HCID 71650762, compound → Ethyl 2-amino-8-(pentafluoroethyl)-3H-1-benzazepine-4-carboxylate

HRID 1873497Notes

Reaction equation

[C:1]([CH2:3]/[C:4](=[CH:10]\[C:11]1[CH:16]=[CH:15][C:14]([C:17]([F:23])([F:22])[C:18]([F:21])([F:20])[F:19])=[CH:13][C:12]=1[N+:24]([O-])=O)/[C:5]([O:7][CH2:8][CH3:9])=[O:6])#[N:2]>[Fe].C(O)(=O)C>[NH2:2][C:1]1[CH2:3][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])=[CH:10][C:11]2[CH:16]=[CH:15][C:14]([C:17]([F:23])([F:22])[C:18]([F:21])([F:20])[F:19])=[CH:13][C:12]=2[N:24]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of (E)-ethyl 2-(cyanomethyl)-3-(2-nitro-4-(perfluoroethyl)phenyl)acrylate (2.60 g, 6.87 mmol) was added iron powder (2.30 g, 41.2 mmol). The mixture was heated to 90° C. for 5 hours. Upon cooling the acetic acid was removed under vacuum and the resulting semisolid was dissolved in 50% K2CO3 (100 mL) and EtOAc (100 mL). The mixture was filtered to remove insoluble material and the phases were separated. The aqueous phase was extracted with EtOAc (2×100 mL). The combined organics were dried and concentrated. The concentrate was purified via flash chromatography (100% CH2Cl2 to 2% MeOH) to yield (1E,4E)-ethyl 2-amino-8-(perfluoroethyl)-3H-benzo[b]azepine-4-carboxylate (1.8 g, 74%). 1H NMR (CDCl3) δ 1.39 (t, 3H), 2.95 (s, 2H), 4.32 (q, 2H), 5.12 (br s, 1-2H), 7.22-7.27 (m, 2H), 7.47-7.51 (m, 2H), 7.80 (s, 1H).

Workup

customwas removed under vacuum
dissolutionthe resulting semisolid was dissolved in 50% K2CO3 (100 mL)
filtrationThe mixture was filtered
customto remove insoluble material
customthe phases were separated
extractionThe aqueous phase was extracted with EtOAc (2×100 mL)
customThe combined organics were dried
concentrationconcentrated
customThe concentrate was purified via flash chromatography (100% CH2Cl2 to 2% MeOH)

Sources & evidence

ORD record: ord-d8e5687f6a2945b1849ea3d7640eb284
Source dataset: uspto-grants-2012_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08304407B2

Reaction notes

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