3- Amino-4- toluene

Bromo-4-aminotoluene, Suspend the hydrochloride in 400 ml, of water in a 1-Utre beaker equipped with a mechanical stirrer. Add a solution of 70 g. of sodium hydroxide in 350 ml. of water. The free base separates as a dark heavy oil. After cooUng to 15-20°, transfer the mixture to a separatory funnel and run off the crude 3-bromo-4-amino-toluene. This weighs 125 g. and can be used directly in the next step (3). 

After the addition of 2 1. of water, the mixture is steam-distilled as long as any oil comes over. The crude, heavy, yellow oil is separated and washed with two 200-cc. portions of 10 per cent sodium hydroxide, once with 100 cc. of water, twice with 150-cc. portions of concentrated sulfuric acid, and finally with 100 cc. of 5 per cent, sodium carbonate solution. It is dried with about 5 g. of calcium chloride, filtered through glass wool, and distilled using a long air condenser. Most of the product boils at i8o-i83°/75o mm. The yield of pure colorless material, b.p. i83°/76o mm., is 125-135 g. (36-39 per cent of the theoretical amount, based on the amount of -toluidine originally used, or 54-59 per cent based on the amount of 3-bromo-4-amino-toluene). 

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. 

Can be prepd by diazotization of 6-nitro-4-amino toluene-3-sulfonic acid with K nitrite and dil sulfuric acid. It has also been isolated by... 

In a 2-1. beaker is placed 75 g. (0.4 mole) of 3-bromo-4-amino-toluene (Note 1), and to it is added the hot diluted acid obtained by adding 72 cc. of concentrated sulfuric acid to 200 cc. of water. The clear solution is stirred and cooled to about 15°, after which 180 g. of ice is added the amine sulfate usually separates. As soon as the temperature has dropped below +5°, a solution of 32.2 g. (0.47 mole) of sodium nitrite in 88 cc. of water is added from a dropping funnel, the stem of which extends below the surface of the liquid. The temperature of the solution is kept below +5° during the addition, which requires about fifteen minutes. The solution is stirred for five minutes after the addition of all the sodium nitrite, and 300 g. of cold water, 3 g. of urea, and 300 g. of cracked ice are then added successively. The solution is kept in an ice bath until used. 

Synonyms l-Amino-2-methylbenzene 2-amino-1-methylbenzene 2-amino-toluene ort/20-aminotoluene 2-methyl-1-aminobenzene 2-methylaniline ortho-methylaniline ort/20-methylbenzenamine 2-methylphenylamine ort/zo-tolylamine... 

Synonyms 2-Amino-5-chlorotoluene 3-chloro-6-aminotoluene 5-chloro-2-amino-toluene 4-chloro-2-methylaniline 4-chloro-6-methylaniline 4-chloro-2-toluidine / ara-chloro-ort/ro-toluidine 2-methyl-4-chloroaniline 2-methyl-4-chlorobenzene-amine... 

All of the Di amino toluenes form cryst salts and addn compds. Other props methods of prepn are given in the Refs Refs 1) Beil 13, 123, (39) [60 ]... 

Di(methylamino)-toluene. See Bis (methyl-amino)-toluene in Vol 2 of Encycl, p B150-L... 

Azidoaminotoluene, C7H N4 and Diazido amino toluene, C7H7N7 - not found in Beil or CA... 

Yel crysts(from benz), mp 02°, defer violently when heated above its mp. Easily sol in ale, eth benz. Can be prepd by treating 6-amino-toluene sulfonic acid with nitric acid(d 1.51) at —10° to 0°. It forms salts, such as AgC7... 

Dinitro4-(N -butyl-N-nitro)-amino toluene 2 B377-B378... 

Aminodinitrotoluenes, x,x-Dinitro-x-amino-toluenes, x,x-Dmitro-x-methyl anilines or x,x-Dinitro- (o-, m-, p-) -toluidines). CH3.C6H2-NH2(N02)2, C7H7N304 mw 197.17 N 21.32% OB to C02 —109.55%, V sol in acet fairly sol in RT ethanol, eth and acetic acid si sol in coned hydrochloric acid... 

Methylnonylthiuronium Picrate A69-L Methylphenylamines. See under Amino-toluenes A265... 

Some idea of the utility of the hydrazine procedure may be inferred from the yields obtained on deaminating the following compounds aniline (45-75%),110 1Ui 118 p-toluidine (55-65%),uo 116 3-chloro-4-amino-toluene (40%),117 5-bromo-6-aminoquinoline ( satisfactory yield ).181 ... 

Nitro-4-amino toluene m-Nitrotoluene (62-72%, pure) H3PO2 gives 75-80% of pure m-nitro toluene. 34... 

Chloro-4-amino toluene m-Chlorotoluene (60%) Via hydrazine get 40% yield of pure product. 164... 

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