Organic Syntheses / An Annual Publication of Satisfactory Methods for the Preparation of Organic Chemicals

by Unknown

XXII

QUINONE

(1)HOC6H4OH(4) + O(Na2Cr2O7 + H2SO4)—> O=C6H4=O + H2O Prepared by E. B. VLIET. Checked by ROGER ADAMS and E. E. DREGER.

1. Procedure

IN a 2.5-l. beaker, 100 g. of hydroquinone are dissolved in 2000 cc. of water heated to about 50'0. After the solid is completely dissolved, the solution is cooled to 20'0, 100 g. of concentrated sulfuric acid are slowly poured in, and the mixture is again cooled to 20'0. A concentrated solution of technical sodium dichromate is prepared by dissolving 140 g. in 65 cc. of water. This solution is then added gradually to the hydroquinone solution, with the use of a mechanical stirrer (see notes), the mixture being cooled so that the temperature never rises above 30'0. At first a greenish-black precipitate forms, but upon further addition of the sodium dichromate solution, the color changes to yellowish green. As soon as this color remains permanent (a slight excess of sodium dichromate does no harm) the reaction is complete. This requires about one-half to three-quarters of an hour; 90 to 110 cc. of sodium dichromate solution is necessary. The mixture is then cooled to about 10'0 and filtered with suction. As much water as possible is pressed out of the crystals.

The filtrate is extracted twice, 150 cc. of benzene being used for each extraction. The precipitate of quinone is transferred to a 1-l. beaker, and 500 cc. of benzene, including the 300 cc. used to extract the filtrate, are added, The mixture is now heated with stirring on a steam-bath, and as soon as most of the quinone has dissolved the benzene layer is decanted into another beaker. It is dried while hot by stirring a short time with a little calcium chloride, and then filtered through an ordinary funnel into a 1-l. distilling flask before it cools. There is a certain amount of quinone which does not go into the 500 cc. of benzene, so that the residue is extracted a second time with about 100 cc. of benzene, which is dried and filtered with the first extract. During these extractions, the benzene should not be at the boiling point, as this will cause a considerable volatilization of the quinone.

The distilling flask is now attached to a condenser set for downward distillation, and the benzene is distilled. As soon as the quinone starts to separate, the residue in the flask is transferred to a beaker and cooled in an ice bath. The precipitate is filtered off with suction and the product spread out for a short time to dry. The product is yellow in color and weighs 75 to 80 g. (76-81 per cent of the theoretical amount). Material made in this way will hold its yellow color over long periods of time, provided it is protected from light.

The benzene distillate is yellow and contains some quinone. This, as well as the benzene from the final filtration of the quinone crystals, may be used in a subsequent run and thus raises the yield of the subsequent runs to about 85-90 g. (85-90 per cent of the theoretical amount).

2. Notes

As the mixture becomes thick during the oxidation, it is very necessary to use a stirrer which will keep the whole mass agitated by reaching to the sides and bottom of the beaker.

If impure hydroquinone is used, a black, sticky precipitate will usually appear after the addition of the sulfuric acid to the hydroquinone solution. This should be removed, before the oxidation is started, by filtration without suction through a fluted filter.

When technical sodium dichromate is used, the solution should be filtered with suction, before it is added to the hydroquinone, in order to remove any insoluble impurities.

In the laboratory it is convenient to make several small runs of the size indicated, as far as the oxidation is concerned; but the benzene extractions can be combined.

It is also possible to obtain good yields of quinone in the following manner: 1500 cc. of water, 465 g. of concentrated sulfuric acid and 300 g. of hydroquinone are mixed in a 3-l. beaker. The mixture is cooled to 0'0, and 330 g. of sodium dichromate are added in powdered form, the temperature being kept below 5'0 at all times. This procedure requires a longer time and much more care in the control of conditions than the method described above.

3. Other Methods of Preparation

Quinone may be prepared by the oxidation of aniline with dichromate or manganese dioxide and sulfuric acid.[1] This is a more feasible commercial method than the one given. However, the oxidation of hydroquinone is more rapid and convenient and, hence is more desirable for use in the laboratory. Various materials have been oxidized by chemical means to give quinone: they are quinic-acid,[2] hydroquinone,[3] benzidine,[4] p-phenylenediamine,[5] sulfanilic acid,[6] p-phenolsulfonic acid,[7] arbutin,[8] aniline black,[9] and the leaves of various plants.[10] Quinone is also formed by several other methods: by the fermentation of fresh grass;[11] by the action of iodine on the lead salt of hydroquinone;[1b] by the decomposition of the compound, C6H4<.>2CrO2Cl with water;[2b] by the action of sulfuric acid on phenol blue;[3b] by the electrochemical oxidation of aniline,[4b] hydroquinone[5b] or benzene;[6b] by the catalytic oxidation of benzene.[7b]

[1] Jahresb. 1863, 415; Ber. 10, 1934, 2005 (1877); 16, 687 (1883); 19, 1468 (1886); 20, 2283 (1887); 31, 1524 (1898); Ann. 200, 240 (1880); 215, 127 (1882).

[2] Ann. 27, 268 (1838).

[3] Ann. 51, 152 (1844) j Am. Chem. J. 14, 555 (1892).

[4] Jahresb. 1863, 415.

5 Jahresb. 1863, 422.

6 Ann. 159, 7 (1871); Ber. 8, 760 (1875).

[7] Ber. 8, 760 (1875).

[8] Ann. 107, 233 (1858).

[9] Ber. 10, 1934 (1877); 34, 1285 (1901).

[10] Ann. 89, 247 (1854); Ber. 34, 1162 (1901).

[11] Ber. 30, 1870 (1897).

[1b] Ber. 31, 1458 (1898); Am. Chem. J. 26, 20 (1901).

[2b] Ann. chim. phys. (5) 22, 270 (1881).

[3b] Ber. 18, 2915 (1885); 21, 889 (1888).

[4b] D. R. P. 109,012; Frdl. 5, 664 (1900); D. R. P. 117,129; Frdl. 6, 112 (1901); J. Soc. Dyers and Colourists, 36, 138 (1920).

[5b] D. R P. 117,129; Frdl. 6, 112 (1901).

[6b] D. R. P. 117,251; Frdl. 6, 109 (1901); U. S. Pat. 1,322,580 (1919); C. A. 14, 287 (1920); Rev. produits chim. 21, 219 (1918); 21, 288 (1918).

[7b] U. S. Pat. 1,318,631 (1919); C. A. 14, 70 (1920).