Acetic Acid → HCID 178490497, compound

HRID 1602228Notes

Reaction equation

HRID 1602228 reaction equation
COC(=O)[C:4]1[CH:9]=[CH:8][C:7]([CH:10]=O)=[CH:6][CH:5]=1.[NH2:13][C:14]1[C:22]2[C:17](=[N:18][CH:19]=[N:20][C:21]=2[NH:23][C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([Cl:30])[CH:25]=2)[NH:16][N:15]=1.[C:31]([OH:34])(=O)C.[BH3-]C#N.[Na+].CN1[C:44](=[O:45])N(C)CC1>C(O)C.CC(C)=O.[Pt]>[Cl:30][C:26]1[CH:25]=[C:24]([NH:23][C:21]2[N:20]=[CH:19][N:18]=[C:17]3[NH:16][N:15]=[C:14]([NH:13][C:10](=[C:31]=[O:34])[C:7]4[CH:6]=[CH:5][C:4]([O:45][CH3:44])=[CH:9][CH:8]=4)[C:22]=23)[CH:29]=[CH:28][CH:27]=1

Participants

9

Reactant 5

HCID 176Acetic AcidHCID 66611,3-Dimethyl-2-imidazolidinoneHCID 15294Methyl 4-Formylbenzoate2×HCID 5003444Sodium cyanoborohydrideHCID 178509242HCID 178509242, compound

Product 1

HCID 178490497HCID 178490497, compound

Reagents, catalysts & solvents 3

HCID 23939PlatinumCatalystHCID 180AcetoneSolventHCID 702EthanolSolvent

Procedure

788 mg (4.8 mmol) of 4-formyl-benzoic acid methyl ester and 300 mg of 5% Pt/C are added to a solution of 1.04 g (4.0 mmol) of 3-amino-4-(3-chloro-phenylamino)-1H-pyrazolo[3,4-d]pyrimidine in 40 ml of DMEU and 961 mg (16 mmol) of acetic acid and hydrogenation is carried out immediately (instead of hydrogenation, reduction with NaCNBH3 is also possible). After two days and after four days, a further 788 mg of 4-formylbenzoic acid methyl ester is added. After 7 days the catalyst is separated off from the reaction mixture by filtration through Celite, the filtrate is decolorized by treatment with activated carbon and then concentrated by evaporation under a high vacuum at 70° C. to give a residue of ≈4 g. Crystallization with diisopropyl ether/toluene yields product of ≈80% purity. Heating in a mixture of 30 ml of ethanol and ≈5 ml of acetone, filtering while hot, concentration by evaporation to half the volume and cooling yield 4-(3-chloro-phenylamino)-3-(4-methoxy-carbonylbenzylamino)-1H-pyrazolo[3,4-d]pyrimidine; m.p. 228° C.; FAB-MS: (M+H)+ =409.

Workup

  1. waitafter four days
  2. customAfter 7 days the catalyst is separated off from the reaction mixture by filtration through Celite
  3. concentrationconcentrated by evaporation under a high vacuum at 70° C.
  4. customto give a residue of ≈4 g
  5. customCrystallization with diisopropyl ether/toluene
  6. customyields product of ≈80% purity
  7. filtrationfiltering while hot,
  8. concentrationconcentration
  9. customby evaporation to half the volume
  10. temperaturecooling

Sources & evidence

ORD record
ord-03f54dbe0b9149769b2d449cfabce302
Source dataset
uspto-grants-1999_11
Patent number
US05981533

Reaction notes

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