Sodium Bicarbonate → Allyl 2-amino-6-(cyanomethyl)-pyrazolo[1,5-a]pyrimidine-3-carboxylate

HRID 524840Notes

Reaction equation

[NH2:1][C:2]1[C:6]([C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8])=[C:5]([NH2:13])[NH:4][N:3]=1.CO[CH:16](OC)[CH:17]([CH:21](OC)OC)[CH2:18][C:19]#[N:20].NC1C(C(ON2C3C=CC=CC=3N=N2)=O)=C2N=CC(CC#N)=CN2N=1.C([O-])(O)=O.[Na+]>CS(C)=O.O.CCOC(C)=O>[NH2:13][C:5]1[C:6]([C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8])=[C:2]2[N:1]=[CH:16][C:17]([CH2:18][C:19]#[N:20])=[CH:21][N:3]2[N:4]=1

Participants

Conditions

Temperature: 85 °C

Procedure

To a suspension of allyl 3,5-diamino-1H-pyrazole-4-carboxylate 3 (63.49 g, 348.5 mmol) in a mixture of DMSO (340 mL) and water (340 mL), was added 3-(dimethoxymethyl)-4,4-dimethoxy-butanenitrile (Scheme 3, below) (85 g, 418.2 mmol), followed by para-toluene Sulfonic acid hydrate (1) (11.27 g, 59.24 mmol). The reaction mixture was heated to 85° C. and stirred overnight. The reaction mixture was cooled with an ice bath. The mixture was diluted with EtOAc (680 mL) and a saturated aqueous solution of NaHCO3 (1.36 L). The precipitate was filtered and rinsed with water, then with a mixture of water and EtOAc. The brown solid was dried under vacuum to give allyl 2-amino-6-(cyanomethyl)-pyrazolo[1,5-a]pyrimidine-3-carboxylate 4c as a brown solid (55.94 g, 62% yield).

Workup

temperatureThe reaction mixture was cooled with an ice bath
filtrationThe precipitate was filtered
washrinsed with water
additionwith a mixture of water and EtOAc
customThe brown solid was dried under vacuum

Sources & evidence

ORD record: ord-affd044ebaba45edab4169a58ed0d336
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09340546B2

Reaction notes

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