o- (CAS NO.: ), with other names like , o-bromo-, could be produced through the following synthetic methods.

In a 3-l. three-necked flask is placed a mixture of 94 g. (1 mole) of phenol and 350 g. (190 cc., 3.5 moles) of concentrated sulfuric acid, and the mixture is heated on a boiling water bath for three hours with constant mechanical stirring. At the end of this time the boiling water bath is replaced by an ice bath. When the reaction mixture has been cooled to room temperature it is made alkaline by the careful addition of a solution of 280 g. (7 moles) of sodium hydroxide in 700 cc. of water. This must be done slowly and with good cooling to prevent boiling. A solid salt, which at first separates, largely dissolves at a later stage.

The alkaline solution is cooled to room temperature; with the stirrer still in constant operation, and after inserting a thermometer, 160 g. (1 mole) of bromine is added from a dropping funnel in the course of twenty to thirty minutes. During this operation the temperature is allowed to rise to 40–50°. Stirring is continued for one-half hour after all the bromine has been added. The solution should still be alkaline and should contain only a small amount of suspended material.

In order to evaporate the solution, the flask is then placed in an oil bath, which is brought to a temperature of 150–155°. As soon as solid material begins to separate, the mixture will bump badly unless a rather rapid current of air is passed through the reaction mixture. This has the further advantage of hastening the evaporation. The heating is continued until a thick, pasty, gray mass is left as a residue, the process requiring thirty to forty minutes. The mixture is allowed to cool and then made strongly acid by the addition of 800 cc. of concentrated sulfuric acid. This must be done slowly and under a hood on account of the rapid evolution of hydrogen bromide.

The flask is then heated in an oil bath maintained at a temperature of 190–210° and the mixture is distilled with steam. The sulfonate groups are hydrolyzed in this process, and the bromophenol passes over as a heavy, colorless or pale yellow oil. In about one hour the distillate is clear. The product is extracted with ether, the ether is removed by distillation from the steam bath, and the residue is distilled at atmospheric pressure. The fraction boiling at 194–200° represents practically pure o-bromophenol. The yield is 70–75 g. (40–43 per cent of the theoretical amount). o-Bromophenol is a colorless liquid with a very characteristic odor. It is rather unstable and decomposes on standing, becoming brown or red in color.