M-Aminotoluene

Arynes are intermediates in certain reactions of aromatic compounds, especially in some nucleophilic substitution reactions. They are generated by abstraction of atoms or atomic groups from adjacent positions in the nucleus and react as strong electrophiles and as dienophiles in fast addition reactions. An example of a reaction occurring via an aryne is the amination of o-chlorotoluene (1) with potassium amide in liquid ammonia. According to the mechanism given, the intermediate 3-methylbenzyne (2) is first formed and subsequent addition of ammonia to the triple bond yields o-amino-toluene (3) and m-aminotoluene (4). It was found that partial rearrangement of the ortho to the meta isomer actually occurs. 

CH3. C6H4.N2 J, C7H7N21 mw 246.06 N 11.39% red-brn cryst mp, decompn below 0° (stable at —180°). Isolated as by-products in the diazotization of (o- and m-) aminotoluene upon the addn of a Na iodide soln to the diazo-tized material... 

SYNS 3-AMINO-l-METHYLBENZENE 3-AM-INOPHENYLMETHANE 3-AMINOTOLUEN (CZECH) m-AMINOTOLUENE 3-AMINOTOLUENE m-METHYLANILINE 3-METHYLANILINE m-METH-... 

Beilstein Handbook Reference) AI3-19859 m-Aminotoluene Aniline, 3-methyl- Benzen-amine, 3-methyl- BRN 0636944 CCRIS 4325 EINECS 203-683-1 HSDB 2043 m-Methylaniline m-Methyl-benzenamine NSC 15349 m-Toluidin m-Toluidine m-Toluidyna m-Tolylamine UN1708. Liquid mp = -31.2° bp= 203.3° d O = 0.9889 Xm = 236, 286 nm (e = 8900, 1460, MeOH) very soluble in MeaCO, EtOH, EtaO, CeHe. 

Synonyms/Trade Names 3-Amino-1-methylbenzene, 1-Aminophenylmethane, m-Aminotoluene, 3-Methylaniline, 3-Methylbenzenamine, 3-Toluidine, meta-Toluidine, m-Tolylamine ... 

Amino-o-toluene. See 3,4-Xylidine a-Aminotoluene. See N-Benzylamine m-Aminotoluene. See m-Toluidine o-Aminotoluene. See o-Toluidine p-Aminotoluene. See p-Toluidine 2-Aminotoluene hydrochloride. See o-Toluidine... 

Synonyms 1-Amino-3-methylbenzene 3-Amino-1-methylbenzene 3-Aminophenyl methane 3-Aminotoluene m-Aminotoluene 3-Methylaniline m-Methylaniline 3-Methylbenzenamine m-Methylbenzenamine m-Methylbenzeneamine m-Toluamine 3-Toluidine m-Tolylamine Classification Aromatic amine Empirical C7H9N Formula CH3C6H4NH2... 

Further nitration of the 2- and 4- isomers yields 2,4-dinitrotoluene, yellow crystals, m.p. 71 "C. This material is reduced to 2,4-di-aminotoluene and treated with phosgene to give 2,4-diisocyanatotoluene, a precursor of polyurethanes. 

An example of this is given in Section IV.63—the conversion of 3-bromo-4-aminotoluene into m-bromotoluene. Another application is to the preparation of. iM.-tribromobenzene (Section IV,72) ... 

Triturate 20 g. of dry o-toluidine hydrochloride and 35 5 g. of powdered iodine in a mortar and then grind in 17 -5 g. of precipitated calcium carbonate. Transfer the mixture to a conical flask, and add 100 ml. of distilled water with vigorous shaking of the flask. Allow the mixture to stand for 45 minutes with occasional agitation, then heat gradually to 60-70° for 5 minutes, and cool. Transfer the contents of the flask to a separatory funnel, extract the base with three 80 ml. portions of ether, diy the extract with anhydrous calcium chloride or magnesium sulphate, and remove the excess of solvent. The crude 5-iodo-2-aminotoluene separates in dark crystals. The yield is 32 g. Recrystallise from 50 per cent, alcohol nearly white crystals, m.p. 87°, are obtained. 

To 500 g. of 95 per cent ethyl alcohol in a 5-I. flask are added 1.70 g. of m-nitro- -toluidine (3-nitro-4-aminotoluene, m. p. 112-1140, Note r) and 250 g. of concentrated sulfuric acid. The solution is chilled to ro° by means of an ice bath, and a solution of 85 g. of technical sodium nitrite in a minimum quantity of water is slowly added, with stirring, the temperature being kept below to0. The mixture is now warmed very gently on the water bath under an efficient reflux condenser (from the upper end of which a tube leads to a hood or through water) until evolution of gas ceases (Note 2). The alcohol and aldehyde are then carefully distilled off, using a fractionating column and heating in an oil or brine bath (Note 3) when the temperature of the vapors reaches 8o° fractionation is stopped and the residue is distilled in a current of steam. The oil is separated from the distillate and the aqueous portion shaken out once with r5o-200 cc. of benzene. The united oil and extract are dried with a... 

Bromo-4-acetaminotoluene, 593, 605 p-Bromoacetanilide, 577, 580 p - Bromoace tophenone. 726, 732 m-Bromo-p-acetotoluidido, 593, 605 3-Bromo-4-aminotoluene, 593, 605 hydrochloride, 605 p-Bromoanilides, 361 p-Bromoaniline, 577, 580 o-Bromoanisole, 404 p-Bromobenzaldehyde, 689, 694, 696 diacetate, 696... 

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