N-Methyl-3-toluidine

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. 

Tolnaftate Tolnaftate, 0-(2-naphthyl)-N-methyl-N-(3-tolyl)-thiocarbamate (35.4.9), is synthesized by reacting equimolar amounts of 2-naphthol and thiophosgene to make a monosub-stituted product of thiophosgene (35.4.8), which is then reacted with N-methyl-3-toluidine to give the desired tolnaftate [61-64],... 

Thiophosgene (1.15 g, 0.01 mol) in chloroform (40 ml) was slowly treated at room temperature with sodium l,4-methano-l,2,3,4-tetrahydro-6-naphthoxide (1.82 g, 0.01 mol). After 30 minutes, N-methyl-m-toluidine (2.42 g, 0.02 mol) in chloroform (40 ml) was added dropwise to the solution so obtained at room temperature. The reaction mixture was stirred for 48 hours at room temperature and then refluxed for 2 hours. The solvent was evaporated, and the residue redissolved in water and extracted repeatedly with diethyl ether. The organic phase was dried (Na2S04) and evaporated to... 

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.)...

Materials. 2, 3-dinitroaniline (8), -methyl-N, N-dimethyl-aniline (9), p-chloro-N, N-dimethylaniline (9), p-nitro-N, N-dimethylaniline (1 ), N-methyl-p-toluidine (11), p-chloro-N-methylaniline (11), N, 2, 4-trinitroaniline (12), 2, 4-dinitro-N-methylaniline (13), 2, 4-dinitro-N, N-dimethylaniline (13) and N, 2, 4-trinitro-N-methylaniline (14) were prepared by known methods. Spectroscopic grade nitromethane and methylene chloride were dried using a molecular sieve. The other substrates were either available from related studies or were purchased and purified by standard methods. 

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. 

Figure 21. Conversion of substituted anilines (OT, MT, and PT are respective ortho-, meta-, and para-toluidine, PA = p-anisidine, and PAA = p-aminoacetophenone), corresponding mono-N-methylated anilines selectivity and yield obtained on Cu0.5Zn0.5Fe204 at 300oC with methanol. Only in the case of PAA, feed with CH30H PAA = 6 was employed to avoid solubility problem, and in all other cases a CH30H Sub. Amline H20 = 3 1 1 was maintained. Reprinted from Applied Catalysis A General, 320, Vijayaraj M., et al., 2007, 64-68 with permission from Elsevier.

Others 1,4-dioxane, 1,3,5-trioxane, terahydrofuran, 2-butyl tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, epsilon-caprolactam, benzothiazole, biphenyl, pyrazine, 2-butanone oxime, l-methyl-2-pyrrolidone, N,N-dimethyl-aniline, N,N-dimethyl-p-toluidine, l-methyl-7-isopropyl phenanthrene, dibenzyl-amine, hexamethylenetetramine, squalene, 2-ethylanthraquinone... 

The preparation of crystalline methyl ethers of iV-phenyl- or Af-p-tolyl-aldosylamine by condensation of aniline or p-toluidine with aldose methyl ethers proceeds, in many cases, readily and quantitatively in methanolic or ethanolic solution, either at room or reflux temperature. For this reason, such derivatives are frequently used to characterize aldose methyl ethers isolated during constitutional studies on polysaccharides. For D-glucose, for example, crystalline 2-0-methyl-, 6-0-methyl-,3,4-di-O-methyl-, 2,3,4-tri-O-methyl-, 2,4,6-tri-O-methyl-, " and 2,3,4,6-tetra-O-methyl-A-phenyl-n-glucosylamine have been prepared in this way. Although anomeric forms of A -arylaldosylamine methyl ethers are possible, such anomeric pairs have not been isolated. No similar derivatives have been obtained from ketose methyl ethers. 

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 ... 

Olefins, synthesis -Butyllithium. 1,3-Dibenzyl-2-methyl-l, 3,2-diazaphospholidine. Dimethyl methylphosphonothioate. Diphenylsulfonium isopropylide. N-Methanesulfinyl-p-toluidine. Methylphosphoric acid bis(dimethylamide). Phosphoryl chloride-Stannous chloride-Pyridine. p- Toluenesulfonylhydrazine. Triphenyl phosphite. 

---