M-Toluidine, acetylation

Acetyl-AT-methyl-o tolnidine Acetyl-AT-raethyl-m-toluidine. Acetyl-AT-methyl-p-toluldine. Acetyl-AT-methyl-a-naphthylam Ine Acety l- /-raethy 1- -naphthy lamlne... 

Acetyl-AT-metbyl-o toluidine. Acetyl-AT-metbyl-m-toluidine. Acetyl-AT-methyl-p-toluidine. Acetyl-A7-methyl-a-napbthylamine Acety 1-AT-metbyl- P-naphthy lamine... 

I Acetyl-Af-methyl-m-toluidine. Acetyl-Af-methyl-p-toluidine. Acetyl-Af-methyl-a-naphthylamine. Acetyl-Af-methyl-P-naphthylamine. ... 

Acetyl-o-toluidine Acetyl-m-toluidine Acetyl-p-toluidine... 

The preparation of 3-alkyl quinolines by traditional Skraup/Doebner-von Miller reaction typically results in very low yields. When ethylacrolein (9) is condensed with m-toluidine (8) under typical Skraup/Doebner-von Miller conditions, the yield of 10 is only 25%, compared to 65% with di-acetyl acetal 11. 

Although practically important in other cases, the replacement of an NH2-group by hydrogen via the diazo-compound naturally has none in the example here given. Thus m-nitrotoluene (and from it m-toluidine) is obtained from p-toluidine by nitration of the acetylated base and replacement of the NH2-group (after elimination of the acetyl) by H, as shown above. 

Boil a mixture of 10 g. (10 ml.) of o-toluidine and 38 g. (35 ml.) of acetic anhydride in a 75 or 100 ml. Claisen flask fitted with a reflux condenser (Fig. Ill, 28, 1, but with trap replaced by a calcium chloride or cotton wool guard tube) for 1 hour. Arrange the flask for distillation under reduced pressure (compare Fig. II, 20, 1) and distil acetic acid and the excess of acetic anhydride pass over first, followed by the diacetyl derivative at 152-153°/20 mm, some mono-acetyl-o-toluidine (1-2 g.) remains in the flask. The yield of diacetyl-o-toluidine is 14-15 g, it is a colourless, somewhat unstable hquid, which slowly sohdifies to yield crystals, m.p. 18°, To prepare the (mono-) acetyl-o-toluidine, warm a mixture of 5 g. 

Columns in which 6-cyclodextrin was immobilized on polyacrylamide or agarose gel were shown to be very useful in the separation of disubstituted benzene isomers (60,61). Acetylating the immobilized 6-cyclodextrin further improves the selectivity, i.e. it can completely separate o-, m- and p-toluidine, and dinitrobenzenes (64) which cannot be done on unmodified stationary phase. 

Acetyl-o-toluidine, m.p. 110-111°, obtained from the Eastman Kodak Company, was used. After the reactants are introduced into the flask, they should be mixed thoroughly with a long spatula. 

Acetoxymercuri - aceto - o toluidide.— Ten grams of o-aceto-toiuidicle in 250 e.c. of hot water are treated with 20 grams of mercuric acetate and the mixture boiled for forty minutes, then Altered whilst hot. It is then cooled in ice for twenty-four hours, the solution yielding 7 grams of needles, 28 per cent, yield. After recrystallisation from 80 per cent, alcohol, the needles melt at 238° C. (eorr.). With iodine it gives 5-iodo-aceto-o-toluidide. Treatment vith sodium chloride solution yields the chloromercuri-aceto-o-toluidide, M.pt. 167° C., which may also be obtained by acetylation of the chloromercuri-o-toluidine. 

As the boiling points of 0-, m-, and p-toluidine are, respectively, 199°, 200°, and 198°, it is impossible to identify these compounds by a determination of their boiling points. The identification can be effected, however, by a determination of the melting points of their acetyl derivatives, which are formed when the amines are treated with acetic anhydride. The acetyl derivatives of 0-, m-, and p-toluidine melt at 107°, 65°, and 147°, respectively. In order to identify a substance it is necessary to determine the physical properties of the substance and of at least one of its derivatives. The method used in the identification of the toluidines is an excellent example of this principle. 

N-Jfe see 3 d-Dinitro-iv-methyl-p-toluidine. IH-Acetyl 3 d-duutro-p-ac t-tolmdide. M.p. 196°. 

Deacetylase activity towards A -hydroxy-acetylaminofluorene (OH-AAF) was indicated to be absent in digestive gland microsomes of M. galloprovincialis (Kurelec and Krca 1987), but present in M. edulis towards AAF and N-acetyl-O toluidine (see Sect. 7.2.2). 

On the other hand, A-[ C]acetylation procedures have found wide application for substances needed either for in vitro studies (for carbon-14 labeling of proteins see next section) or as valuable synthetic intermediates. In the latter case, 3-substituted 7V-[1- C]-acetylated toluidine M served as a key intermediate for the synthesis of [2- C]mepindolol... 

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