Ethyl bromoacetate → N-benzyl-3-ethoxycarbonylmethoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine

HRID 274045Notes

Reaction equation

HRID 274045 reaction equation
[CH2:1]([NH:8][CH:9]1[CH2:15][C:14]2[CH:16]=[C:17]([OH:20])[CH:18]=[CH:19][C:13]=2[CH2:12][CH2:11][CH2:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].[Na+].Br[CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26].[Cl-].[NH4+]>C1(C)C=CC=CC=1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:1]([NH:8][CH:9]1[CH2:10][CH2:11][CH2:12][C:13]2[CH:19]=[CH:18][C:17]([O:20][CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])=[CH:16][C:14]=2[CH2:15]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 7748Ethyl bromoacetateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 18007284HCID 18007284, compound

Product 1

HCID 18007287N-benzyl-3-ethoxycarbonylmethoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
70 °C

Procedure

To an ice-cooled solution of 8-benzylamino-6,7,8,9-tetrahydro-5H-benzocyclohepten-2-ol (1.7 g) in toluene (56 ml) was added portionwise sodium hydride (60% dispersion in mineral oil; 0.31 g). After the addition was complete, the mixture was stirred at 70° C. for 1 hour. After cooling, a mixture of ethyl bromoacetate (0.81 ml) and tetra-n-butylammonium bromide (0.10 g) in toluene (14 ml) was added, and the mixture was stirred at 70° C. for 4 hours. After cooling, the reaction mixture was poured into saturated aqueous ammonium chloride, and extracted once with ethyl acetate. The extract was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (gradient elution; chloroform-ethanol; 25:1 to 5:1) to give N-benzyl-3-ethoxycarbonylmethoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine (2.0 g) as an oil.

Workup

  1. additionAfter the addition
  2. temperatureAfter cooling
  3. additionwas added
  4. stirringthe mixture was stirred at 70° C. for 4 hours
  5. temperatureAfter cooling
  6. extractionextracted once with ethyl acetate
  7. washThe extract was washed with water and brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by column chromatography on silica gel (gradient elution; chloroform-ethanol; 25:1 to 5:1)

Sources & evidence

ORD record
ord-917169f2c68442e1b65b96da33f0367f
Source dataset
uspto-grants-1995_02
Patent number
US05387710

Reaction notes

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