Toluidides

Amides, anilides and p toluidides. The dry acid is first converted by excess of thionyl chloride into the acid chloride ... 

The by-products are both gaseous and the excess of thiouyl chloride (b.p. 78°) may be readily removed by distillation. Interaction of the acid chloride with ammonia solution, aniline or p-toluidiiie yields the amide, anilide or p-toluidide respectively ... 

Anilides and p-toluidides may also be prepared directly from the acide% by heating them with aniline or p toluidine respectively ... 

The above simple experiments illustrate the more important properties of aliphatic acid chlorides. For characterisation, the general procedure is to hydrolyse the acid chloride by warming with dilute alkali solution, neutralise the resulting solution with dilute hydrochloric acid (phenol-phthalein), and evaporate to dryness on a water bath. The mixture of the sodium salt of the acid and sodium chloride thus obtained may be employed for the preparation of solid esters as detailed under Aliphatic Acids, Section 111,85. The anilide or p-toluidide may be prepared directly from the acid chloride (see (iii) above and Section III,85,i). 

Anilides or p-toluidides of acids from esters. Esters are converted into the corresponding anilides or p-toluidides by treatment with anilino- or with p-toluidino-magnesium bromide, which are readily obtained from any simple Grignard reagent and aniline or p-toluidine ... 

Acyl hahdes may be identified by —hydrolysis to the corresponding acids (the latter may be further characterised as in Section IV,175) conversion into amides (Section IV,191), anihdes or p-toluidides (Section IV,100) and conversion into sohd esters (Section IV,183). 

Upon warming with 10-20 per cent, sodium or potassium hydroxide solution, no ammonia is evolved (distinction from primary amides). The base, however, is usually liberated upon fusion with soda lime (see experimental details in Section IV,175) and at the same time the acyl group yields a hydrocarbon. Thus benz-p-toluidide affords p-tolu-idine and benzene. 

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... 

Aceto-m-toluidide [537-92-8] from H2O, EtOH or aqueous EtOH. 

Aceto-p-toluidide [103-89-9] M 149.2, m 146 , b 307 /760mm. Crystd from aqueous EtOH. 

Hydroxy-2-naphtho-4 -chloro-o-toluidide [92-76-2] M 311.8, m 243.5-244.5 . Crystd from xylene [Schnopper, Broussard and La Forgia Anal Chem 31 1542 1959]. 

One mol of o-bromopropio-ortho-toluidide is mixed with a solution of 3 mols of n-propyl-amine in 500 ml of water-free benzene and the reaction mixture is heated in an autoclave to OO C for 8 hours. After cooling the reaction mixture is treated as described above. The base is obtained as a colorless oil. BP 159°-162 C/0.1 mm. Yield 55%. The base is then converted to the hydrochloride by reaction with HCl. 

The most extensive study of the effect of conditions upon the kinetics of bromination was made by Robertson et al.23l 279, who measured the rates of bromination of alkylbenzenes, acetanilide, aceto-p-toluidide, mesitylene, anisole and p-tolyl methyl ether in acetic acid at 24 °C. They found that at relatively high concentrations of bromine (A//40-M/100) the reaction is second-order in bromine, i.e. the rate equation is... 

C H24C1FN20 32566-12-4) see Flurazepam 4 -chloro-fV-[2-(diethyIamino)ethyl]-a-(o-ffluorophenyl)-W hydroxy-13-dioxo-2-isoindolineaceto-o-toluidide (C29H29CIFN3O4 32566-13-5) see Flurazepam... 

Chemical name 2-Chloro-A/-ethoxymethyl-6 -ethylacet-o-toluidide... 

By oxidation of acet-/>-toluidide, followed by esterification of the 7>-aminobenzoic acid. Chemnitius, Pharm. Zentralh. 68, 765 (1927). 

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