Pyridine → 2-((2-Cyano-3-nitrophenoxy)methyl)allyl acetate

HRID 471666Notes

Reaction equation

[OH:1][CH2:2][C:3](=[CH2:17])[CH2:4][O:5][C:6]1[CH:13]=[CH:12][CH:11]=[C:10]([N+:14]([O-:16])=[O:15])[C:7]=1[C:8]#[N:9].N1C=CC=CC=1.[CH3:24][C:25](OC(C)=O)=[O:26]>CN(C)C1C=CN=CC=1.C(Cl)Cl.CCOC(C)=O>[C:25]([O:1][CH2:2][C:3]([CH2:4][O:5][C:6]1[CH:13]=[CH:12][CH:11]=[C:10]([N+:14]([O-:16])=[O:15])[C:7]=1[C:8]#[N:9])=[CH2:17])(=[O:26])[CH3:24]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 2-(2-(hydroxymethyl)allyloxy)-6-nitrobenzonitrile (Example 200d) (0.40 g, 1.73 mmol), 4-dimethylaminopyridine (0.21 g, 1.73 mmol) and pyridine (0.68 g, 8.64 mmol) in CH2Cl2 (10.0 mL) at 0° C., was added Ac2O (0.53 g, 5.19 mmol) under a nitrogen atmosphere. After being stirred at 0° C. for 10 min, the mixture was stirred at rt overnight. The reaction mixture was diluted with EtOAc (100 mL), washed with 1.5M HCl, saturated aqueous NaHCO3 and brine, and was dried over MgSO4. The filtrate was evaporated and the residue was purified by chromatography on silica gel using the solvent gradient hexanes→hexanes/EtOAc (3:7), to furnish 0.40 g (84%) of the title compound as a yellow solid. 1H-NMR (400 MHz, DMSO-d6) δ 7.95 (dd, J=8.4 Hz, J=1.2 Hz, 1H), 7.91 (t, J=8.4 Hz, 1H), 7.74 (dd, J=8.4 Hz, J=1.2 Hz, 1H), 5.43-5.46 (m, 1H), 5.36-5.40 (m, 1H), 4.90 (s, 2H), 4.66 (s, 2H), 2.05 (s, 3H).

Workup

stirringthe mixture was stirred at rt overnight
washwashed with 1.5M HCl, saturated aqueous NaHCO3 and brine
dry with materialwas dried over MgSO4
customThe filtrate was evaporated
customthe residue was purified by chromatography on silica gel using the solvent gradient hexanes→hexanes/EtOAc (3:7)

Sources & evidence

ORD record: ord-8c7a8eca2e67413bb34cb5506173c7b4
Source dataset: uspto-grants-2014_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08633186B2

Reaction notes

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