7V- -methylanilines

V-Methylaniline hydrochloride [2739-12-0] M 143.7, m 123.0-123.1°. Crystd from dry benzene/CHCl3 and dried under vacuum. 

Two investigations on coupling reactions with aromatic amines to yield N- and C-coupling products have been carried out, namely the 7V-couplings with aniline (Beranek and Vecera, 1970) and with 7V-methylaniline (Beranek et al., 1972). ... 

Primary aromatic amines (e.g., aniline) and secondary aliphatic-aromatic amines (e. g., 7V-methylaniline) usually form triazenes in coupling reactions with benzenedi-azonium salts. If the nucleophilicity of the aryl residue is increased by addition of substituents or fused rings, as in 3-methylaniline and 1- and 2-naphthylamine, aminoazo formation takes place (C-coupling). However, the possibility has also been noted that in aminoazo formation the initial attack of the diazonium ion may still be at the amine N-atom, but the aN-complex might rearrange too rapidly to allow its identification (Beranek and Vecera, 1970). 

CjHijNO, 4136-97-4) see Bromopride Metoclopramide (3a,5a,17P)-17-mcthylandrostane-3,17-diol (C2oH,402 641-82-7) see Mestanolone (3p,5a,17P)-17-methylandrostane-3,17-diol (C20H34O2 641-83-8) see Mestanolone (3p,17P)-17-methylandrost-5-ene-3,17-diol diacetate (C24H3,i04 2061-86-1) see Methandriol 7V-methylaniline... 

Like the OH absorption of an alcohol, the NH absorption is not split by adjacent protons, nor does it cause spiitting of adjacent C - H absorptions in a H NMR spectrum. The NH peak of an amine is sometimes somewhat broader than other peaks in the spectrum. The H NMR spectrum of 7V-methylaniline is shown in Figure 25.4. 

Evidence in favor of the electron-transfer mechanism has also come from studies on substrates such as Ai-ethyl-7V-methylaniline which show a demethylation/... 

Ring opening is characteristic of the reactions of the fully conjugated systems. For example, on reaction of the dibenz[d/][l,3]oxazepine (25) with methylamine, the phenolic imine (27) was obtained in near quantitative yield, most probably via the intermediate adduct (26) (Scheme 2) <78CPB2508>. Ring opening of 1,3-benzoxazepine and 3,1-benzoxazepine was also observed on treatment with piperidine, and with 7V-methylaniline in the latter case <79TL376I>. 

V-Methylaniline [100-61-8] M 107.2, b 57"/4mm, 81-82"/14mm, df 0.985, ng 1.570, pK s 4.56. Dry it with KOH pellets and fractionally distil it imder vacuum. Acetylate, and the acetyl derivative is recrystallised to constant melting point (m 101-102°), then hydrolysed with aqueons HCl and distilled from zinc dust under reduced pressure. [Hammond Parks JAm Chem Soc 11 340 1955, Beilstein 12 IV 241.]... 

Secondary amines have a single N—H peak that occurs over a range from 3250 to 3550 cm. 7V-methylaniline provides an example (Figure 2.17). Thus, comparing the N—H peaks of primary and secondary amines easily allows us to distinguish them. 

Propiophenone has a carbonyl group bonded to the benzene ring that directs the bromine to the meta position. 7V-methylaniline resembles aniline, and the bromine will be directed to the ortho and para positions. The third compound has two nitro groups. Each one directs the electrophile onto the ring in positions meta to itself. Thus, both groups direct the bromine into the same position. The product... 

Penton and Zollinger (1979, 1981 b) reported that this could indeed be the case. The coupling reactions of 3-methylaniline and A,7V-dimethylaniline with 4-methoxy-benzenediazonium tetrafluoroborate in dry acetonitrile showed a number of unusual characteristics, in particular an increase in the kinetic deuterium isotope effect with temperature. C-coupling occurs predominantly (>86% for 3-methylaniline), but on addition of tert-butylammonium chloride the rate became much faster, and triazenes were predominantly formed (with loss of a methyl group in the case of A V-di-methylaniline). Therefore, the initial attack of the diazonium ion is probably at the amine N-atom, and aminoazo formation occurs via rearrangement. 

Table 13-1. General characteristics of reactions of 4-methoxybenzenediazonium tetrafluoroborate with 3-methylaniline and (partly) with 7V,7V-dimethylaniline in acetonitrile (after Penton and Zollinger, 1981b).

Nickel chloride promoted desulfurization and reductive cleavage of N,N -diarylthioureas gives corresponding anilines and tV-methylanilines (Scheme 69). While 7V,tV -dialkylthioureas undergo desulfurization to give formami-dines, and benzimidazoline-2-thiones underwent desulfurization to benzimidazoles (Scheme 69).159... 

Synonyms AI3-19498 AIDS-18972 Anilinomethane BRN 0741982 CCRIS 2870 EINECS 202-870-9 MA (Methylamino)benzene 7V-Methylaminobenzene A-Methylaniline IV-Methyl-benzenamine Methylphenylamine 7V-Methylphenylamine Monomethylaniline A-Monomethyl-aniline NSC 3502 7V-Phenylmethylamine UN 2294. 

V-nitramines too were reduced to disubstituted hydrazines. Electrolysis in 10% sulfuric acid over copper or lead cathodes reduced AT-nitrodimethylamine to. /V,JV-dimethylhydrazine (yield 69%), 7V-nitro-JV-methylaniline to N-methyl-JV-phenylhydrazine (yield 54%), W-nitropiperidine to JV,A -penta-methylenehydrazine (yield 52%) [734], and nitrourea to semicarbazide (yield 61-69%) [755]. 

The enamines 132, formed from 7V-(cyanomethyl)-Af-methylaniline and ethyl esters of aliphatic or aromatic carboxylic acids in the presence of sodium hydride, react with hydrazine to yield the pyrazoles 133 (equation 58)78. 

High-speed Pd-catalyzed amination of 2-chloropyrazine with 2V-methylaniline under temperature-controlled microwave heating produced 2-(7V-methyl-7V-phenyl)pyrazine in high yield (151) [73]. 

Among the different C-alkylated products, A,A-dimethyltoluidine is by far the most abundant. It can be concluded that aniline methylation on > -Al203 follows a sequential reaction path of formation of A-methylaniline, then A,7V-dimethylani-line, then C-alkylated products. This is typical of acid catalysts [2]. a-Methylbenzylamine has also been tested (Table 3). 

Motherwell s group developed an original approach to the synthesis of biaryls based on the intramolecular free-radical zjo o-substitution reaction. This includes the reaction of ortho-io o (or bromo) phenols, A -methylanilines or 7V-methylbenzamides with various arylsulfonyl chlorides to give the respective sulfonates XXX, Ai-methyl sulfonamides XXXI, or Y-acylsulfonamides XXXII. The latter are reacted with tri- -butyltin hydride in the presence of azobisisobutyronitrile (AIBN) in refluxing benzene to produce spirocyclic intermediate XXXIII, which, upon extrusion of sulfur dioxide, afforded the ort/jo-hydroxy- XXXIV, methyamino- XXXV, or iV-methyl carboxamido-substituted biphenyls XXXVI in moderate to good yields [1-4], Scheme 1. 

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