A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1932, 12, 80
DOI: 10.15227/orgsyn.012.0080
Submitted by G. H. Coleman and David Craig.
Checked by Henry Gilman and J. B. Dickey.
1. Procedure
The apparatus shown in Fig. 18 is set up in a hood. The narrow reaction bottle A, of about 500-cc. capacity and having a wide mouth, is provided with an efficient mercury-sealed mechanical stirrer, an inlet tube B for admitting the mixture of gases, and an outlet tube connected with the wash bottle E. Into A, contained in a water bath at 20°, is placed 200 g. (2.17 moles) of dry toluene; then 30 g. (0.3 mole CuCl) of cuprous chloride (Note 1) and 267 g. (2 moles) of finely powdered anhydrous aluminum chloride are added rapidly with active stirring.
Fig. 18
Fig. 18
A mixture of hydrogen chloride and carbon monoxide (Note 2) is led to the bottom of the reaction bottle through tube B at such rates that the carbon monoxide is admitted uniformly during seven hours and the hydrogen chloride at about one-half this rate. The rates of flow of the two gases may be compared by the bubbling in wash bottles C and D. The extent of absorption can be estimated from the bubbling of the effluent gases in wash bottle E. The carbon monoxide is absorbed almost quantitatively at the beginning, and as the mixture thickens the absorption becomes less complete.
The mixture is hydrolyzed by adding it (Note 3) slowly and with shaking to 1.5 kg. of cracked ice in a 3-l. flask. The resulting mixture is then steam-distilled until all the aldehyde and unchanged toluene are driven over. Fifty cubic centimeters of ether is added to the distillate, the two layers are separated, and the aqueous layer is washed with 150 cc. of ether which is then added to the first non-aqueous layer (Note 4). After drying with calcium chloride, the aldehyde is obtained by distilling from a 500-cc. flask provided with a short fractionating column (Note 5). The yield of p-tolualdehyde distilling at 201–205° is 121–132 g. (46–51 per cent of the theoretical amount based on the toluene). Redistillation involves but a slight loss and gives an almost colorless product which distils at 203–205° (Note 6).
2. Notes
1. The cuprous chloride may be prepared according to Org. Syn. Coll. Vol. I, 1941, 170. The precipitate is washed several times by decantation with sulfurous acid, collected on a large Büchner funnel, washed with glacial acetic acid, and dried in an evaporating dish until the odor of acetic acid has disappeared. The cuprous chloride obtained is pure white and should not be exposed unnecessarily to the air.
An alternative procedure for preparing cuprous chloride is given on p. 131.
2. The carbon monoxide may be forced by water from a 75-l. container, after which it is dried by bubbling through two wash bottles containing concentrated sulfuric acid.
In place of this large container for carbon monoxide it is possible to generate the gas more conveniently by adding 170 g. (141 cc., 3.69 moles) of pure formic acid (sp. gr. 1.2) to 250 g. (135.8 cc.) of concentrated sulfuric acid contained in a 1-l. distilling flask heated on an oil bath to 70–80°. The side arm of the flask is connected to the sulfuric acid wash bottles. In order to ensure a smooth and constant flow of carbon monoxide, the formic acid is placed in a dropping funnel which extends through a two-holed rubber stopper in the neck of the distilling flask. The other hole of this stopper is connected by rubber tubing to a one-holed stopper in the dropping funnel. No frothing was evident under these conditions, but should frothing occur it is recommended that a small quantity of paraffin be added to the sulfuric acid in the generating flask.
3. The mixture frequently is too thick to be poured, and a spatula must be used to remove it.
4. The extraction of the aldehyde from the unchanged toluene with sodium bisulfite at this point in the preparation does not appreciably increase the purity of the product.
5. It is necessary to use a water-condenser until the temperature reaches 150°, after which an air-condenser is used.
6. The use of a few crystals of hydroquinone has been recommended for the storage of p-tolualdehyde.
3. Discussion
The method described is that of Gattermann and Koch.1 p-Tolualdehyde has also been prepared from toluene, hydrogen cyanide, hydrogen chloride, and aluminum chloride;2 from toluene, nickel carbonyl, and aluminum chloride;3 from p-tolunitrile by reduction with stannous chloride followed by hydrolysis of the aldimine;4 from p-xylene by oxidation, particularly with chromyl chloride;5 and from p-tolylmagnesium bromide with formaldehyde phenylhydrazone,6 ethyl orthoformate, methylformanilide, ethoxymethyleneaniline, or carbon disulfide. The syntheses involving the Grignard reagent, except the first mentioned, have been examined and evaluated by Smith and Bayliss7 and Smith and Nichols:7 the use of ethoxymethyleneaniline or of ethyl orthoformate is recommended.
This preparation is referenced from:

References and Notes
  1. Gattermann and Koch, Ber. 30, 1622 (1897).
  2. Bayer and Company, Ger. pat. 99,568 [Frdl. 5, 98 (1897–1900)]; Hinkel, Ayling, and Morgan, J. Chem. Soc. 1932, 2796; Hinkel, Ayling, and Beynon, ibid. 1935, 677.
  3. Dewar and Jones, J. Chem. Soc. 85, 216 (1904).
  4. Stephen, ibid. 127, 1874 (1925); Williams, J. Am. Chem. Soc. 61, 2248 (1939).
  5. Law and Perkin, J. Chem. Soc. 91, 258 (1907).
  6. Grammaticakis, Compt. rend. 210, 303 (1940).
  7. Smith and Bayliss, J. Org. Chem. 6, 437 (1941); Smith and Nichols, ibid. 6, 489 (1941).

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

calcium chloride (10043-52-4)

sulfuric acid (7664-93-9)

hydrogen chloride (7647-01-0)

acetic acid (64-19-7)

ether (60-29-7)

methylformanilide (103-84-4)

carbon monoxide (630-08-0)

hydroquinone (123-31-9)

hydrogen cyanide (74-90-8)

formic acid (64-18-6)

stannous chloride

sodium bisulfite (7631-90-5)

aluminum chloride (3495-54-3)

toluene (108-88-3)

carbon disulfide (75-15-0)

cuprous chloride (7758-89-6)

p-xylene (106-42-3)

Ethyl orthoformate

p-Tolunitrile (104-85-8)

sulfurous acid (7782-99-2)

chromyl chloride

nickel carbonyl

formaldehyde phenylhydrazone

ethoxymethyleneaniline (6780-49-0)

p-tolylmagnesium bromide (4294-57-9)

p-Tolualdehyde (104-87-0)