Arylamine Mixtures

Yamaguchi et al. (1990, 1990a, 1991, 1991a, 1991b) and Yamaguchi (1992) described a bipolar doped polymer comprised of 3,5-dimethyl-3, 5 -di-/-butyl-4,4 -diphenoquinone (DMDB) and N,N,N, N -tetrakis(/M-methylphenyl)-l,3-diaminobenzene (PDA) in poly(4,4 -cyclohexylidenediphenylcarbonate) (PCZ). 

Yamaguchi and coworkers concluded that each transport-active component functions independently with no charge-transfer interaction. 

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Phosphonylated aminoquinolines are prepared from phosphonylated arylamines obtained as above in refluxing toluene from diethyl 2-phenyl-2-oxoethylphosphonate and arylamines [mixture of the P-imino- and (Z)-P-enamino derivatives]. Metallation of p-unino and p-enaminophosohonates with n-BuLi in THF followed by sequential treatment with isocyanates, triphenylphosphine, hexachloroethane, Et3N, and aqueous workup produces, after deprotection, 3-phosphonylated-4-aminoquinolines (Scheme 7.1 IS). - ... 

Kinetic mles of oxidation of MDASA and TPASA by periodate ions in the weak-acidic medium at the presence of mthenium (VI), iridium (IV), rhodium (III) and their mixtures are investigated by spectrophotometric method. The influence of high temperature treatment with mineral acids of catalysts, concentration of reactants, interfering ions, temperature and ionic strength of solutions on the rate of reactions was investigated. Optimal conditions of indicator reactions, rate constants and energy of activation for arylamine oxidation reactions at the presence of individual catalysts are determined. 

The yield of 3//-azepine appears to be influenced by substituents on the azide ring although no in-depth study has been reported. 4-Halophenyl azides, in most cases, give rise to complex mixtures of products.177 4-Tolyl azide, on thermolysis in aniline, yields 5-methyl-iV-phenyl-3//-azepin-2-amine (18% mp 157-158°C), whereas the thermolyses of 4-methoxy-, 4-methyl-, 4-chloro-, and 4-nitrophenyl azides in a range of arylamines (4-chloro-, 4-methoxy-, and pen-tafluoroaniline) yield only azo compounds and uncharacterized tarry products.178... 

The Pd°-catalyzed arylations using arenediazonium tetrafluoroborates are limited to those diazonium salts that can be manipulated at room temperature. The reaction can, if necessary, be performed at temperatures up to 50 °C by using a mixture of an arylamine and tert-butyl nitrite in chloroacetic acid or in a mixture of chloroacetic and acetic acid (Kikukawa et al., 1981a). Styrene reacted with fourteen arylamines in the presence of 5 mol-% Pd(dba)2 to give the corresponding substituted stilbenes in yields of 46-97%. It is important for good yields to carry out these reactions in an acidic system. Without acid the yield was low (11%), and diazo tars were also formed. 

The BASF route started from hydroquinone, which was converted to 2,5-dihydroterephthalic acid by a Kolbe-Schmitt reaction. One mole of this acid was treated with two moles of an arylamine, both components being in the form of a suspension in aqueous methanol. This was added to a small amount of a solution of vanadium(III) chloride and sodium chlorate. Gentle heating gave a 95% yield of 2,5-bis(arylamino)benzo-l,4-quinone-3,6-dicarboxylic acid. Ring closure to the trans-quinacridonequinone took place in the presence of concentrated sulphuric acid at 60-80 °C. This was then reduced to the required crude pigment by zinc or aluminium powder in caustic soda under pressure,in an aluminium chloride/urea melt or by the use of a sulphuric acid/polyphosphoric acid mixture. 

Similarly, benzene and hydrazoic acid in the presence of a mixture of fluorosulphonic and trifluoromethanesulphonic acid give aniline quantitatively. From toluene 100% of a mixture of o-, m- and p-toluidines is obtained and bromobenzene yields 42% o-bromoaniline and 47% p-bromoaniline, Butyl azide gives iV-butylarylamines under these conditions89. Photolysis of 1-aminoquinolinium perchlorate (76) in aromatic hydrocarbons (benzene, toluene, ethylbenzene or mesitylene) in the presence of 18-crown-6 affords arylamines, e.g. aniline and p-toluidine, by way of the nitrenium ion90 cf Reference 91. 

Anilines are converted into nitrosoarenes ArNO by the action of hydrogen peroxide in the presence of [Mo(0)(02)2(H20) (HMPA)]224, whereas catalysis of the reaction by titanium silicate and zeolites results in the formation of azoxybenzenes ArN (0)=NAr225. Azo compounds ArN=NAr are formed in 42-99% yields by the phase-transfer assisted potassium permanganate oxidation of primary aromatic amines in aqueous benzene containing a little tetrabutylammonium bromide226. The reaction of arylamines with chromyl chloride gives solid adducts which, on hydrolysis, yield mixtures of azo compounds, p-benzoquinone and p-benzoquinone anils 234227. 

Method B The amide (5 mmol) and TEBA-Br, (1.95 g, 5 mmol) are added to aqueous NaOH (2.5M, 30 ml) and the mixture is stirred at room temperature until a brown colour persists. The mixture is steam distilled and the distillate is extracted with CH2CI2 (4 x 40 ml). The combined extracts are dried (MgS04) and evaporated to yield the arylamine. Aliphatic amines are isolated by extraction of the reaction mixture with Et20 and saturating the dried (MgSQ,) solution with HCI gas to produce the ammonium chlorides. 

Catalysed oxidation of primary and secondary amines generally has little synthetic value. Primary amines yield either a mixture of nitriles and amides (ca. 30%) or, in the case of arylamines, the azo derivatives (42-99%) [39], Symmetrical and non-symmetrical azoarenes are also produced in good yields ( 60%) from the reaction of acetanilides with nitroarenes under basic solidtliquid conditions, although higher yields are obtained using TDA-1 [40],... 

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). 

The required arylamine 973 was prepared starting from the aryl acetate 937. The compound 937 was also used for the palladium(II)-catalyzed total synthesis of carbazoquinocin C (274) (545) (see Scheme 5.124) and carbazomycin G (269) (652). The acetate 937 was transformed to the corresponding 5-nitro derivative 974 by reacting with fuming nitric acid in a mixture of acetic anhydride and glacial acetic... 

The reaction of the iron-complex salts 602 and 779 with the arylamine 973 afforded the iron complexes 976 and 977, both in 96% yield. Subsequent O-acetylation provided the corresponding acetates 978 and 979 in almost quantitative yield. The iron-mediated arylamine cyclization of the O-acetyl derivative 978 using very active manganese dioxide provided the carbazole 971 in 72% yield. Under similar reaction conditions, the O-acetyl derivative 979 gave a mixture of the carbazoles 972 and 980 in 35% and 17% yield, respectively (650,651) (Scheme 5.136). 

Cyclohexadecadiyne (104) adds arylamines to form IV-arylpyrrolophanes such as (105), whereas alkylamines produce a mixture of heterophanes such as (106) and (107) (78TL2821). The reaction is catalyzed by Cu(I). 

The assay of arylamine-glass-bound -hydroxysteroid dehydrogenase (100 mg) is carried out as described for its free form with only one exception the reaction mixture is kept under continuous stirring. 

Serum or bile samples (0.2 ml) are incubated with 100 mg arylamine glass bound to -hydroxysteroid dehydrogenase, 200 mg arylamine-glass-bound diaphorase and 0.5 ml colour reagent in a 15 ml conical flask, in the dark at 30°C for 15 min (standard assay conditions for mixture of immobilised enzyme) under continuous stirring. The A54o of the reaction mixture is read. 

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