Chemicals arylamine

The orbital and resonance models for bonding in arylamines are simply alternative ways of describing the same phenomenon Delocalization of the nitrogen lone pair decreases the electron density at nitrogen while increasing it m the rr system of the aro matic ring We ve already seen one chemical consequence of this m the high level of reactivity of aniline m electrophilic aromatic substitution reactions (Section 12 12) Other ways m which electron delocalization affects the properties of arylamines are described m later sections of this chapter... 

The aromatic ring of a phenol like that of an arylamine is seen as an electron rich functional unit and is capable of a variety of reactions In some cases however it IS the hydroxyl oxygen that reacts instead An example of this kind of chemical reac tivity IS described m the following section... 

Toluenediamine (diaminotoluene, is an important iadustrial chemical iatermediate it is produced ia the largest volume of any arylamine and is the... 

The classic syntheses of the antibacterial sulfonamides involve reaction of the appropriate arylamine with an acid addition salt of p-amino-benzenesulfonyl chloride, or p-nitrobenzenesulfonyl chloride followed by reduction. Chemical interest largely resides in preparation of the corresponding arylamines. For the synthesis of sulfacytine (134), N-ethyl uracil (131) was converted to its thioamide (132) by reaction with phosphorous pentasulfide. The newly introduced sulfur is then displaced with ammonia in methanol to give 133. Standard reactions complete... 

Chemical Properties of Ultimate Carcinogenic Metabolites of Arylamines and Arylamides... 

SCHEME 3.65 Chemical structures of substituted anthracene arylamine. 

A different mode of reaction, however, is observed in photoreductions of nitroaromatics by aromatic tertiary amines. Irradiation of benzene solutions of N-methylated anilines and either m-chloronitrobenzene or 1-nitronaphthalene results in oxidative demethylation of the amines accompanied with reduction of the nitro compound to the corresponding arylamine 49). The authors suggest that hydrogen abstraction from the methyl group takes place as the primary chemical event. 

Synonyms AI3-03053 Aminobenzene Aminophen Aniline oil ANL Anyvim Aromatic amine Arylamine Benzenamine Benzidam Blue oil BRN 0605631 Caswell No. 051C CCRIS 44 C.I. 76000 C.l. oxidation base 1 Cyanol EINECS 200-539-3 EPA pesticide chemical code 251400 Krystallin Kyanol NCI-C03736 Phenylamine RCRA waste number U012 UN 1547. 

Principally the same, but chemically simpler, sequence was used to prepare arylnitro anion-radicals from arylamines, in high yields. For instance, aqueous sodium nitrite solution was added to a mixture of ascorbic acid and sodium 3,5-dibromo-4-aminobenzenesulfonate in water. After addition of aqueous sodium hydroxide solution, the cation-radical of sodium 3,5-dibromo-4-nitro-benzenesulfonate was formed in the solution. The latter was completely characterized by its ESR spectrum. Double functions of the nitrite and ascorbic acid in the reaction should be underlined. Nitrite takes part in diazotization of the starting amine and trapping of the phenyl a-radical formed after one-electron reduction of the intermediary diazo compound. Ascorbic acid produces acidity to the reaction solution (needed for diazotization) and plays the role of a reductant when the medium becomes alkaline. The method described was proposed for ESR analytical determination of nitrite ions in water solutions (Lagercrantz 1998). 

S H compounds. They may be generated during oxidation of ortho/para (but not meta) hydroquinones or aromatic diamines or hydroxytoluene compounds. The oxidation process may involve one-electron oxidation that could generate free radicals. There is increasing evidence that free radical metabolites represent possible toxic intermediates and/or ultimate carcinogens of chemicals (e.g., arylamines, haloalkanes). 

H and, 3C NMR spectra of monoimines have been reported and are shown in Table 3. These data fit the Hammett relationship and good correlations are found between various o constants and, 3C chemical shifts at positions remote from the substituent.1413C chemical shifts of imines derived from BA and variously substituted benzylamines are affected by substituents through up to 11 bonds.15 The influence of ZjE isomerism (Figure 3) and the effect of substituents on NMR spectra of some unsaturated imines have been studied.16 The photochemically induced isomerization of several substituted Schiff bases derived from BA and arylamines and their chemical shifts, as well... 

In general, EC reactions are typically observed according to the following general rank order (by relative ease of oxidation) o,p-quinol and o,p-aminophenol > tertiary amine > m-quinol rv phenol rv arylamine > secondary amine thiol > thioether primary amines, aliphatic alcohols. (HDVs) each redox active metabolite are obtained from the response across adjacent EC-Array sensors. These data are a reflection of the kinetic and thermodynamic components of electron transfer reactions. Since chemical structure is a critical determinant of an analyte s redox behavior, the intrinsic generation of an HDV with EC-Array provides qualitative information for each species. 

Since the discovery of this phenomenon with isoniazid over 40 years ago, nearly a dozen related drugs and chemicals have been found to be similarly influenced by genetic variation in this acetylase enzyme. Therefore, the likelihood of a slow acetylator encountering such a chemical/drug has increased. DNA amplification assay techniques of samples obtained from leukocytes, single hair roots, buccal epithelia, or other tissue have been developed that can be used to predict the acetylation phenotype of an individual. The availability of such information could, theoretically, be used to assess workers at high risk for toxicity (e.g., chemical workers exposed to arylamines normally inactivated by acetylation). 

Fig. 5.5. GC separation of TFA derivatives of arylamines. Peak 1 = solvent (CH2CI2) 2 = N-methyl-aniline 3 = N,N-dimethylaniline 4 = N-ethylaniline 5 = N-methyl-o-toluidine 6 = N-methyl-m-toluidine 7 = N-methyl-p-toluidine 8 = o-toluidine 9 = o-ethylaniline 10 = aniline 11 = 2,5-dimethyl-aniline 12 = 2,6-dimethylaniline 13 = 2,4-dimethylaniline 14 = m- toluidine 15 = p-toluidine 16 = 2,3-dimethylamline 17 = 3,5-dimethylaniline 18 = m-ethylaniline 19 = p-ethylaniline 20 = 3,4-dimethylaniline. Conditions stainless-steel column, 18 ft. X 0.125 in. O.D., 9.5% Apiezon L + 3.6% Carbowax 20M on Aeropack 30 (80—100 mesh) helium flow-rate, 100 ml/min column temperature, 152°C. (Reproduced from Anal. Chem., 39 (1967) 1188, by courtesy of the American Chemical Society.)...

The reduction of quinizarin using sodium hydrosulfite produces leuco quinizarin, which, in turn, undergoes condensation with alkyl- or arylamines and reoxidation to produce blue and green disperse and solvent dyes. Although chemical oxidation can be used, air oxidation is normally sufficient. See steps A and B in Fig. 13.112 for the general reaction scheme. The use of boric acid in the reduction step follows the course outlined in Fig. 13.H3, where the synthesis of C.I. Solvent Green 3 is given as an example.56... 

Since the chemical behavior of these unstable compounds deviated in many respects from that of the arylamines, it was first thought that they preferably exist in the imino form 257. In 1960 <1960AK515>, it was proved by NMR spectroscopy that the parent aminothiophene occurs exclusively in the amino form 256. This was confirmed later by more detailed investigations <1967TL5201, 1969JHC147>. Several other 2-N-substituted thiophenes have been... 

Hole transport in polymers occurs by charge transfer between adjacent donor functionalities. The functionalities can be associated with a dopant molecule, pendant groups of a polymer, or the polymer main chain. Most literature references are of doped polymers. The more common donor molecules include various arylalkane, arylamine, enamine, hydrazone, oxadiazole, oxazole, and pyrazoline derivatives. Commonly used polymers are polycarbonates, polyesters, and poly(styrene)s. Transport processes in these materials are unipolar. The mobilities are very low, strongly field and temperature dependent, as well as dependent on the dopant molecule, dopant concentration, and the polymer host This chapter reviews hole transport in polymers and doped polymers of potential relevance to xerography. The organization is by chemical classification. The discussion mainly includes molecularly doped, pendant, and... 

Uetrecht (71) provided further evidence that the arylamine group of procainamide is implicated in the development of drug-induced lupus by demonstrating that procainamide is metabolized to a hydroxylamine (HAPA) (Figure 16.11). HAPA is in equilibrium with a chemically unstable nitroso compound that is capable of covalent binding to histones and other proteins and/ by rendering them antigeniC/ may initiate the... 

---