Ethyl bromoacetate → HCID 22396780, compound

HRID 2307012Notes

Reaction equation

HRID 2307012 reaction equation
[H-].[Na+].[Cl:3][C:4]1[C:12]2[N:11]([CH2:13][C:14]([O:16]CC)=O)[C:10]3[CH2:19][CH2:20][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:22][CH2:23][C:9]=3[C:8]=2[CH:7]=[C:6](Cl)[CH:5]=1.[Cl:32]C1C2NC3CCN(C(OC(C)(C)C)=O)CCC=3C=2C=C(Cl)C=1.BrCC(OCC)=O>CN(C=O)C>[Cl:3][C:4]1[C:12]2[N:11]([CH2:13][CH2:14][OH:16])[C:10]3[CH2:19][CH2:20][N:21]([C:24]([O:26][C:27]([CH3:29])([CH3:28])[CH3:30])=[O:25])[CH2:22][CH2:23][C:9]=3[C:8]=2[CH:7]=[CH:6][C:5]=1[Cl:32]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 22396592HCID 22396592, compoundHCID 86590376HCID 86590376, compound

Product 1

HCID 22396780HCID 22396780, compoundYield 107.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Preparation of tert-Butyl 7,9-dichloro-6-(2-ethoxy-2-oxoethyl)-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate Sodium hydride (60% dispersion in mineral oil, 0.25 g, 6.3 mmol) was added to a solution of tert-butyl 7,9-dichloro-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate (1.5 g, 4.2 mmol) in DMF (15 mL). After 20 min, ethyl bromoacetate (0.94 mL, 8.4 mmol) was added. The reaction was quenched with saturated aqueous NH4Cl after 2 h and extracted with EtOAc (3×20 mL). The combined organic extracts were washed with brine, dried over Na2SO4, decanted, and concentrated. The crude product was purified by column chromatography (Biotage, 40M) with heptane/EtOAc (3:1) to give 1.8 g (98%) of a white solid: mp 117.0-120.0° C.; IR (diffuse reflectance) 2972, 1744, 1690, 1464, 1409, 1377, 1366, 1349, 1294, 1222, 1204, 1190, 1167, 1111, 861 cm−1; MS (EI) m/z 440 (M+), 440, 386, 385, 384, 339, 311, 310, 300, 298, 57; Anal. Calcd for C21H26Cl2N2O4: C, 57.15; H, 5.94; N, 6.35; found: C, 56.97; H, 5.97; N, 6.19.

Workup

  1. customThe reaction was quenched with saturated aqueous NH4Cl after 2 h
  2. extractionextracted with EtOAc (3×20 mL)
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried over Na2SO4
  5. customdecanted
  6. concentrationconcentrated
  7. customThe crude product was purified by column chromatography (Biotage, 40M) with heptane/EtOAc (3:1)

Sources & evidence

ORD record
ord-6ee33d2a1b4c472f9bf922487a4cd0d1
Source dataset
uspto-grants-2004_12
Patent number
US06828314B2

Reaction notes

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