Formaldehyde → 3-iodo-1-(1-methyl-4-piperidyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amine

HRID 897892Notes

Reaction equation

HRID 897892 reaction equation
Cl.Cl.[I:3][C:4]1[C:12]2[C:7](=[N:8][CH:9]=[N:10][C:11]=2[NH2:13])[N:6]([CH:14]2[CH2:19][CH2:18][NH:17][CH2:16][CH2:15]2)[N:5]=1.[C:20](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C=O.[OH-].[Na+]>ClC(Cl)C>[I:3][C:4]1[C:12]2[C:7](=[N:8][CH:9]=[N:10][C:11]=2[NH2:13])[N:6]([CH:14]2[CH2:19][CH2:18][N:17]([CH3:20])[CH2:16][CH2:15]2)[N:5]=1

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 14798Sodium HydroxideHCID 5049666Sodium triacetoxyborohydrideHCID 223473623-iodo-1-(4-piperidyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amine dihydrochloride

Product 1

HCID 223471833-iodo-1-(1-methyl-4-piperidyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amineYield 70%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

To a mixture of 3-iodo-1-(4-piperidyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amine dihydrochloride (0.5 g, 0.0012 mol) and sodium triacetoxyborohydride (0.36 g, 0.00168 mol) in dichloroethane (40 mL) was added formaldehyde solution (37% in water, 0.037 mL, 0.00132 mol) at room temperature. The mixture was stirred at room temperature under an atmosphere of nitrogen for 4 hours. A 5 N aqueous solution of sodium hydroxide (2 mL) was added to the mixture. The solvent was removed under the reduced pressure. The residue was partitioned between water and dichloromethane. 20 The aqueous layer was extracted with dichloromethane (3×150 mL). The combined organic extracts were washed with water, and brine, and dried over magnesium sulfate. The solvents were evaporated under the reduced pressure to leave solid. The solid was resubjected to the same reaction and work-up conditions as above to yield 3-iodo-1-(1-methyl-4-piperidyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amine (0.3 g, 0.00084 mol). TLC (methanol/dichloromethane=10:90) Rf 0.63 MS: MH+ 359.

Workup

  1. customThe solvent was removed under the reduced pressure
  2. customThe residue was partitioned between water and dichloromethane
  3. extraction20 The aqueous layer was extracted with dichloromethane (3×150 mL)
  4. washThe combined organic extracts were washed with water, and brine
  5. dry with materialdried over magnesium sulfate
  6. customThe solvents were evaporated under the reduced pressure
  7. customto leave solid
  8. customThe solid was resubjected to the same reaction

Sources & evidence

ORD record
ord-487247a639344e319073f7037aae3815
Source dataset
uspto-grants-2005_07
Patent number
US06921763B2

Reaction notes

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