A Publication of Reliable Methods for the Preparation of Organic
Compounds Annual Volume Org. Synth. 1942, 22, 96 DOI:
10.15227/orgsyn.022.0096 [Benzene, azido-] Submitted by R. O.
Lindsay and C. F. H. Allen. Checked by R. L. Shriner and J. C.
Lawler. 1. Procedure In a 1-l. three-necked flask fitted with a
stirrer, a thermometer, and a dropping funnel are placed 300 ml.
of water and 55.5 ml. of concentrated hydrochloric acid. The
flask is surrounded by an ice-salt bath, the stirrer is started,
and 33.5 g. (0.31 mole) of phenylhydrazine (Note 1) is added
dropwise (5–10 minutes is required). Phenylhydrazine
hydrochloride separates as fine white plates. Stirring is
continued, and, after the temperature has fallen to 0°, 100 ml.
of ether is added, after which a previously prepared solution of
25 g. of technical sodium nitrite in 30 ml. of water is added
from the dropping funnel at such a rate that the temperature
never rises above 5°. This requires 25–30 minutes. The reaction
mixture is subjected to steam distill