Aniline, Ring-substituted

Suatoni, J. C., R. E. Snyder, and R. O. Clark (1961), "Voltammetric Studies of Phenol and Aniline Ring Substitution," Anal. Chem. 33, 1894-1897. 

Sulfonation. Aniline reacts with sulfuric acid at high temperatures to form -aminoben2enesulfonic acid (sulfanilic acid [121 -57-3]). The initial product, aniline sulfate, rearranges to the ring-substituted sulfonic acid (40). If the para position is blocked, the (9-aminoben2enesulfonic acid derivative is isolated. Aminosulfonic acids of high purity have been prepared by sulfonating a mixture of the aromatic amine and sulfolane with sulfuric acid at 180-190°C (41). 

Zeyer J, A Wasserfallen, KN Timmis (1985) Microbial mineralization of ring-substituted anilines through an ort/jo-cleavage pathway. Appl Environ Microbiol 50 447-453. 

In order to understand these results it is necessary to consider the nature of the intermediates formed upon photolysis of arylamines. The absorption spectra of transients produced upon photolysis of aniline and various alkyl ring-substituted arylamines was obtained by Land and Porter (18) in different solvents using a flash photolysis apparatus. On this basis they identified both an anilinyl radical (PhNH-) and an anilinyl radical cation (PhNHj). The radical cation is present in polar media (H2O) but absent in cyclohexane. From these results, a homolytic cleavage... 

Figure 3. Four compounds designed by Jones et at12. The upper is the common structure and the lower shows different substitutions for these compounds. Each compound is named as the letter appearing on the aniline ring.

In the presence of tetramethyltin, 1-bromonauclefine reacts with CO in a Pd-catalyzed carbonylation to give the alkaloid naucletine [202], Dong and Busacca effected a new synthesis of tryptamines and tryptophols via a Rh-catalyzed hydroformylation of functionalized anilines that are prepared by a standard Heck reaction, as shown for the preparation of tryptamine sulfonamide 325 [423]. This reaction is applicable to ring-substituted tryptamines (Cl, Br, F. OMe, CF3). Likewise, the Rh-catalyzed carbonylation of o-alkynylanilines, which were prepared by a Pd-catalyzed Sonogashira coupling, leads to oxindoles (60-86% yields) [424],... 

The chemical character of a compound is not fundamentally altered by the introduction of a nitro-group. Thus the ring-substituted nitro-derivatives of the hydrocarbons are neutral compounds like the hydrocarbons themselves. If, however, a nitro-group enters a substance having, for instance, an acid character, then this character is thereby intensified the nitrophenols, for example, are more acidic than phenol. Correspondingly, the strength of bases is decreased by nitration the nitranilines are less basic than aniline. 

The fate of dissolved amines during disinfection of water by chlorination was determined by membrane injection MS. Aliphatic amines undergo TV-chlorination to exhaustion of the N-H atoms by one of the tentatively proposed paths shown in reaction 28. Aromatic amines undergo mainly ring substitution however, the possible intervention of N-C1 intermediates is not excluded. At pH 10.6 aniline chlorination is much slower than that of n-butylamine383. 

The study on the reaction of several ring-substituted anilines with HS in aqueous solutions showed that the free radical intermediates were converted to stable products by self-coupling or cross-coupling with other radical species (i. e., indigenous humic free radicals becoming incorporated into the HS macromolecule). 

Quinolines (2-substituted) Quinolines (8-substituted) a-Naphthylamines /TNaphthylamines Benzylamines (ring substituted) A-Substituted anilines 1 -Aminoanthracene ... 

A,A-Dialkylformamide acetals (7) react with primary amines to give the corresponding amidines (8). Kinetics of the reaction of a range of such acetals with ring-substituted anilines—previously measured in neutral solvents such as methanol or benzene —have been extended to pyridine solution. In pyridine, the reactions are irreversible, with first-order kinetics in each reactant, and mechanistically different from those in non-basic solvents. Two mechanisms are proposed to explain Hammett plots for a range of anilines, in which the p value switches from negative to positive at a cr value of ca 0.5. The pyridine solvent substantially enhances the rate in the case of very weakly basic anilines. 

Martin-Villodre, A., Pla-Delfina, J.M., Moreno. J.. Perez-Buendia, M.D., Miralles, J., Collado,E.F., Sanchez-Moyano, E.,and Del Pozo, A. Studies on the reliability of a bihyperbolic functional absorption model. 1. Ring-substituted anilines. J. 

OrtAo-substitution in the aniline ring favours the formation of a biphenyl derivative. Thus, in the electrochemical reduction of the 1-naphthylamide 54 the 1-... 

The procedure described here is based on a method outlined in U. S. patent 2,444,536.2 N-Phenylmaleimide has also been prepared by the dry distillation of the aniline salt of malic acid, 4 by treating the aniline salt of malic acid with phosphorus pent-oxide,5 and by treating maleanilic acid with phosphorus trichloride or with phosphorus pentoxide.5 Ring-substituted N-phenylmaleimides, viz., N-(/>-methoxyphenyl)-, N-(p-ethoxy-phenyl)-, and N-(/>-nitrophenyl)maleimide, have been prepared by treatment of the appropriate maleanilic acids with acetic anhydride and fused potassium acetate.7... 

Very recently, Genet and Michelet developed a diastereoselective reaction that took place by hydroamination of an unactivated alkene followed by a cydization process under very mild conditions. This 1,6-enyne reaction was compatible with electron-poor aromatic amines, including amines bearing chloride atoms (Equation 8.73), which is very useful for further functionalization of the substituted aniline ring [164]. 

Some examples of three-membered chelate rings containing N and S are known. iV-Sulfinyl-aniline, and substituted forms, has been shown to bond in this manner to give chelates of the type (43) with a number of metal ions in low oxidation states. Such compounds have been reported with Ni0,150 with Rh1 and Ir1,151 and with Fe0.152 A similar bonding mode has been demonstrated for 4-(methyl)thionitrosobenzene in a bridged adduct of general form [Fe2(CO)6L].153... 

The diarylurea is very sparingly water-soluble and is therefore easily separated from the monoarylurea which is readily soluble. Diarylurea formation is less extensive when ring-substituted anilines are used. 

Of course this new finding initiated the synthesis of a large number of 2,6-difluorobenzoyl-phenyl ureas and again QSAR was used for the optimisation of the series. A combined analysis of the 2,6-difluorobenzoyl and 2,6-dichlorobenzoyl subseries (IV) was performed both as a function of variation of the substitution pattern in the aniline ring. 

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