Dimethylformamide → 5-(1,3-Dioxolan-2-yl)pyridine-2-carbonitrile

HRID 1747519Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[O:12][CH2:11][CH2:10][O:9]2)=[CH:4][N:3]=1.[CH3:13][N:14](C=O)C>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[O:9]1[CH2:10][CH2:11][O:12][CH:8]1[C:5]1[CH:6]=[CH:7][C:2]([C:13]#[N:14])=[N:3][CH:4]=1

Participants

Conditions

Temperature: 80 °C

Procedure

In DMF (30 mL) were dissolved 2-bromo-5-(1,3-dioxolan-2-yl)pyridine (895 mg, 3.89 mmol) obtained in Step 1, zinc cyanide (1.14 g, 5.83 mmol) and tetrakis(triphenylphosphine)palladium (899 mg, 0.778 mmol) and the mixture was stirred under a nitrogen atmosphere at 80° C. for 12 hours. The reaction mixture was concentrated and water was added. Extraction with ethyl acetate, washing with saturated brine and drying over anhydrous sodium sulfate were performed. After filtration, the solvent in the filtrate was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=7/3) to give 5-(1,3-dioxolan-2-yl)picolinonitrile (506 mg, 740 yield).

Workup

concentrationThe reaction mixture was concentrated
additionwater was added
extractionExtraction with ethyl acetate
washwashing with saturated brine
dry with materialdrying over anhydrous sodium sulfate
filtrationAfter filtration
customthe solvent in the filtrate was evaporated under reduced pressure
customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=7/3)

Sources & evidence

ORD record: ord-8aaa84933db74ea0b3c3dc014148c523
Source dataset: uspto-grants-2015_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09150569B2

Reaction notes

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