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Org. Synth. 1934, 14, 68
DOI: 10.15227/orgsyn.014.0068
NITROMESITYLENE
[Mesitylene, 2-nitro-]
Submitted by Garfield Powell and F. R. Johnson.
Checked by W. W. Hartman and J. B. Dickey.
1. Procedure
In a 500-cc. three-necked, round-bottomed flask, provided with a mechanical stirrer, a dropping funnel, and a thermometer well, are placed 40 g. (0.333 mole) of mesitylene (Org. Syn. Coll. Vol. I, 1941, 341) and 60 g. (55.5 cc.) of acetic anhydride (Note 1). The flask is placed in a bath of ice and water, and the reaction mixture is cooled below 10°. A solution of 31.5 g. (20.8 cc., 0.5 mole) of fuming nitric acid (sp. gr. 1.51) in 20 g. (19.1 cc.) of glacial acetic acid and 20 g. (18.5 cc.) of acetic anhydride (Note 2) is added, with stirring, over a period of forty minutes, the temperature being kept between 15° and 20°.
When the addition of the nitric acid solution is complete, the reaction mixture is removed from the ice bath and allowed to stand at room temperature for two hours. The flask is then warmed, with shaking, to 50° on a water bath (Note 3) and maintained at that temperature for ten minutes. The cooled reactants are then poured slowly into 800 cc. of ice water and well stirred. About 40 g. of sodium chloride is added, and the aqueous layer is decanted and extracted with 200–250 cc. of a commercial grade of ether. The ethereal extract is added to the residual nitromesitylene, and this ethereal solution is washed with three or four 30-cc. portions of a 10–15 per cent sodium hydroxide solution until the water extract is distinctly alkaline. The ether is then distilled from a steam bath. The residue, after the addition of about 150 cc. of 10 per cent sodium hydroxide solution, is steam-distilled until a test sample of the distillate is clear and free of oil drops. The steam distillation requires about three hours, during which time 1.5 l. of distillate is collected. The nitromesitylene settles to the bottom of the distillate. The water is decanted through a filter paper, and the residue is dissolved in 30 cc. of ether. The filter paper, if it contains any solid particles, is washed with 10 cc. of ether, and the two fractions are combined and placed in a 150-cc. distilling flask with a water-cooled receiver. After removal of the ether on a steam bath, the yellow residue is distilled with a free flame. All but 0.5 to 1.5 g. of material distils at 243–250°, and the distillate, which weighs 47 g., solidifies on cooling. The yellow crystalline product is purified by dissolving in 25 cc. of commercial methyl alcohol and cooling with stirring in a bath of ice and salt. The crystals are then filtered on a small Büchner funnel and washed twice with 5-cc. portions of cold methyl alcohol. From the wash alcohol, by exactly the same procedure, there is obtained 6–8 g. of crude crystals boiling at 243–249°. This material yields on crystallization 4 g. of pure nitromesitylene. The pure nitromesitylene, which has a light yellow color, melts at 43–44°. The yield is 41–42 g. (74–76 per cent of the theoretical amount).
2. Notes
1. A commercial grade of 85 per cent acetic anhydride is of sufficient purity.
2. The nitric acid is added with care to the acetic acid-acetic anhydride solution, the temperature being kept below 20° by means of a bath of ice and salt. An explosive reaction will take place if the nitric acid is added too rapidly.
3. A higher temperature is not advisable.
3. Discussion
Nitromesitylene has been prepared by the direct nitration of mesitylene with concentrated nitric acid;1 by the action of benzoyl nitrate on mesitylene in carbon tetrachloride at low temperature;2 and from dinitromesitylene by reduction of one nitro group and replacement of the resulting amino group by hydrogen.3

References and Notes
  1. Fittig and Storer, Ann. 147, 1 (1868); Biedermann and Ledoux, Ber. 8, 58 (1875); Schultz, ibid. 17, 477 (1884); Bamberger and Rising, ibid. 33, 3625 (1900).
  2. Francis, ibid. 39, 3801 (1906).
  3. Ladenburg, ibid. 7, 1135 (1874).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

acetic acid (64-19-7)

methyl alcohol (67-56-1)

ether (60-29-7)

acetic anhydride (108-24-7)

hydrogen (1333-74-0)

sodium hydroxide (1310-73-2)

nitric acid (7697-37-2)

sodium chloride (7647-14-5)

carbon tetrachloride (56-23-5)

Mesitylene (108-67-8)

Nitromesitylene

Mesitylene, 2-nitro- (603-71-4)

benzoyl nitrate

dinitromesitylene