Organic Syntheses Part 7

XI

MESITYLENE

3 CH3COCH3 + (H2SO4)--> C6H3(CH3)3 +3H2O

Prepared by ROGER ADAMS and R. W. HUFFERD. Checked by H. T. CLARKE and W. W. HARTMAN.

1. Procedure

IN a 12-l. round-bottom flask, arranged so that the contents can be mechanically stirred, are placed 4600 g. (5750 cc.) of technical acetone. The flask is then well cooled with an ice-and-salt mixture, until the temperature of the acetone is between 0'0 and 5'0. Stirring is started, and 4160 cc.

of commercial concentrated sulfuric acid is run in at such a rate that the temperature of the mixture never rises above about 10'0.

This addition is accomplished in about five to ten hours.

The stirring is continued for three to four hours longer, while the flask still remains immersed in the original freezing mixture to which no further amount of ice is added.

The mixture is then allowed to stand at room temperature for eighteen to twenty-four hours.

A 5-l. round-bottom flask is fitted with a rubber stopper or a cork stopper coated with pitch, carrying two gla.s.s tubes, one of which (for the entrance of steam) reaches to the bottom of the flask, while the other extends into the open end of a condenser set for downward distillation. The stopper should be wired into the flask.

The gla.s.s delivery tube into the condenser should not be less than a 12-mm. bore, and the condenser should consist of two 120-cm. water-cooled condensers attached end to end. To the end of the condensing system, an adapter is attached, the small end of which is at least 8 mm.

in bore and is fitted tightly into a stopper in a 2-l. suction flask.

To the side-arm of the suction flask is attached a tube leading to an exhaust fan, in order to carry away the gases which are evolved during the subsequent distillation. In the 5-l. flask are placed about 2 l.

of the sulfuric acid-acetone reaction mixture, and the flask is then heated with a free flame and shaken occasionally.

A reaction starts at the end of about fifteen or twenty minutes, as shown by the evolution of gas (chiefly sulfur dioxide), and is allowed to run for about three minutes. At the end of this time, a current of steam is pa.s.sed in and continued for about three minutes.

During this period a large proportion of the mesitylene distils and should be kept separate from the subsequent distillate.

The steam distillation is continued at such a rate that about 800 cc.

distils in twenty-five to thirty minutes and is collected as a second distillate. At the end of this time, the distillation is stopped, the water poured off from the distilling flask and the tarry material emptied out while hot into waste jars.

The total amount of original reaction mixture requires five distillations similar to the one just described.

The first distillates from each of the five distillations are mixed, and the layer of mesitylene is separated from the water.

This is shaken with sodium hydroxide solution until no more odor of sulfur dioxide is noticeable, then washed twice with water and distilled.

The first portion of the distillate consists of a small amount of water and mesitylene and is added to the combined second distillates.

The fraction which distils up to 210'0 is saved. The second distillates are combined, washed in the same way as the first and then distilled; the fraction which distils up to 210'0 is combined with the corresponding fraction from the first distillates.

These combined fractions (which boil up to 210'0) and 15 g.

of sodium are placed in a 2-l. distilling flask, the side-arm of which is closed with a rubber tube and pinchc.o.c.k and which is fitted with a reflux condenser. The mixture is heated just below the boiling point for about three hours, during which time the impurities are attacked by the molten sodium, and a gelatinous, reddish ma.s.s forms.

The reflux condenser is now removed and one set for downward distillation is attached to the side-arm. The mixture is distilled and about two-thirds of the liquid removed in this way.

The residue is cooled, the liquid poured off from solid material and distilled up to 210'0.

The distillates from the sodium treatment are now fractionated with a good column (at least 30 cm. long), and the portion which boils at 163-167'0 is collected. The yield of this fraction varies in different runs from 430 to 470 g. (13-15 per cent of the theoretical amount), but very often will be as high as 500 g., and has reached, in certain experiments, 600 g.

An alternative method for the purification of the crude material has been employed by Clarke and Hartman, and yields a slightly higher-grade product than the sodium method. It is as follows:

The combined distillates are treated with an equal volume of concentrated sulfuric acid and the solution warmed on a water bath for an hour, under a reflux condenser, with occasional shaking or, better, with mechanical stirring. Upon cooling, mesitylene sulfonic acid crystallizes and the unsulfonated material remains as an oil on the surface.

The mixture is filtered through flannel or a "filtrose" plate, and the crystals are washed with 60-70 per cent sulfuric acid.

The oily layer is again warmed with sulfuric acid, as before.

The acid and oily filtrates from the two sulfuric acid treatments are steam distilled, and the distillate combined with the next batch of material.

The crystals are mixed with 2 l. of 15 per cent hydrochloric acid and heated under a reflux condenser for two to three hours.

The reaction mixture is now steam distilled, the mesitylene separated, dried over calcium chloride and fractionated; the portion which boils at 163-167'0 is collected.

2. Notes

The cooling of the reaction flask must be very efficient, a 10-15 cm.

blanket of a thorough mixture of ice and salt being used.

If this precaution is not employed, the time for the addition of the sulfuric acid is greatly increased, provided the temperature of the reaction mixture is still kept within the limits mentioned.

If a cork is used for the steam distillation of the reaction mixture of acetone and sulfuric acid, it should be coated well with pitch and wired into the flask. This is necessary because the vapors of the reaction mixture attack an ordinary cork very badly, and soften it so much that it is necessary to rewire it to prevent it from slipping out.

A rubber stopper is satisfactory and may be used in several runs.

The evolution of gas is so vigorous that it is not possible to distil more than 2 l. of the original reaction mixture at one time in the apparatus described. The connections on the apparatus, in which the mesitylene is obtained from the crude reaction mixture, should be tight, since the fumes evolved during the heating are very irritating.

The product which distils during the initial heating and the three minutes of steam distillation is mainly satisfactory material; the rest of the steam distillation yields only a small amount of pure product.

The two portions of the distillate are, therefore, kept separate, since the second distillate always contains a considerable amount of high-boiling product which tends to cause emulsification of the alkali in the purification. No recovery of acetone is made.

The mechanism of the reaction is undoubtedly as follows: when the sulfuric acid and acetone are in contact for long periods of time, several molecules of the acetone condense to form aldol condensation products. These do not break down into mesitylene until the temperature is raised in the second part of the experiment.

While the original reaction mixture is standing, the temperature gradually rises to 40'0 or 50'0 in the course of six to ten hours, and then gradually cools off again. It is probable that at the end of this time (when the flask has cooled again) the reaction mixture could be distilled with nearly as good a yield as is obtained after standing eighteen to twenty-four hours.

The wide variation in yields which are mentioned in the experimental part is probably due to a slight change in the grade of the chemicals which are used in this preparation. 3. Other Methods of Preparation

The cheapest and most convenient method by which mesitylene may be prepared is by the action of a dehydrating agent upon acetone; the agent most commonly used is sulfuric acid.[1] It has been shown also that phosphoric acid will convert acetone to mesitylene.[2] A number of other methods have also been used for the preparation of mesitylene: the action of sulfuric acid on methyl acetylene;[3] the action of sulfuric acid on mesityl oxide and phorone;[4] the action of aluminium{sic(british)} chloride on methyl chloride and benzene;[5]

the action of mineral acids upon mesitoyl or benzoyl mesitylene;[6]

the action of phosphoric acid upon diaceto-mesitylene;[7] the treatment of methylene-3-dimethyl-1, 5-cyclo-hexene-1 with bromine and then with alcoholic potash.[8]

[1] Ann. 141, 131 (1867); 147, 43 (1868); 278, 210 (1893); Bud.

soc. chim. (2) 40, 267 (1883); J. prakt. Chem. (1) 15, 129 (1838); Am. Chem. J. 15, 256 (1893); 20, 807 (1898).

[2] J Chem. Soc. 99, 1251 (1911).

[3] Ber. 8, 17 (1875).

[4] Ber. 7, 1169 (1874); 10, 858 (1877).

[5] Ber. 12, 329 (1879); Ann. chim. phys. (6) 1, 461 (1884).

[6] Ber. 32, 1910 (1899).

[7] Ber. 32, 1563 (1899).

[8] Ber. 43, 3093 (1910).

XII

METHYL RED

(_o_)HO2CC6H>4s>NH2 + HNO2 + HCl-->(_ o_)HO2CC6H4N2Cl + H2O (_o_) HO2CC6H4N2Cl + C6H5N(CH3)2-->(_ o_)HO2CC6H4N = NC6H4N(CH3)2 + HCl

Prepared by H. T. CLARKE and W. R. KIRNER. Checked by ROGER ADAMS and J. B. DAVIS.