Oxalyl chloride → (4-Bromomethyl-2-phenylbenzoyl)methionine methyl ester
Reaction equation
[Br:1][CH2:2][C:3]1[CH:11]=[CH:10][C:6]([C:7]([OH:9])=O)=[C:5]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:4]=1.C(Cl)(=O)C(Cl)=O.Cl.[CH3:25][O:26][C:27](=[O:34])[C@H:28]([CH2:30][CH2:31][S:32][CH3:33])[NH2:29].C(N(C(C)C)CC)(C)C>ClCCl.CCOCC>[CH3:25][O:26][C:27](=[O:34])[C@H:28]([CH2:30][CH2:31][S:32][CH3:33])[NH:29][C:7](=[O:9])[C:6]1[CH:10]=[CH:11][C:3]([CH2:2][Br:1])=[CH:4][C:5]=1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Procedure
To a solution in dichloromethane (25 mL) of 4-bromomethyl-2-phenylbenzoic acid (2.16 g, 7.42 mmol), prepared as in Example 234B, was added oxalyl chloride (0.84 mL, 965 mmol) and 2 drops on DMF and the reaction mixture was stirred for 2 hours. The reaction mixture was concentrated in vacuo and azeotroped with toluene. The residue was dissolved in dichloromethane (15 mL) and then was added to a solution in dichloromethane (15 mL) of methionine methyl ester hydrochloride (1.78 g, 8.90 mmol) and diisopropylethylamine (3.10 g, 17.81 mmol) (prepared at −10° C.) dropwise. The reaction mixture was stirred for 30 minutes and then was poured into ether and extracted with water, aqueous 3N HCl (2×) and brine, dried, filtered and concentrated in vacuo. Chromatography on silica gel (5% ethyl acetate-chloroforn) to give (4-bromomethyl-2-phenylbenzoyl)methionine methyl ester (2.42 g, 75%).
Workup
- concentrationThe reaction mixture was concentrated in vacuo
- customazeotroped with toluene
- dissolutionThe residue was dissolved in dichloromethane (15 mL)
- stirringThe reaction mixture was stirred for 30 minutes
- extractionextracted with water, aqueous 3N HCl (2×) and brine
- customdried
- filtrationfiltered
- concentrationconcentrated in vacuo
Sources & evidence
- ORD record
- ord-6535fdc3bacd48aea04de25869f6359c
- Source dataset
- uspto-grants-2004_02
- Patent number
- US06693123B2
Reaction notes
Loading…