Ethyl bromoacetate → HCID 22219598, compound

HRID 1793805Notes

Reaction equation

HRID 1793805 reaction equation
[H-].[Na+].[NH:3]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12][C:10]3=2)[CH:5]=[CH:4]1.Br[CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27]>CN(C=O)C>[CH2:29]([O:28][C:26](=[O:27])[CH2:25][N:3]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12][C:10]3=2)[CH:5]=[CH:4]1)[CH3:30]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 24758Sodium hydrideHCID 22219596HCID 22219596, compound

Product 1

HCID 22219598HCID 22219598, compoundYield 124.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

Under N2, a flame-dried, 250-mL, three-necked flask was charged with sodium hydride (0.56 g, 13.9 mmol) and anhydrous DMF (20 mL) and cooled to 0° C. A suspension of tert-butyl 6,7,9,10-tetrahydroazepino[4,5-g]indole-8(1H)-carboxylate (2.66 g, 9.3 mmol) in anhydrous DMF (30 mL) was added and the mixture was stirred at 0° C. for 1 hour and then at room temperature for 30 m. Ethyl bromoacetate (2.06 mL, 18.6 mmol) was added and the mixture was stirred at room temperature for 16 hours. The mixture was partitioned between EtOAc and water and the organic layer was washed with water and the organic layer concentrated to give 4.32 g of a brown oil. Dissolving the oil in CH2Cl2 and filtration of the resulting precipitate removes unreacted starting material. Column chromatography of the filtrate (elution with 20–50% Et2O/hexane) gave 2.11 g (61%) of the title compound as a white solid: mp 111 –115° C.; 1H NMR (300 MHz, CDCl3) δ 7.37 (d, J=8 Hz, 1 H), 6.93–6.90 (m, 2 H), 6.48 (d, J=3 Hz, 1 H), 4.98 (s, 2 H), 4.24 (q, J=7 Hz, 2 H), 3.60–3.57 (m, 4 H) 3.17–3.13 (m, 2 H), 3.04–3.00 (m, 2 H), 1.44 (s, 9 H), 1.29 (t, J=7 Hz, 3 H); MS (EI), m/z 372 (M+); HRMS (FAB) calcd for C20H26N2O4+H 359.1971. found 359.1972. Anal. Calcd for C21H28N2O4: C, 67.72; H, 7.58; N, 7.52. Found: C, 68.06; H, 7.70; N, 7.73.

Workup

  1. additionwas added
  2. customat room temperature
  3. stirringthe mixture was stirred at room temperature for 16 hours
  4. customThe mixture was partitioned between EtOAc and water
  5. washthe organic layer was washed with water
  6. concentrationthe organic layer concentrated

Sources & evidence

ORD record
ord-3dfd5150937b47448d59d2791a911848
Source dataset
uspto-grants-2006_04
Patent number
US07022694B2

Reaction notes

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