Sulfuric Acid → Drometrizole

참여 물질

반응 단계

Example 5 of U.S. Pat. No. 4,835,284 is duplicated. Water (70 ml), 97% sodium hydroxide 5.2 g, 2-nitro-2'-hydroxy-5'-methylazobenzene (12.9 g) and toluene (10 ml) are mixed and heated to 60° C. After stirring, hydroquinone (0.6 g) is added and glucose (5.0 g) is added to the mixture over one hour at 40° to 45° C. The mixture is further stirred for two hours, and the azobenzene disappears. The reaction liquor is neutralized with 62% sulfuric acid 5.8 g, and is cooled to 20° C. to precipitate a crystal. The crystal thus precipitated is separated by filtration to obtain a wet product 12 g of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole-N-oxide (dry weight: 10.8 g, yield 90.0%, and melting point: 138° C. to 140° C.). To the wet product (12 g) thus obtained, are added methanol (60 ml), water (30 ml), 97% sodium hydroxide (13.0 g) and 9-fluorenone (0.5 g), and glucose (5.5 g) is further added to the mixture over one hour while stirring at 50° to 55° C. The mixture is reacted while stirring at 75° C. (boiling point) for 5 hours. As a result, the N-oxide disappears. The reaction liquor is neutralized with 62% sulfuric acid 19.8 g to pH 8 to precipitate a crystal. The precipitated crystal is separated by filtration, and the separated crystal is fully washed with water and further with methanol. The washed crystal is then dried, thus obtaining 9.4 g of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole having a melting point of 128° to 130° C. at the yield of 92.8%. One can see that the reaction using an aromatic ketone takes over 9 hours to complete. Two catalysts are also required.

출처 및 근거