Hydrochloric Acid → Pratol

Temperature

-10 °C

Dry, pulverulent lithium hydroxide (38.7 mmol, 3 equivalents) is added in one portion to a well-stirred solution of 2′,4′-dihydroxyacetophenone (12.9 mmol) in dry THF (15 ml) at −78° C. under an argon atmosphere. The reaction mixture is stirred at −78° C. for one hour and subsequently at −10° C. for two hours. After re-cooling it −78° C., a solution of 4-methoxybenzoyl chloride (14.2 mmol) in THF (20 ml) is added in one portion. The mixture is stirred at −78° C. for one hour and at room temperature for 4 hours until the starting material has disappeared. The reaction mixture is emptied onto a mixture of ice (300 g) and concentrated HCl (10 ml) and extracted with dichloromethane (3×50 ml). The solvents are removed from the dried extracts, and the residue is dried under reduced pressure for 24 hours. Glacial acetic acid (100 ml) and sulfuric acid (0.5 ml) are added to the residue, and the mixture is heated at 95–100° C. under an argon atmosphere for from 30 minutes to one hour. Approximately one third of the acetic acid is stripped off, and the residue is emptied into water. The precipitated product is filtered, washed and dried and recrystallised from methanol to give 4′-methoxy-7-hydroxyflavone. 1H NMR (250 MHz, d6-DMSO): δ 10.90 (br s, OH), 8.01–7.11 (dm, 4H), 7.87 (d, 1H), 7.00 (d, 1H), 6.93 (d, 1H), 6.81 (s, 1H), 3.86 (s, 3H); 13C NMR (62.90 MHz, d6-DMSO): δ176.24 (s), 162.58 (s), 162.00 (s), 161.87 (s), 157.39 (s), 127.93 (s), 126.41 (s), 123.42 (s), 116.07 (s), 114.83 (s), 114.48 (s), 105.07 (s), 102.48 (s), 55.46 (s); EI-MS (70 eV) m/e (rel. abund.)=268.07356 (100). The product is beige and exhibits the UV absorption maximum at λ=323 nm with ε=26450 (in 2-propanol) (cf. FIG. 2).

1. customDry
2. temperatureAfter re-cooling it −78° C.
3. stirringThe mixture is stirred at −78° C. for one hour and at room temperature for 4 hours until the starting material
4. extractionextracted with dichloromethane (3×50 ml)
5. customThe solvents are removed from the dried extracts
6. customthe residue is dried under reduced pressure for 24 hours
7. additionGlacial acetic acid (100 ml) and sulfuric acid (0.5 ml) are added to the residue
8. temperaturethe mixture is heated at 95–100° C. under an argon atmosphere for from 30 minutes to one hour
9. filtrationThe precipitated product is filtered
10. washwashed
11. customdried
12. customrecrystallised from methanol

ORD record

ord-2a04aaa8ac8442fab556a75e3f6b2a35

Source dataset

uspto-grants-2006_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07128900B2