2-(Dimethylamino)ethanol → Allyl 2-amino-5-(2-(dimethylamino)ethoxy)pyrazolo[1,5-a]pyrimidine-3-carboxylate

HRID 1850676Notes

Reaction equation

HRID 1850676 reaction equation
[NH2:1][C:2]1[C:11]([C:12]([O:14][CH2:15][CH:16]=[CH2:17])=[O:13])=[C:5]2[NH:6][C:7](=[O:10])[CH:8]=[CH:9][N:4]2[N:3]=1.N1C[CH2:20][CH2:21][N:22]2[CH2:28]CCCC[C:23]=12.N1(O[P+](N2CCCC2)(N2CCCC2)N2CCCC2)C2C=CC=CC=2N=N1.CN(C)CCO.C(=O)([O-])[O-].[Cs+].[Cs+]>CC#N>[NH2:1][C:2]1[C:11]([C:12]([O:14][CH2:15][CH:16]=[CH2:17])=[O:13])=[C:5]2[N:6]=[C:7]([O:10][CH2:20][CH2:21][N:22]([CH3:28])[CH3:23])[CH:8]=[CH:9][N:4]2[N:3]=1

Participants

7

Reactant 5

HCID 79022-(Dimethylamino)ethanolHCID 10796Cesium carbonateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 2724700Benzotriazol-1-yl-oxytripyrrolidinophosphoniumHCID 136629519allyl 2-amino-5-oxo-4H-pyrazolo[1,5-a]pyrimidine-3-carboxylate

Product 1

HCID 90412007Allyl 2-amino-5-(2-(dimethylamino)ethoxy)pyrazolo[1,5-a]pyrimidine-3-carboxylateYield 35%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a mixture of allyl 2-amino-5-oxo-4H-pyrazolo[1,5-a]pyrimidine-3-carboxylate (1 g, 4.270 mmol) in MeCN (15 mL) was added 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (975.1 mg, 957.9 μL, 6.405 mmol) and benzotriazol-1-yloxy(tripyrrolidin-1-yl)phosphonium (Phosphorus Hexafluoride Ion) (2.666 g, 5.124 mmol). After 5 minutes, 2-dimethylaminoethanol (3.806 g, 4.291 mL, 42.70 mmol) and cesium carbonate (5 g) were added and the mixture was stirred at room temperature for 30 minutes, followed by heating to 50° C. for 30 minutes. After cooling to room temperature the mixture was filtered and the solid was rinsed with acetonitrile. The filtrate was concentrated in vacuo to an orange oil and purified by column chromatography using 4% MeOH/DCM as eluant. Solvent evaporations in vacuo afforded allyl 2-amino-5-(2-(dimethylamino)ethoxy)pyrazolo[1,5-a]pyrimidine-3-carboxylate as a light orange solid. (450 mg, 35% yield).

Workup

  1. temperatureby heating to 50° C. for 30 minutes
  2. temperatureAfter cooling to room temperature the mixture
  3. filtrationwas filtered
  4. washthe solid was rinsed with acetonitrile
  5. concentrationThe filtrate was concentrated in vacuo to an orange oil
  6. custompurified by column chromatography

Sources & evidence

ORD record
ord-afa2765ea8db40c88531490c8bcc8ad6
Source dataset
uspto-grants-2015_02
Patent number
US08957078B2

Reaction notes

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