Derivatives Toluidides

Appllca.tlons. Various A/-derivatives of amino acids (qv) are resolvable on BSA columns. These /V-amino acid derivatives include ben2enesulfonyl-, phthalimido-, S-dimethylarnino-l-naphthalenesulfonyl- (DANSYL-), 2,4-dinitrophenyl- (DNP-), and 2,3,6-trinitrophenyl- (TNP-) derivatives (30). Amines such as Prilocain, ( )-2-(prop5lamino)-(9-propiono-toluidide, a local anesthetic (Astra Pharm. Co.), are also resolved on BSA. The aromatic amino acids DL-tryptophan, 5-hydroxy-DL-tryptophan, DL-kynurenine [343-65-7] C qH 2N 2 3 3-hydroxy-DT.-kynurenine [484-78-6] and dmgs... 

Other common intermediates for azo pigment production are 2,4-dinitro-aniline, acetoacet-o-chloroanilide, acetoacet-o-toluidide, phenyl- and p-tolyl-methylpyrazolone, 2-hydroxy-3-naphthoic acid, Naphtol AS and its derivatives, and 2-chloro-4-aminotoluene-5-sulfonic acid. 

A considerable number of acylarylamines, among them o-chloroacet-anilide, 2,6-dichloro-4-nitroacetanilide, and l-acetamido-2-methylan-thraquinone, form abnormal nitroso compounds with nitrous fumes others, such as 4-dimethylamino-4 -acetamidoazobenzene, benzene-p-toluidide, and diacetyl-1,3-phenylene diamine, do not yield nitroso compounds with nitrous fumes a third group, which includes p-nitroacet-anilide and a- and /3-acetamidoanthraquinone, is recovered unchanged after the same treatment.63 In general, the acetamido group submits to nitrosation, whereas the benzoyl and benzenesulfonyl and toluenesul-fonyl derivatives of amines are resistant to the notion of nitrous fumes. 

The more important dinitroaniline derivatives known today are N,N-bis(2-chloroethyl)-4-trifluoromethyl-2,6-dinitroaniline (BAS 3870 H, 1) N-butyl-N-ethyl-a,a,a-trifluoro-2,6-dinitro-p-toluidide (benfluralin, 2) N-jec-butyl-4-r-butyl-... 

Sulfene trapping competition experiments have been carried out with a series of aromatic amines132. In each case phenylsulfene was formed from phenylmethanesulfonyl chloride with triethylamine in the presence of an equimolar mixture of p-toluidine and another aniline derivative. The product ratio ( X-anilide p-toluidide) varied from 1.12 for p-anisidine to 0.12 for m-nitroaniline, and gave a good fit to a Hammett plot with cr = — 1.04 this accords with a transition state possessing a partial positive charge in the aromatic amine. 

Hydroxymethylene camphor phosphinic acid, CioHi40=CH. P0(0H)2, is isolated as a by-product in the preparation of hydroxymethylene camphor by treating oxymethylene camphor (3 mols.) with phosphorus trichloride (2 mols.). It crystallises with half a molecule of water, which may be expelled at 110° C. The ammonium, silver and lead salts are known, also the following derivatives oxychloride, CioHi40 = CH.POCl2, white tablets, M.pt. 51° C, B.pt. 175° to 180° C-., decomposed by water aniline salt, M.pt. 195° to 196° C. anilide, slender yellow needles, M.pt. 227° to 228° C. p-toluidide, M.pt. 210° C. p-phenetidide, M.pt. 137° C. diethyl ester, B.pt. 195° to 205° C. at 20 mm., decomposed by water. 

The most common derivatives are the amides, the anilides, and the p-toluidides. O O... 

Working in a hood, place 0.50 g of the acid and 2 mL of thionyl chloride into a small round-bottom flask. Add a magnetic stir bar, and attach a water-jacketed condenser and a drying tube packed with calcium chloride to the flask. While stirring, heat the reaction mixture to boiling for 30 minutes on a hot plate. Allow the mixture to cool to room temperature. Use this mixture to prepare the amide, anilide, or p-toluidide derivatives by one of the following three procedures. 

Three satisfactory solid derivatives of carboxylic acids are amides (Eq. 25.46), anilides (Eq. 25.47), and p-toluidides (Eq. 25.48). These derivatives are prepared by treating the corresponding acid chlorides with ammonia, aniline, or p-tolui-dine. The amides are generally less satisfactory derivatives than the other two because they tend to be more soluble in water and thus are harder to isolate. The acid chlorides are most conveniently prepared from the acid, or its salt, and thionyl chloride (Eq. 25.49). 

Reference should be made to Tables 4, 5, 29, for amides, anilides and p-toluidides of carboxylic and sulphonic acids Tables 14, 15, 16, for formyl, acetyl, benzoyl and p-toluenesulphonyl derivatives of primary and secondary amines Table 18 for acyl derivatives of amino-acids Table 7 for acyl derivatives of aminophenols. 

Acetoacet-o-toluidide 104 conc. H2SO4) at 0° gives p-nitro- deriv., 182. Violet colour with FeCls. 

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