Tetrahydrofuran → HCID 22219611, compound

HRID 1793808Notes

Reaction equation

HRID 1793808 reaction equation
[N+:1]([C:4]1[C:14]2[CH2:13][CH2:12][N:11]([C:15]([O-:17])=[O:16])[CH2:10][CH2:9][C:8]=2[CH:7]=[CH:6][CH:5]=1)([O-])=O.[CH:18]([Mg]Br)=[CH2:19].[Cl-].[NH4+].[CH2:24]1COCC1>>[NH:1]1[C:4]2[C:5](=[CH:6][CH:7]=[C:8]3[CH2:9][CH2:10][N:11]([C:15]([O:17][CH3:24])=[O:16])[CH2:12][CH2:13][C:14]3=2)[CH:19]=[CH:18]1

Participants

5

Reactant 4

HCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 22219616HCID 22219616, compoundHCID 178418507HCID 178418507, compound

Product 1

HCID 22219611HCID 22219611, compound

Conditions

Temperature
-40 °C

Procedure

Under N2, a flame-dried, 100-mL, two-necked flask was charged with 6-nitro-1,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxylate (0.85 g, 3.4 mmol) and THF (20 mL) and cooled to −40° C. Vinyl magnesium bromide (11.2 mL, 11.2 mmol) was added and the solution was stirred for 30 min allowing to warm to −20° C. Ammonium chloride was added and the mixture partitioned between EtOAc and water. The organic layer was concentrated to give 0.88 g of a brown oil. Column chromatography (elution with 10–30% EtOAc/heptane) afforded 0.28 g (34%) of the title compound as a solid. Crystallization from EtOAc/hexane affords 0.192 g of a white solid: mp 169–171° C.; 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J=8 Hz, 1 H), 7.19–7.17 (m, 1 H), 6.90 (d, J=8 Hz, 1 H), 6.53–6.52 (m, 1 H), 3.76 (s, 3 H), 3.72–3.63 (m, 4 H), 3.19–3.10 (m, 1 H), 3.00–3.10 (m, 3 H); 13C NMR (100 MHz, CDCl3) δ 156.6, 135.5, 134.1, 133.6, 126.6, 124.3, 122.7, 118.3, 102.9, 52.7, 47.4, 46.0, 37.3, 30.4; IR (diffuse reflectance) 3313, 1673, 1476, 1446, 1414, 1275, 1260, 1237, 1217, 1115, 947, 805, 764, 745, 731 cm31 1; MS (EI) m/z 244 (M+); Anal. Calcd for C14H16N2O2: C, 68.83; H, 6.60; N, 11.47. Found: C, 68.78; H, 6.58; N, 11.43.

Workup

  1. temperatureto warm to −20° C
  2. customthe mixture partitioned between EtOAc and water
  3. concentrationThe organic layer was concentrated

Sources & evidence

ORD record
ord-691c976afd524b79838a0095eeca6158
Source dataset
uspto-grants-2006_04
Patent number
US07022694B2

Reaction notes

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