Acetic Acid → 1,4-Naphthalenedione, 2-bromo-

Temperature

45 °C

A 3-L, three-necked, round-bottomed flask fitted with a mechanical stirrer, a 500 mL addition funnel and a thermometer was charged with glacial acetic acid (500 mL), water (1000 mL) and N-bromosuccinimide (71.2 g, 0.40 mol). The mixture was warmed to 45° C. during which time a yellow solution was obtained. An acetic acid (500 mL) solution of 1-naphthol (14.4 g, 0.10 mol) was then added dropwise over a period of 75 minutes so as to give a red solution, the latter of which was stirred an additional 30 minutes at 45° C. before cooling to room temperature. The resulting mixture was diluted with water (1500 mL) and extracted with methylene chloride (6×400 mL). The combined organic extracts were in turn washed with water (4×400 mL) and saturated sodium bicarbonate solution (4×300 mL). Rotary evaporation of the solvent following drying over magnesium sulfate yielded a yellow solid that was recrystallized from 95% ethanol to yield pure 2-bromo-1,4-naphthoquinone (18.50 g, 78%); mp 130.5°-132° C. (lit. mp 131°-132° C.). IR (KBr) 3050, 1675, 1655, 1585, 1570, 1330, 1310, 1295, 1270, 1245, 1220, 1120, 1060, 910, 890, 820, 790, 775, 670, 665 cm−1; 1H NMR (CDCl3) δ 8.21-8.14 (m, 1H), 8.11-8.05 (m, 1H), 7.80-7.73 (m, 2H), 7.52 (s, 1H); 13C NMR (CDCl3) 182.4 (0), 177.8 (0), 140.3 (1), 140.1 (0), 134.4 (1), 134.1 (1), 131.7 (0), 130.9 (0), 127.8 (1), 126.9 (1) ppm.

1. customwas obtained
2. customto give a red solution
3. temperaturebefore cooling to room temperature
4. extractionextracted with methylene chloride (6×400 mL)
5. washwashed with water (4×400 mL) and saturated sodium bicarbonate solution (4×300 mL)
6. customRotary evaporation of the solvent
7. dry with materialfollowing drying over magnesium sulfate
8. customyielded a yellow solid
9. customthat was recrystallized from 95% ethanol

ORD record

ord-4ac4878d3e6d4b388714acdaa60d4c75

Source dataset

uspto-grants-2005_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06844353B2