N-Methyl-o-toluidine

Indole (1) Cyclization of o.amino phenyl + acetaldehyde (2) Cyclization of N-formyl, o.toluidine (3) Cyclization of N-methyl, o.toluidine... 

Fig. 5.5. GC separation of TFA derivatives of arylamines. Peak 1 = solvent (CH2CI2) 2 = N-methyl-aniline 3 = N,N-dimethylaniline 4 = N-ethylaniline 5 = N-methyl-o-toluidine 6 = N-methyl-m-toluidine 7 = N-methyl-p-toluidine 8 = o-toluidine 9 = o-ethylaniline 10 = aniline 11 = 2,5-dimethyl-aniline 12 = 2,6-dimethylaniline 13 = 2,4-dimethylaniline 14 = m- toluidine 15 = p-toluidine 16 = 2,3-dimethylamline 17 = 3,5-dimethylaniline 18 = m-ethylaniline 19 = p-ethylaniline 20 = 3,4-dimethylaniline. Conditions stainless-steel column, 18 ft. X 0.125 in. O.D., 9.5% Apiezon L + 3.6% Carbowax 20M on Aeropack 30 (80—100 mesh) helium flow-rate, 100 ml/min column temperature, 152°C. (Reproduced from Anal. Chem., 39 (1967) 1188, by courtesy of the American Chemical Society.)...

Methylaniline Ethylaniline n-Propylaniline n-Butylaniline Benzylaniline 2 -MethyIbenzylamine N-Ethylbenzylamine 2 -Methyl o-toluidine N-Methyl m-toluidine 2 -MethyI p-toluidine N-Ethyl o-toIuidine N-Ethyl m-toIuidine 2S -Ethyl p-toluidine 2 -MethyI a-naphthylamine N-Methyl p-naphthylamine N-Phenyl- a-naphthylamine 2 -Phenyl-P-naphthylamine... 

A mixture of 4.0 grams of N-methyl-3-toluidine and 2.8 grams of sodium hydrogencarbon-ate in 50 cc of acetone was stirred at 0° to 10°C and 7.4 grams of 2-naphthyl chlorothiono-formate was added in small portions thereto and the mixture was heated under reflux for 30 minutes. The cooled mixture was poured into about 150 cc of cold water and 2-naphthvl-N-methvl-N-(3-tolyl)thionocarbamate was obtained as white crystals. Yield is 9.1 grams (90 o). Recrystallization from alcohol gave colorless needle crystals, MP 110.5° to 111.5°C. 

Ethy Ibenzy lamine A -Methyl o-toluidine A -Methyl m-toluidine. 2V-Methyl p-toluidine A -Ethyl o-toluidine -Ethyl m-toluidine -Ethyl p-toluidine 2V-Methyl a-naphthylamine 2V-Methyl p-naphthylamine 2V-Phenyl- a-naphthylamine N-Phenyl- p-naphthylamine... 

V-Ethylbenzylamine A -Methyl o-toluidine TV-Methyl m-toluidine. A7-Methyl p-toluidine A7-Ethyl o-toluidine A7-Ethyl m-toluidine A7-Ethyl p-toluidine A7-Methyl a-naphthylamine. . ZV-Methyl p-naphthylamine. 2V-Phenyl-a-naphthylamine. N-Phenyl- p-naphthylamine. ... 

A = 13778 C9H12O C9H1.N Phenyl Propyl Ether Di methyl-o-toluidine 190.5 185.35 Nonazeotrope 265... 

The tetrahydrodiazepine (112) was found107 to be a highly unstable substance. On the other hand, the 4-keto derivative (110, R = H) was quite stable, although refluxing a dilute aqueous hydrochloric acid solution led to the formation of what was believed to be an oxindole polymer. This ready acid hydrolysis was attributed to the essentially acetal-like character of the grouping N—CH2—N. The low basicity of 110 (R = H) (pK < 2) is of interest since A-methyl-o-toluidine has a pK of 4.87. The inductive effect plus the mesomeric influence of the amide carbonyl and internal strain effects resulting in a certain amount of bond opposition appear to explain this basicity.107... 

An interesting case of intramolecular azo coupling to an activated methyl group is the well-known synthesis of indazoles 72 starting from o-toluenediazonium salts 69 or from N-nitroso-N-acetyl-o-toluidine 67 . Recently the reaction mechanism (32) was elucidated When the reaction is run in the presence of D O or... 

C12H15N04 N-carbobenzyloxy-2-methyl alanine 15030-72-5 25.00 1.1892 2 24307 C12H17NO N-pivaloyl-o-toluidine 61495-04-3 23 1 050 ... 

Methyl groups of other ligands may also be involved in cyclopalladation. Thus N, N-dimethyl-o-toluidine with Pd acetate in acetic acid gives a trinuclear complex... 

Methylaniline Ethylaniline n-Propylaniline n-Butylaniline Benzylaniline AT-Methylbenzylamine N -Ethy Ibenzy lamine AT-Methyl o-toluidine M-Methyl m-toluidine iV-Methyl p-toluidine Al-Ethyl o-toluidine N-Ethyl TO-toluidine N-Ethyl p-toluidine A -Methyl a-naphthylamine A -Methyl p-naphthylanaine A -Phenyl- a-naphthylanaine Af-Phenyl- p-naphthylamine... 

N-i/e see 3 5-Dinitro-ilT-methyl-o-toluidine. N-Acetf 3 5-dinitro-o>acet-toluidide. M.p. 205-2°. 

Methyl-6-nitroaniline (3-N itro-o-toluidine) 92 305d ISg 167 l-Naphthylthiourea. 171... 

Preparation of Intermediate Compound 2-Methyl-3-o-Tolyl-6-Sulfamyl-7-Chloro-4(3H)-Quinazoiinone Set up a 5-liter 3-necked flask fitted with a stirrer, condenser and a drying tube. To a stirred mixture of 100 g (0.342 mol) of powdered 4-chloro-5-sulfamyl-N-acetylanthranilic acid, 40.2 g (0.376 mol) of o-toluidine and 2.0 liters of dry toluene was added dropwise, over a period of 15 minutes, 21.7 ml (34.1 g) (0.248 mol) of phosphorus trichloride. The mixture was then refluxed for 10 hours. The solid turned somewhat gummy towards the latter part of the first hour. The mixture then became more free flowing as heating was continued. Let stand overnight. The yellow solid was filtered, washed with toluene and dried. The toluene filtrate was discarded. The dried solid was triturated with 1.5 liters of 10% sodium bicarbonate, filtered and the cake washed with water. The filtrate on acidification yielded 11.5 g of the starting acid. The damp product was dissolved in 4,5 liters of 95% ethanol and the solution treated with charcoal and filtered. On cooling filtrate yielded 69.5 g (55.5%) of the title compound, MP 271.5° to 274°C. 

A detailed investigation of aniline N-methylation on Cui xZnxFc204 was carried out through in situ FTIR spectroscopy. The reactants (aniline and methanol) and possible products (NMA, DMA and o-toluidine) were adsorbed on the catalysts and analyzed [106,107]. Adsorption of methanol indicated a dissociative chemisorption as methoxy species on catalyst surface at 100°C. As the temperature increased, oxidation of methoxy species to formaldehyde to dioxymethylene to formate species was observed, and above 300°C complete oxidation takes place to CO, CO2 and H2. Indeed methanol alone on Cui xZnxFc204 and Cui.xCoxFc204 behaves in a similar way [79,107]. 

The Madelung synthesis of indoles (79 — 80) from A-acyl-o-toluidines originally necessitated heating with sodamide at 250°C however, the stronger bases n-butyllithium or LDA cause reaction at 20°C <81JOC4511 >. Milder conditions can also be employed if the methyl group is activated as in (81 — 82) (68JA7008). 

Tetranitro-2-methyldiphenylamine or N-(2, 4 -Dinitrophenyl)-4,6- dinitro-o-toluidine, (02N)2C8H3,NH. C6H2(CH3)(N02)2 yel ndls, mp 190° Can be prepd by heating, on a steam bath, 2 4 -dinitro-2-methyl-diphenyl amine with a mixt of glacial AcOH and nitric acid (dl.42) until a straw colored soln is obtained (ca A hr). Its expl props were not examined... 

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