1.4- Phenylenediamine Phenylenedi amine

Diacetyl-o-phenylenediamine AT -Diacetyl-m-phenylenedi amine AT -Diacetyl-p-phenylenediamine... 

Frequent inflammation of the pharynx and larynx has heen reported in exposed workers. Very small quantities of the dust have caused asthmatic attacks in workers after periods of exposure ranging from 3 months to 10 years. Sensitization dermatitis has heen reported from its use in the fur dyeing industry. In this process, oxidation products of p-phenylenedi-amine are generated that are also strong skin sensitizers. Many instances of inflammation and damage of periocular and ocular tissue have been reported from contact with hair dyes containing p-phenylenediamine, presumably in sensitized individuals. ... 

Preparative applications have been found with the anhydrous bis-hy-drochlorides of various o-phenylenediamines 46. These were produced at the 50-g scale and all of these were required for enabling gas-solid condensation reactions with acetone [5]. If the monohydrochlorides of the o-phenylenedi-amines are required, the dihydrochlorides 47 are simply milled with a stoichiometric amount of the corresponding free solid diamine 46 in order to get... 

Chlorophenoxy herbicides (oeeupational exposures to) 4-Chloro-ort/io-phenylenediamine 4-Chloro-meta-phenylenedi amine Chloroprene... 

Quinoxaline has been prepared by the reaction of glyoxal with o-phenylenediamine, and 2-methylquinoxaline by the reaction of pyruvic aldehyde or isonitrosoacetone with < -phenylenedi-amine. 2,3-Pyrazinedicarboxylic acid has been prepared only by the permanganate oxidation of quinoxaline. 2-Methyl-5,6-pyrazinedicarboxylic acid has been prepared from 2-methyl-quinoxaline in the same way. - ... 

An alternahve method had been reported in the literature [12] to prepare [1,2,4] triazolo[4,3-a]piperazines (Route B, Scheme 5.9) via the condensahon of a chloromethyl oxadiazole with 1,2-phenylenediamine to afford the benzo fused compounds. The reachon condihons reported for this approach were harsh and the yields were low, presumably due to the poor nucleophilicity of 1,2-phenylenedi-amine. However, we felt that the synthesis of 3 could potentially be accomplished under milder reachon condihons because of the enhanced nucleophilicity of... 

Aminoirinitrophenylmefhylnitramine. See N-Methyl-N-nitro-2,4,6-trinitro-m-phenylenedi-amine, under Methylphenylenediamines 3-Amino-2,4,6-trinitrophenyInitramine. See N1 -Nitro-2,4,6-m-phenylenediamine, under Phenyl-enedi amines... 

However, the production of the />-phenylenediamine [106-50-3] intermediate is more complex, because it involves the diazotization and coupling of aniline [65-53-3]. Aniline reacts with nitrogen oxides, produced via the oxidation of ammonia, to form 1,3-diphenyltriazene [136-35-6] in the process used by Du Pont (208,209) (see Amines, aromatic-aniline and its derivatives). In the Akzo process a metal nitrite salt and acid in water is used (210). The triazene rearranges in the presence of acid and an excess of aniline to form predominately the p-aminoazobenzene [60-09-3] and a small amount of the ortho isomer, 0-aminoazobenzene [2835-58-7]. The mixture of isomers is catalytically reduced to the respective diamines, and they are then separated from the aniline, which is recycled (208,209). The 0-phenylenedi amine [95-54-5] is used in the manufacture of herbicides (see Amines, aromatic-phenylenediamines). 

An alternative procedure starts from a metal complex of o-phenylenedi-amine. For example, the bis(o-phenylenediamine) complex of nickel(II) chloride reacts with acetylacetone to give a mixture of a nickel complex of the diamine and diketone together with 2,4-dimethylbenzodiazepinium chloride (76CPB1934 91JPR327). Chromium complexes have been used in the same way [91JCS(D)2045]. 

Trinitro-4-rapid heating sol in et acet amyl ale, v sol in boiling AcOH or chlf. Can be prepd by treating picryl chloride with p-phenylenedi amine in ale, or by other methods... 

METHOXYBENZENE FURRO L 4-METHOXY-l,3-BENZENEDIAMINE p-METHOXY-m-PHENYLENEDI-AMINE 4-METHOXY-m-PHENYLENEDIAMINE 4-MMPD PELAGOL DA PELAGOL GREY L PELAGOL L... 

SYNS m-. MINOANILINE 3-AMINOANTLINE APCO 2330 m-BENZENEDlAxMINE 1,3-BENZENE-DLAMINE C.L 76025 DEVELOPER 11 m-DIAMINOBENZENE 1,3-DLAMINOBENZENE DIRECT BROWN BR m-FENYLENDIAMIN (CZECH) METAPHENYLENEDIAMINE 1,3-PHENYLENEDI-AMINE m-PHENYLENEDIAMINE (DOT) PHENYL-EXEDIAMINE, META, solid pOT)... 

The electrocatalytic reaction starts with electron transfer from p-phenylenedi-amine to the cobalt(lll) complex via the silver at a high reaction rate. A competitive reaction involving the oxidative formation of silver halide then begins. This silver halide may be reduced by p-phenylenediamine, which is thus is oxidized directly by the cobalt(III) complex and also by the silver halide formed by the oxidation of silver. 

Permanent hair dyes are often derivatives of an aromatic amine, discovered as a hair dye in 1883, called /Mra-phenylenediamine (H2N-C6H4-NH2), including primary intermediates such as pcirci-aminophenol, dihydroxybenzene, 4-methylaminophenol, tetraaminopyrimidine, 2-aminomethyl-4-aminophenol, and / ara-aminodiphenylamine. The / zrra-phenylenedi-amine compound produces a black color, with its derivative parci- mmo-diphenylaminesulfonic acid used in blond formulations. Couplers are generally aromatic phenols or amines that have an available site that is subject to electrophilic interaction. Typical couplers include chemicals such as resorcinol, wrte-phenylenediamine, 2,4-diaminoanisole, mrm-aminophenol,... 

The primary toxicological concerns of hair dyes, primarily oxidation hair dyes, are with contact dermatitis and long-term potential systemic effects [5]. Of all hair products, the most sensitizing are the paradiamine oxidation dyes [63], and the most sensitizing ingredients of these products are p-phenylenediamine, p-toluenediamine sulfate, and o-chloro-p-phenylenedi-amine, although other related aromatic amines have also been shown to provide some sensitizing potential [62]. 

The success of the diaUtyl-p-phenylenediamines led to the development of related antiozonants, i.e., aUtyl/aryl-analogs, N-isopropyl-N -pheny-p-phenylenediamine (IPPD) and N-cyclohexyl-N -phenyl-p-phenylenediamine, and mixed N,N -diaryl-p-phenylenedi-amine mixtures. 

A large number of antioxidants of organic structure, of the type of amines and phenols, were investigated in [42, 43]. The additives were introduced by powdering the capron in the form of crumbs before spinning of the fiber, as well as into the fused caprolactam before polymerization. The antioxidants beloi ing to the amine class, such as N,N -di-/3 -naphthyl-p-phenylenediamine, N, N-phenylcyclohexyl-p-phenylenedi-amine, N,N -diphenyl-p-phenylenediamine, and phenyl-jS-naphthylamine, preserve the strength of the fiber by 70-95% when it is heated for 2 hr... 

Aromatic Amines /3-naphthylamine, phenyl-Q -naphthylamine, diphenylguanidine, phenthiazine [3] phenyl-)3-naphthylamine [35], N,N -diphenyl-p-phenylenediamine [56 ] N, N -di-/S -naphthyl-p-phenylenedi-amine [42, 44] N,N -phenylcyclohexyl-p-phenylenediamine [35, 42]. 

Whilst there are no reports in the literature of crystalline products having been obtained from the interactions of adrenochrome with o-phenylenedi-amine. Auterhoff and Hamacher have prepared a phenazine derivative (103) by the interaction of o-phenylenediamine with rubreserine (66) (a compound structurally similar to the aminochromes) [193]. In the same paper, the authors describe the reaction of rubreserine with ammonia in alcohol at reflux temperatures. A complex mixture of products including the phenoxazone derivative, eserine blue was obtained [193]. 

Fig. 3.39 Effect of amines on change in rubber molecular weight during plasticization (a) at 130°C (b) at 30 C. (1) Unmodified rubber (2) with phenyl-/f-naphthylamine (3) with JV,A -di(methylheptyl)-/ -phenylenediamine (4) with V-phenyl-A -isopropyl-/ -phenylenedi-amine (5) with A, A -diphenyl-p-phenylenediamine [36].

---