Diamines Phenylenediamines

Only the mono-amines are described here. The diamines are more frequently encountered as reduction products of dinitrobenzenes and nitro-anilines, and the chief reactions of the phenylenediamines are therefore given in Section 23, pp. 384-388. 

Compounds containing two primary amino groups attached to a benzene ring can be prepared by the reduction of dinitro compounds and of nitroanilines, usually with tin or stannous chloride and hydrochloric acid or with iron and very dilute hydrochloric acid. / ara-diamines may also be obtained by the reduction of aromatic amino-azo compounds (e.g., p-aminodimethylanihne from methyl orange, see Section IV,78). p-Phenylenediamine may also be prepared from p-nitroacetanilide reduction with iron and acid yields p-amino-acetaniUde,.which may be hydrolysed to the diamine. 

Primary aromatic diamines cannot be diazotised (tetrazotised) and coupled normally. Thus o-])henylenediamiiie yields a triazole derivative and m-phenylenediamine gives an azo dye (Bismarck brown) by selfcoupling. 

AMINES - AMINES,AROMATIC - PHENYLENEDIAMINES] (Vol 2) N,NQBis(3-methylphenyl)-N,NQdiphenyl-[l,lpbiphenyl]-4,4p diamine [65181-78-4]... 

Oxidation H ir Colorant. Color-forming reactions are accompHshed by primary intermediates, secondary intermediates, and oxidants. Primary intermediates include the so-called para dyes, -phenylenediamine, -toluenediamine, -aminodiphenylamine, and p- am in oph en o1, which form a quinone monoimine or diimine upon oxidation. The secondary intermediates, also known as couplers or modifiers, couple with the quinone imines to produce dyes. Secondary intermediates include y -diamines, y -aminophenols, polyhydroxyphenols, and naphthols. Some of the more important oxidation dye colors are given in Figure 1. An extensive listing is available (24,28). 

Use of 1,3 cycloaHphatic diamines in polyamides may be similarly limited by internal amide dehydration of the conformationaHy labile cis isomers to form a tetrahydropyrimidine (38) rather than high molecular weight polyamide. 1,3-Cyclohexanediamine is, however, a component of Spandex polyureas Du Pont uses the hydrogenation product of y -phenylenediamine [108-45-2] (24) captively to produce Lycra (see Fibers, elastomeric). 

Paraphenylene-diamine derivatives A/,N -Diphenyl-p-phenylenediamine (IV) /V,A/ -Di-p-naphthyl-p-phenylenediamine (V) Yes Yes Powerful antioxidants. Have been used in a variety of plastics materials. Tendency to bloom, bleed and stain mitigates against more extensive use. Compound (V) now withdrawn by some suppliers. 

In 1973 Du Pont commenced production of another aromatic polytunide fibre, a poly-(p-phenyleneterephthalamide) marketed as Kevlar. It is produced by the fourth method of polyamide production listed in the introductory section of this chapter, namely the reaction of a diamine with a diacid chloride. Specifically, p-phenylenediamine is treated with terephthalyl chloride in a mixture of hexamethylphosphoramide and V-methylpyrrolidone (2 1) at -10°C Figure 18.32). 

Polyfluorinated a-diketones react with 1,2-diainino compounds, such as ortlio-phenylenediamine, to give 2,3-substituted quinoxalmes [103] Furthermore, the carboxyl function of trifluoropyruvates offers an additional electrophilic center. Cyclic products are obtained with binucleophiles [13, 104] With aliphatic or aromatic 1,2-diamines, six-memhered heterocycles are formed Anilines and phenols undergo C-alkylation with trifluoropyruvates in the ortho position followed by ring closure to form y-lactams and y-lactones [11, 13, 52, 53, 54] (equation 23). 

Condensation of o-phenylenediamine or xV-methyl-o-phenylcne-diamine with alloxan (8) in neutral solution gives the ureides (9) and (10), respectively However, reaction of o-phenylenediamine with 1,3-dimethylalloxan (13) yields quinoxalin-3-one-2-carboxymethyl-amide (14), rather than the dimethyl ureide. Methylation of (9) in acetone in the presence of potassium carbonate gives the spiro-hydantoin (11). 

The reaction of o-diamines with w-nitroacetophenone in the presence of sodium dithionite furnishes 2-phenylquinoxalines, and reaction of o-phenylenediamine with p-N0..C,-.H4C0CH2X02 similarly gives 2- (4 -nitrophenyl) quinoxaline ... 

Peroxides N,N-Dimethyl-1,4-phenylenediamine (N,N-DPDD), N,N,N, N -tetra-methyl-l,4-phenylene-diamine (TPDD) Peroxides, e. g. alkyl hydroperoxides, oxidize N,N-DPDD to Wurster s red and TPDD to Wurster s blue. [17] [34]... 

N,N-Dimethyl-1,4-phenylenediamine (N,N-DPDD), N,N,N, N -tetra-methyl-l,4-phenylene-diamine (TPDD)... 

Many other useful pol3Tners can be made by combining different diamines and diacids. One example is Kevlar, a polyamide made by condensing terephthalic acid with phenylenediamine ... 

Secondary amines synthesized by catalytic reductive alkylation of primary amines are used in a variety of fine and specialty chemical indnstries. For example, derivatives of cyclohexylamine are used as corrosion inhibitors, N-(l,3-dimethylbntyl)-N -phenyl-p-phenylenediamine (6-PPD) is nsed as an anti-oxidant in rabber indnstiy, several dialkylated diamines are used in the coatings indnstiy, while they are nsed in the pharmacentical industry as pharmacophores (1-7). Harold Greenfield and co-workers have examined the ability of platinum group metals (PGM), base metals, and their snlfides to catalyze rednctive alkylation of primary and secotrdary amines (8-11). They found that different catalysts are optimal for the... 

It is especially important to control the acidity when aromatic diamines are treated with nitrous acid to form either the mono or bis diazonium salts, a process of some importance in the synthesis of disazo dyes and pigments (see later). p-Phenylenediamine is an example of a... 

In acid media, the complexes undergo rapid hydrolysis to yield free diamines, as shown for [Tc02(en)2] + [43]. The stability of the complexes is between that of O-coordinated and S-coordinated complexes, as shown in the reaction sequence of Tc(V) gluconate with pyridine, ethylenediamine or o-phenylenediamine to give the cationic N-coordinated species these, in turn, are able to exchange the nitrogen ligands by dithiols, such as DMSA [40]. 

For the preparation of CoSalophen Y the Co—Y was impregnated by salicy-laldehyde, and 1,2-phenylenediamine in methanol was added slowly to the mixture.107 This was a successful encapsulation of a salen-type complex with larger diamine than the ethylenediamine, a successful preparation of an encaged metal-salen complex by the intrazeolite ligand synthesis method, and a successful intrazeolite synthesis using two different precursor molecules. 

The 3tf,9tf-diazaperylenium dication 33 was synthesized for the first time in two steps from />-phenylenediamine. When reacted with l-bromo-3-chloropropane, this diamine gave the diazaperylene 359, containing two quinolizidine fragments <2001CC1742>, and this product was oxidized with HgO in acetic acid to give a low yield of a mixture of quinolizinium products 33 and 360 in a 1 3 molar ratio (Scheme 81) <20020L4113>. 

Azide 367 is prepared from 4-r -butyl-2-nitroaniline in 76% yield by its diazotization followed by treatment with sodium azide. In a 1,3-dipolar cycloaddition with cyanoacetamide, azide 367 is converted to triazole 368 that without separation is directly subjected to Dimroth rearrangement to give derivative 369 in 46% yield. Reduction of the nitro group provides ortfc-phenylenediamine 371 in 91% yield <2000EJM715>. Cyclocondensation of diamine 371 with phosgene furnishes benzimidazol-2-one 370 in 39% yield, whereas its reaction with sodium nitrite in 18% HC1 leads to benzotriazole derivative 372, which is isolated in 66% yield (Scheme 59). Products 370 and 372 exhibit potassium channel activating ability <2001FA841>. 

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