and allowed to stand at room temp, for a further 10 min. o-aminophenol. Y 79%.—Similarly Dimethyl-p-nitrosaniline -> p-aminodimethylaniline. Y 93%. F. amines from nitro compounds s. T. Neilson, H. G. S. Wood, and A. G. Wylie, Soc. 1962, 371. 

A wide range of aromatic nitro and nitroso compounds are rapidly and smoothly reduced to the corresponding amines by sodium boron hydride in the presence of palladized charcoal . Selective and stereospecific reductions can be performed with di-imide, an unstable reagent prepared in situ from a number of precursors . Peroxyacetic acid is an excellent oxidizing agent for a variety of hydrazine derivatives... 

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