反应详情

A mixture of 10.0 g (37.4 mM) of 4-chloro-1-ethyl-6-methyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylic acid ethyl ester, prepared according to Examples 1b and 1c from 5-amino-1-ethylpyrazole in place of 5-amino-1-pentylpyrazole, and 7.65 g (43.0 mM) of N-bromosuccinimide in 75 ml of carbon tetrachloride was illuminated with a sunlamp and stirred under N2 at gentle reflux for 2 hours. The cooled reaction mixture was filtered and the filtrate concentrate to leave an orange residue which was dissolved in 50 ml of THF. 35 ml of saturated aqueous sodium carbonate were added, and the mixture was stirred vigorously at rt for 18 hours and then diluted with water and extracted with EtOAc. The combined extracts were dried with MgSO4, filtered and concentrated to leave a white solid which was chromatographed over silica gel using the solvent system of EtOAc:hexane (1:3) as the eluant. The fractions containing the desired product were combined and concentrated to leave a white solid. Recrystallization of the solid from toluene/hexane gave 4.88 g of the desired ester as white needles, mp=156°-157.5° C.; tlc, Rf =0.2, silica gel, EtOAc:hexane (1:3).

1. customprepared
2. customwas illuminated with a sunlamp
3. temperatureat gentle reflux for 2 hours
4. customThe cooled reaction mixture
5. filtrationwas filtered
6. concentrationthe filtrate concentrate
7. customto leave an orange residue which
8. stirringthe mixture was stirred vigorously at rt for 18 hours
9. extractionextracted with EtOAc
10. dry with materialThe combined extracts were dried with MgSO4
11. filtrationfiltered
12. concentrationconcentrated
13. customto leave a white solid which
14. customwas chromatographed over silica gel using the solvent system of EtOAc:hexane (1:3) as the eluant
15. additionThe fractions containing the desired product
16. concentrationconcentrated
17. customto leave a white solid
18. customRecrystallization of the solid from toluene/hexane