Dimethylformamide → Methyl 7-cyano-2,3-dihydro-1-benzoxepine-4-carboxylate

HRID 2228301Notes

Reaction equation

Br[C:2]1[CH:3]=[CH:4][C:5]2[O:11][CH2:10][CH2:9][C:8]([C:12]([O:14][CH3:15])=[O:13])=[CH:7][C:6]=2[CH:16]=1.[CH3:17][N:18](C=O)C>[C-]#N.[Zn+2].[C-]#N.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:17]([C:2]1[CH:3]=[CH:4][C:5]2[O:11][CH2:10][CH2:9][C:8]([C:12]([O:14][CH3:15])=[O:13])=[CH:7][C:6]=2[CH:16]=1)#[N:18]

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of methyl 7-bromo-2,3-dihydro-1-benzoxepine-4-carboxylate (1416 mg, 5.00 mmol), zinc cyanide (352 mg, 3. 00 mmol), tetrakis(triphenylphosphine)-palladium (347 mg, 0.30 mmol) and DMF(10 ml) was stirred at 80° C. for 3 hours. The mixture was concentrated under reduced pressure, and to the residue was added ethyl acetate. Insoluble materials were filtered off, which were washed with ethyl acetate. The filtrate was concentrated under reduced pressure. The resulting crude product was recrystallized from ethyl acetate to give methyl 7-cyano-2,3-dihydro-1-benzoxepine-4-carboxylate (800 mg, 3.49 mmol, 70%). IR (KBr): 2222, 1721 cm−1.

Workup

concentrationThe mixture was concentrated under reduced pressure
additionto the residue was added ethyl acetate
filtrationInsoluble materials were filtered off
washwhich were washed with ethyl acetate
concentrationThe filtrate was concentrated under reduced pressure
customThe resulting crude product was recrystallized from ethyl acetate

Sources & evidence

ORD record: ord-886a025cb6044477a043eb41249a4edc
Source dataset: uspto-grants-2002_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06413947B1

Reaction notes

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