2(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl- → 4-(3-chloroanilino)-6-formyl-7H-pyrrolo[2,3-d]pyrimidine

HRID 567751Notes

Reaction equation

HRID 567751 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][CH:19]=1)[NH:5][C:6]1[C:7]2[CH:14]=[C:13]([CH2:15][OH:16])[NH:12][C:8]=2[N:9]=[CH:10][N:11]=1.CN1CCCN(C)C1=O>C(Cl)Cl.[O-2].[O-2].[Mn+4]>[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][CH:19]=1)[NH:5][C:6]1[C:7]2[CH:14]=[C:13]([CH:15]=[O:16])[NH:12][C:8]=2[N:9]=[CH:10][N:11]=1

Participants

5

Reactant 2

HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 212626544-(3-chloroanilino)-6-hydroxymethyl-7H-pyrrolo[2,3-d]pyrimidine

Product 1

HCID 110976994-(3-chloroanilino)-6-formyl-7H-pyrrolo[2,3-d]pyrimidine

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

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]).

Workup

  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

Sources & evidence

ORD record
ord-bd252a0939b44a3bbd8f99e13b06ac3b
Source dataset
uspto-grants-2001_01
Patent number
US06180636B2

Reaction notes

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