反应详情

With ice-cooling, 1.9 g of manganese dioxide (85%) are added to a suspension of 715 mg (2.6 mmol) of 4-(3-chloroanilino)-6-hydroxymethyl-7H-pyrrolo[2,3-d]pyrimidine in 170 ml of methylene chloride and the mixture is stirred at RT for 20 h. 20 ml of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) are then added to the reaction mixture, and it is stirred for 1 h and then filtered through Hyflo. The filtration residue is again stirred (1 h) in 50 ml of methylene chloride/DMPU (1:1) and again filtered. The two filtrates are combined, evaporated and taken up in ethyl acetate/THF and water. The aqueous phases are extracted twice with ethyl acetate; the organic phases are washed 4 times with water and brine, dried (MgSO4) and evaporated down to a residual volume of ≈20 ml. Addition of diethyl ether and filtration yields 4-(3-chloroanilino)-6-formyl-7H-pyrrolo[2,3-d]pyrimidine; HPLC: tRet(Grad20)=10.1; TLC-Rf=0.24 (CH2Cl2/methanol [10:1]).

1. temperatureWith ice-cooling
2. stirringis stirred for 1 h
3. filtrationfiltered through Hyflo
4. stirringThe filtration residue is again stirred (1 h) in 50 ml of methylene chloride/DMPU (1:1)
5. filtrationagain filtered
6. customevaporated
7. extractionThe aqueous phases are extracted twice with ethyl acetate
8. washthe organic phases are washed 4 times with water and brine
9. dry with materialdried (MgSO4)
10. customevaporated down to a residual volume of ≈20 ml
11. additionAddition of diethyl ether and filtration