Thionyl Chloride → 4-Chloro-7H-pyrrolo(2,3-d)pyrimidine-5-carbonitrile

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Reaction Steps

To a suspension of 4-chloro-7H-pyrrolo[2,3-d]pyrimidine-5-carbaldehyde oxime (865 mg, 4.40 mmol, 1.0 eq) in DCM (20 mL), thionyl chloride (3.1 mL, 43.7 mmol, 10.0 eq) was added and the resulting mixture was stirred at RT overnight. The reaction mixture was concentrated in vacuo. The residue was suspended in water (60 mL) and saturated aqueous NaHCO3 was added to adjust the pH to 4. The solid was collected by filtration, rinsed with water followed by ethyl acetate to afford the first batch of product. The filtrate was then extracted with ethyl acetate (50 mL×3). The combined organic layer was washed with brine, dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo and the residue was combined with the above-obtained solid. The crude product was then re-crystallized in ethyl acetate/hexanes (1:1) and dried in vacuo to afford 4-chloro-7H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile (763 mg, 97% yield). ESI-MS m/z: 178.8 [M+H]+, 176.8 [M−H]−.

Provenance & Evidence