Phenylamine, substituted

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Nitroderivatives of toluene and/or naphthalene and/or di-phenylamine in which up to 4% of the total expl may be substituted with NC 20-30 20-30 15-20... 

A very similar explosive reaction was obtained with the same epoxide and with phenylamine, heterocyclic amines and N-substituted amines. In the Ie case, the reaction was described as not dangerous below 60 C and dangerous above 70 C. The large number of accidents that bring this epoxide and the amines mentioned into play were all caused by the fact that the reaction exothermicity was badly controlled. 

The regiochemistry for the substituted t-S with ammonia and DCNB was also studied (equation 43). When there is an alkoxy substituent on the para position, the reaction yields selectively l-amino-2-aryl-l-phenylamine (equation 44). 

Palmisano et al. [41] in a study on the selectivity of hydroxyl radical in the partial oxidation of different benzene derivatives have investigated how the substituent group affect the distribution of the hydroxylated compounds. The reported results show that the primary photocatalytic oxidation of compounds containing an electron donor group (phenol, phenylamine, etc.) leads to a selective substitution in ortho and para positions of aromatic molecules while in the presence of an electron-withdrawing group (nitrobenzene, benzoic acid, cyanobenzene, etc.) the attack of the OH radicals is nonselective, and a mixture of all the three possible isomers is obtained. 

Mononitromili nes, CjHjN,Oj, mw 138.12, N 20o28%, OB to CO, -150.6%. If the substitution takes place in the ring, 0,N. C H,. NH, the compd may be called nitromiline, mono-nitroaniline or nitroaminobenzene. It the substitution takes place in the -NH, group, the compd may be called nitraniline, N-rutro-aniline or phenylnitramine. In order to avoid confusion the last group of nitrated anilines is described under phenylamine... 

An interesting example of a formal [4 + 2]-cycloaddition has been found to occur on condensing A-substituted anilines with co-unsaturated aldehydes in the presence of Lewis Acids. In this study, A-phenylamines 162 underwent condensation with 163 to provide acridine products 165 in ca. 60-75% yields (Scheme 29) (96CC1213). The intermediate iminium ions 164 that are first formed either participate in a concerted [4 + 2]-cycloaddition (followed by proton transfer) or else undergo polar addition to the pendant alkene by addition of the resultant benzylic carbocation onto the aniline ring. 

These substances are derivable from benzene and its homo-logues by the substitution of one or more univalent groups (NHj) radical phenyl (CeHj), or its homologues, derivable from the benzene nucleus, for the hydrogen of ammonia. They all are strongly basic in character. 

In addition, PAs from adamantane substituted tri-phenylamine (TPA) moiety have been prepared to study the effect of the fluorinated monomer on the final properties of PAs (Figure 4.27) [63]. All these TPA-containing polymers showed high gas permeabihty and permselectivity. But among these, the PA (PA-xl) derived from 4,4 -(hexafluoroisopropy lidene)te(benzoic acid) exhibited the highest gas... 

Aniline, which is essentially phenylamine, is the simplest aromatic amine. Commercial aniline can be chemically synthesized from nitrobenzene which is prepared from benzene with nitric acid by electrophilic substitution reaction, as shown in Fig. 7.3, or from chlorobenzene by heating with ammonia in the presence of a copper catalyst. Some aromatic amines are natural, such as 2- and 4-aminobenzoic... 

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