Dimethylformamide → 1,1-Dimethylethyl 8-cyano-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

HRID 1514198Notes

Reaction equation

FC(F)(F)S(O[C:7]1[CH:24]=[CH:23][C:10]2[CH2:11][N:12]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:13][CH2:14][O:15][C:9]=2[CH:8]=1)(=O)=O.[CH3:27][N:28](C=O)C>CCOC(C)=O.O.[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>[C:27]([C:7]1[CH:24]=[CH:23][C:10]2[CH2:11][N:12]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:13][CH2:14][O:15][C:9]=2[CH:8]=1)#[N:28]

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 1,1-dimethylethyl 8-{[(trifluoromethyl)sulfonyl]oxy}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (Preparation 31) (0.397 g, 0.999 mmol), zinc cyanide (0.176 g, 1.499 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.115 g, 0.100 mmol) in DMF (4 ml) was stirred and heated at 80° C. for 2 hours then cooled and diluted with EtOAc/water (40 ml of each) and the organic washed with 3×20 ml of water, dried (magnesium sulphate), evaporated and purified by flash chromatography eluting with 1:4 EtOAc/iso-hexane to give the title compound (198 mgs) as a gum which crystallised slowly. MS (ES) C15H18N2O3 requires 274; found 175 [M+H−100]+.

Workup

temperaturethen cooled
washorganic washed with 3×20 ml of water
dry with materialdried (magnesium sulphate)
customevaporated
custompurified by flash chromatography
washeluting with 1:4 EtOAc/iso-hexane

Sources & evidence

ORD record: ord-ca352a763f9e49b1ae60bee125fbbb13
Source dataset: uspto-grants-2012_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08222245B2

Reaction notes

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