PURPOSE: To industrially and advantageously obtain a compound useful as an intermediate for dye for fiber, pigment, agricultural chemical, medicine and optical material by chlorinating p-aminophenol with a chlorine gas in a specific alcohol-hydrochloric acid-based mixed solvent.

CONSTITUTION: An alcohol of the formula ROH (R is 1-4C lower alkyl)(e.g. methyl alcohol)-hydrochloric acid-based mixed solvent are packed into a reactor equipped with a central stirrer with blades, a cooler, a thermometer and a chlorine introduction pipe, p-aminophenol is added to the reactor, the reaction raw materials are heated to 70°C and a chlorine gas is introduced from a chlorine feed pipe to carry out chlorination reaction. The reaction product is cooled to a room temperature, the reaction product is filtered and separated by a glass filter, washed with pure water and the prepared crystal is dried by a dryer in an atmosphere at 60°C for 12 hours to give the chloranil useful as an intermediate for dye for fibers, pigment, agricultural chemical, medicine and optical material or chloranil electrode, additive for lubricant, etc., high yield and in high purity.