Benzenamine through

A. N-Trijluoroacetanilide. In a two-necked, round-bottomed flask fitted with a thermometer, a Drierite tube, and a magnetic stirring bar are placed 4.56 ml. (4.66 g., 0.050 mole) of aniline [Benzenamine] (Note 1) and 15 ml. of dimethyl sulfoxide (Note 2). The resulting solution is stirred and cooled in an ice water bath, and when the internal temperature has dropped to 10-15°, 21.5 g. (0.10 mole) of 1,1,1-tri-chloro -3,3,3 -trifiuoroacetone [2 -Propanone, 1,1,1 -trichloro-3,3,3-tri-fluoro-] (Note 3) is added in portions through the condenser. A mild exotherm results, and the addition is extended over ca. 5 minutes to... 

Both inductive and resonance effects are involved. The favored reaction proceeds through the most stabilized (or least destabilized) intermediate carbocation. Study carefully the re.sonance forms pictured for the possible cations derived from electrophilic attack on meihylbenzene and (trilluoromethyl)benzene (Section I6-I), and on benzenamine (aniline), benzoic acid, and a haiobenzene (Section 16-2). Notice the types of groups that fall into the different categories in Table 16-1. In particular, notice the following two general trends ... 

Maes and co-workers have synthesized 5//-pyridazino[4,5-6]indole skeleton 39 through an intramolecular Heck reaction. Intermediate 38, 5-(2-bromo-4-(trifluoromethoxy)phenylamino)-2-benzyl-l,2-dihydropyridazin-3-(6//)-one was prepared via chemoselective Pd-catalyzed amination of 2-benzyl-5-iodopyridazin-3(2//)-one 36 and 2-bromo-4-(trifluoromethoxy)-benzenamine 37 in 66% yield and followed by an intra molecular cyclozition to yield the desired target compound 39 by a microwave iradiations. ... 

A Synthesis of 2-Nitrobenzenamine (o-Nitroaniline) Through Protected Benzenamine (Aniline)... 

Amines react with nitrous acid, through nucleophilic attack on the nitrosyl cation, NO. The product depends very much on whether the reactant is an alkanamine or a benzenamine (aniline) and on whether it is primary, secondary, or tertiary. This section deals with alkanamines aromatic amines will be considered in the next chapter. 

As mentioned in Section 22-4, V-nitrosation of primary benzenamines (anilines) furnishes arenediazonium salts, which can be used in the synthesis of phenols. Arenediazonium salts are stabilized by resonance of the tt electrons in the diazo function with those of the aromatic ring. They are converted into haloarenes, arenecarbonitriles, and other aromatic derivatives through replacement of nitrogen by the appropriate nucleophile. 

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