Ethyl bromoacetate → HCID 67359980, compound

HRID 1664486Notes

Reaction equation

HRID 1664486 reaction equation
[CH2:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH2:4][CH:3]([C:14]([OH:16])=[O:15])[CH2:2]1.[H-].[Na+].Br[CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22].OP([O-])(O)=O.[K+]>CN(C=O)C>[CH2:24]([O:23][C:21]([CH2:20][N:12]1[C:13]2[CH2:1][CH2:2][CH:3]([C:14]([OH:16])=[O:15])[CH2:4][C:5]=2[C:6]2[C:11]1=[CH:10][CH:9]=[CH:8][CH:7]=2)=[O:22])[CH3:25]

Participants

6

Reactant 4

HCID 7748Ethyl bromoacetateHCID 24758Sodium hydrideHCID 516951Monobasic potassium phosphateHCID 13491214HCID 13491214, compound

Product 1

HCID 67359980HCID 67359980, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of 2,3,4,9-tetrahydro-1H-carbazole-3-carboxylic acid (0.40 g, 1.86 mmol) in dry DMF (4 ml) is added NaH (0.16 g, 4.1 mmol, 60% in mineral oil) in one portion. After gas evolution has ceased, the reaction mixture is kept stirring at rt for 1 h. Then, ethyl bromoacetate (0.21 ml, 1.9 mmol) is added and stirring is continued overnight. Saturated KH2PO4 solution is added and the mixture is extracted with dichloromethane. The organic layers are combined and washed with H2O and brine, dried over Na2SO4, filtered and concentrated. The residue is purified by flash chromatography on silica gel (hexane/EtOAc 3:1) to afford pure title compound as an off-white solid (0.34 mg) in 61% yield. tR (LC-3) 2.05 min; ESI-MS (positive ion): m/z 324.15 [M+Na]+ (calcd 301.13 for C17H19NO4). 1H-NMR (DMSO-d6): 1.13 (t, J=7.0 Hz, 3H); 1.79 (m, 11-1); 2.14 (m, 1H); 2.64 (m, 4H); 2.86 (dd, J=14.3 Hz, 4.8 Hz, 1H); 4.05 (q, J=7.0 Hz, 2H); 4.88 (s, 2H); 6.90 (dd, J=7.6 Hz, 7.0 Hz, 1H); 6.97 (dd, J=7.6 Hz, 7.0 Hz, 1H); 7.23 (d, J=8.1 Hz, 1H); 7.3 (d, J=6.8 Hz, 1H); 12.08 (s br, 1H).

Workup

  1. stirringstirring
  2. waitis continued overnight
  3. extractionthe mixture is extracted with dichloromethane
  4. washwashed with H2O and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue is purified by flash chromatography on silica gel (hexane/EtOAc 3:1)

Sources & evidence

ORD record
ord-4210e644048a4584b586bd7bdc5ae6c2
Source dataset
uspto-grants-2011_10
Patent number
US08039474B2

Reaction notes

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