Organic Syntheses Part 12

[6] Jahresb. 1876, 308; Gazz. chim. ital. 22 (2), 67 (1892); Bull. soc. chim. (3) 25, 309 (1901).

[1b] Ber. 39, 4146 (1900).

[2b] Ber. 31, 1023 (1898).

[3b] J. Am. Chem. Soc. 44, 425 (1922).

XIX

PHENYLHYDRAZINE

C6H5NH2<.>HCl + NaNO2 + HCl--> C6H5N2Cl + NaCl + 2H2O C6H5N2Cl + 4H(Na2SO3)--> C6H5NHNH2<.>HCl

Prepared by G. H. COLEMAN. Checked by J. B. CONANT and H. R. THOMPSON.

1. Procedure

IN a 12-l. round-bottom flask, fitted with a mechanical stirrer, are placed 1045 cc. of concentrated commercial hydrochloric acid (sp. gr. 1.138). The flask is surrounded with a freezing mixture of ice and salt, and when the contents are at 0'0, stirring is started and 500 g. of cracked ice are added; then 372 g. of aniline, also cooled to 0'0, are run in during five minutes. The mixture is treated with 500 g. more of cracked ice, and a cold solution (0'0) of 290 g. of technical sodium nitrite dissolved in 600 cc.

of water are allowed to run in slowly (twenty to thirty minutes) from a dropping funnel, the end of which is drawn to a small tip, and reaches nearly to the bottom of the flask. During this addition, the stirrer is operated rather vigorously, and the temperature is kept as near 0'0 as possible by the frequent addition of cracked ice (about 1 kg).

In the meantime, a sodium sulfite solution is prepared by dissolving 890 g. of sodium hydroxide, of about 90 per cent purity, in about 1 l.

of water and then diluting to 6 l. A few drops of phenolphthalein solution are added and sulfur dioxide pa.s.sed in, first until an acid reaction is indicated and then for two or three minutes longer.

During the addition of the sulfur dioxide, the solution is cooled with running water. On account of the strong alkaline solution, the original color produced by the phenolphthalein is very faint, but this slowly increases until it becomes deep just before the acid point is reached. It is best to remove a small sample of the liquid from time to time, dilute with three or four volumes of water and add a drop more of phenolphthalein.

The sodium sulfite solution is placed in a 12-l. flask and cooled to about 5'0. Approximately 500 g. of cracked ice are added, and then, with mechanical stirring, the diazonium salt solution is run in as rapidly as possible. The mixture becomes a bright orange-red. The flask is now warmed to about 20'0 on a steam bath, until the solid sodium sulfite, which has separated while cooling, redissolves.

The total amount of liquid is now about 10 l. One-half of this is poured into another 12-l. flask, and both halves are warmed on the steam bath to 60-70'0, until the color becomes quite dark (thirty to sixty minutes). Sufficient hydrochloric acid (300-400 cc.) is now added to each flask to make the solutions acid to litmus.

The heating is continued and the color gradually becomes lighter until, after four to six hours, the solutions have become nearly colorless; they may be heated overnight, if desired.

To the hot solutions are now added about one-third of their volume of concentrated hydrochloric acid (2 l. to each portion) and the mixtures cooled, first in running water, then in a freezing mixture, to 0'0. The phenylhydrazine hydrochloride precipitates in the form of slightly yellowish or pinkish crystals which may be filtered off and dried.

The free base is liberated by adding to the phenylhydrazine hydrochloride 1 l. of a 25 per cent solution of sodium hydroxide.

The phenylhydrazine separates and is taken up with benzene (two 300-cc. portions). The combined extractions are well dried with 200 g. of solid sodium hydroxide, poured off, and distilled.

Most of the benzene may be distilled under ordinary pressure, and the remainder, and any low-boiling impurities, under diminished pressure. The pure phenylhydrazine boils at 137-138'0/18 mm., and is obtained as a pale-yellow liquid.

It can be crystallized on cooling in an ice bath; the crystals melt at 230. The crude phenylhydrazine from two lots of aniline (744 g.) is best distilled at one time and gives 695-725 g.

of pure product (80-84 per cent of the theoretical amount).

2. Notes

If the sodium sulfite solution contains an excess of alkali, a black tar tends to form when the solution is warmed, and very little phenylhydrazine is obtained. Great care must be taken in determining the end point in the neutralization of the sodium hydroxide by the sulfur dioxide.

If the sodium sulfite-diazonium salt mixture is acidified before warming or before becoming dark, the red color of the solution does not disappear on heating, and the precipitated phenylhydrazine hydrochloride obtained is colored red.

The benzene solution of phenylhydrazine should be well dried before distilling, since the presence of moisture causes an increased amount of foaming to take place just after the benzene has distilled off.

When the distillation is carried out carefully, practically no phenylhydrazine distils with the benzene or other low-boiling impurities.

In order to obtain the maximum yield, it is necessary to cool the hydrochloric acid solution of the phenylhydrazine hydrochloride from 20'0 to 0'0, before filtration. From 5 to 10 per cent of product separates between these two temperatures. When this is done, no more phenylhydrazine hydrochloride is obtained by concentration of the mother liquor.

An increase in the amount of hydrochloric acid above 2 l.

for the precipitation of the hydrochloride produces no increase in yield of product.

Most published directions for the preparation of phenylhydrazine specify the use of zinc dust and acetic acid following the reduction with sodium sulfite. No improvement in the quality or quant.i.ty of the product was obtained by using zinc and acetic acid.

It is best to use freshly prepared sodium sulfite for the reduction, since the commercial quality is poor and gives a lower yield of phenylhydrazine. A cylinder of liquid sulfur dioxide should, of course, be available.

The rapid addition of the diazonium salt solution to the sodium sulfite seems to be advantageous.

Pure phenylhydrazine dissolves in dilute acetic acid to yield a perfectly clear solution.

The phenylhydrazine hydrochloride may be purified by crystallizing from water. A 600-cc. portion of water is used for 100 g.

of crude hydrochloride, and the solution boiled a short time with a few grams of animal charcoal. After filtering, 200 cc.

of concentrated hydrochloric acid are added, and the mixture cooled to 0'0. Pure white crystals in a yield of 85-90 g. are obtained.

Rubber gloves should be worn when working with large quant.i.ties of phenylhydrazine, since the product may cause serious injury to the skin. The vapors of phenylhydrazine should not be inhaled.

3. Other Methods of Preparation

Phenylhydrazine has been prepared by the reduction of benzene diazonium salts with sulfites;[1] by the reduction of benzene diazonium chloride with stannous chloride;[2] by the reduction of benzene diazonium hydrate with zinc or sulfur dioxide;[3] by the reduction of sodium benzene diazotate with sodium stannite;[4] by the reduction of diazoamino benzene;[5] by the reduction of nitrosophenyl hydroxylamine or its methyl ether;[6] and by the action of hydrazine hydrate on phenol.[7]

[1] Ann. 190, 79 (3878); Ber. 20, 2463, (1887).

[2] Ber. 16, 2976 (1883); 17, 572, footnote (1884).

[3] Ber. 31, 346 (1898).

[4] Ber. 36, 816 (1903).

[5] Ber. 31, 582 (1898).

[6] Ann. 190, 77 (1878).

[7] Ber. 31, 2910 (1898).

The most feasible method consists in the reduction of diazonium salts with sodium sulfite. Although this method is given in several laboratory manuals, the results were not found entirely satisfactory.

The present directions provide for a lengthy but essential heating of the diazonium-sulfite mixture, omit the useless zinc dust reduction, and supply exact details for preparation on a fairly large laboratory scale.

XX

PHTHALIMIDE CO CO C6H4<>O + NH4OH--> C6H4<>NH + 2H2O CO CO CO CO 2C<><>4<>O + (NH4)2CO3--> 2<><>NH + CO2 + 3H2O CO CO

Prepared by W. A. NOYES and P. K. PORTER. Checked by H. T. CLARKE and J. H. BISHOP.