Bromine → 2-(S)-(2-Acetoxymethyl-4-amino-5-bromo-3-methyl-benzyl)-succinic acid diethyl ester

HRID 1985509Notes

Reaction equation

HRID 1985509 reaction equation
[CH2:1]([O:3][C:4](=[O:26])[C@@H:5]([CH2:12][C:13]1[CH:18]=[CH:17][C:16]([NH2:19])=[C:15]([CH3:20])[C:14]=1[CH2:21][O:22][C:23](=[O:25])[CH3:24])[CH2:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH3:2].C([O-])(=O)C.[Na+].[Br:32]Br.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(O)(=O)C>[CH2:1]([O:3][C:4](=[O:26])[C@@H:5]([CH2:12][C:13]1[CH:18]=[C:17]([Br:32])[C:16]([NH2:19])=[C:15]([CH3:20])[C:14]=1[CH2:21][O:22][C:23](=[O:25])[CH3:24])[CH2:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH3:2]

Participants

6

Reactant 4

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 517045Sodium AcetateHCID 597319272-(S)-(2-Acetoxymethyl-4-amino-3-methyl-benzyl)-succinic acid diethyl ester

Product 1

HCID 597318802-(S)-(2-Acetoxymethyl-4-amino-5-bromo-3-methyl-benzyl)-succinic acid diethyl esterYield 77%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

2-(S)-(2-Acetoxymethyl-4-amino-3-methyl-benzyl)-succinic acid diethyl ester (7.6 g, 21 mmol) was dissolved in acetic acid (100 mL). Sodium acetate (4.2 g, 51 mmol) was added to the solution. Reaction vessel was placed in a cool water bath to control reaction exotherm. Bromine (1.1 mL, 22 mmol) was added to the mixture in one portion. Reaction stirred at ambient temperature for 10 minutes. Mixture was poured into 1N aqueous sodium thiosulfate solution (400 mL). Material was extracted twice with ethyl acetate. Organic phase was washed successively with water and brine. Organic was dried (magnesium sulfate), filtered and concentrated in vacuo. Silica gel chromatography (ethyl acetate-hexanes) afforded the desired product in 77% yield as an amber oil. MS m/e (M−H)−=440.0, 442.0.

Workup

  1. customReaction vessel
  2. customwas placed in a cool water bath
  3. customreaction exotherm
  4. customReaction
  5. extractionMaterial was extracted twice with ethyl acetate
  6. washOrganic phase was washed successively with water and brine
  7. dry with materialOrganic was dried (magnesium sulfate)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d3e190c5509b45bfbc31ae50e49314b1
Source dataset
uspto-grants-2009_06
Patent number
US07544680B2

Reaction notes

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