Acetic Acid → HCID 178478158, compound

HRID 1068927Notes

Reaction equation

HRID 1068927 reaction equation
[NH2:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[N:8][C:9]=2[NH:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([Cl:18])[CH:13]=2)[NH:4][N:3]=1.C(O)(=O)C.[NH:23]1[C:27]([CH:28]=O)=[N:26][N:25]=[N:24]1>CO>[Cl:18][C:14]1[CH:13]=[C:12]([NH:11][C:9]2[N:8]=[CH:7][N:6]=[C:5]3[NH:4][N:3]=[C:2]([N:1]=[CH:28][C:27]4[NH:26][N:25]=[N:24][N:23]=4)[C:10]=23)[CH:17]=[CH:16][CH:15]=1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 178509242HCID 178509242, compoundHCID 178520064HCID 178520064, compound

Product 1

HCID 178478158HCID 178478158, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

With gentle heating, 195 mg (0.75 mmol) of 3-amino-4-(3-chloro-phenylamino)-1H-pyrazolo[3,4-d]pyrimidine (see Step 1.6) and 135 mg of acetic acid are dissolved in 20 ml of methanol. Then, at RT, 1.0 mmol of tetrazole-5-carbaldehyde is added and the reaction mixture is stirred overnight to complete the reaction, during which a solid separates out. Concentration by evaporation to approximately half volume and filtration yield 4-(3-chloro-phenylamino)-3-[(tetrazol-5-yl)-methyleneamino]-1H-pyrazolo[3,4-d]pyrimidine. More material can be recovered from the mother liquor by concentration by evaporation and stirring the residue in isopropanol. Under a nitrogen atmosphere, 208 mg of the above intermediate are dissolved in 27 ml of DMEU and, with ice cooling, 4.2 ml (4.2 mmol) of DIBAL-H are added and the mixture is stirred for 7 hours. 13 ml of ethyl acetate are added and the mixture is stirred for 30 min and diluted with 130 ml of methanol. 0.9 ml of water and 9 g of Na2SO4 are added to the precipitate, followed by stirring for 30 min and then filtration. The filtrate is concentrated by evaporation (RV, HV) and chromatographed (SiO2; CH2Cl2/−methanol=4:1) and the crude product is stirred in isopropanol/diethyl ether to yield 4-(3-chloro-phenylamino)-3-[(tetrazol-5-yl)-methylamino]-1H-pyrazolo[3,4-d]pyrimidine:HPLC: tRet(grad20-100)=6.7; FAB MS (M+H)+=343.

Workup

  1. customthe reaction
  2. concentrationConcentration
  3. customby evaporation
  4. filtrationto approximately half volume and filtration

Sources & evidence

ORD record
ord-abdc08c17a16415094354aa3bf0d1533
Source dataset
uspto-grants-2001_06
Patent number
US06251911B1

Reaction notes

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