Dichloromethane → Methyl 2-methanesulfonyloxy-3-phenyl-propionate

HRID 1656689Notes

Reaction equation

HRID 1656689 reaction equation
ClCCl.[OH:4][CH:5]([CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:6]([O:8][CH3:9])=[O:7].C(N(CC)CC)C.[CH3:24][S:25](Cl)(=[O:27])=[O:26]>ClCCl.CCOCC>[CH3:24][S:25]([O:4][CH:5]([CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:6]([O:8][CH3:9])=[O:7])(=[O:27])=[O:26]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 518800Methyl 2-hydroxy-3-phenylpropanoate

Product 1

HCID 13662406Methyl 2-methanesulfonyloxy-3-phenyl-propionateYield 93%

Reagents, catalysts & solvents 1

HCID 21881112Ethyl ether methylene chlorideSolvent

Procedure

To a stirred solution of phenylalanine (16.5 g, 0.1 mole) in 2N sulfuric acid at 0° C., was added sodium nitrite (10.5 g, 1.5 equiv) in small portions over a period of 0.5 hours and the mixture stirred overnight. Aqueous phase was extracted with ether (5×250 mL) and the ethereal extracts were washed with saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated to give phenyllactic acid (1 equiv) in methanol (15 equiv) at 0° C. and the mixture stirred at room temperature overnight. Removal of volatiles in vacuo and chromatographic purification of the oil (20-25% ethyl acetate in hexane) gives methyl 2-hydroxy-3-phenylpropionate. 1H NMR (300 MHz, CDCl3): δ7.33-7.196 (m, 5H), 4.451 (dd, 1H), 3.764 (s, 3H), 3.1225 (dd, 4.45 Hz, 13.95 Hz, 1H), 2.9575 (dd, 7 Hz, 14 Hz, 1H), 2.787 (br s, 1H). A dichloromethane solution of methyl 2-hydroxy-3-phenylpropionate is treated with triethylamine (1.1 equiv) and methanesulfonyl chloride (1.1 equiv) at 0° C. Upon completion of reaction, the mixture is dissolved in dichloromethane/ether and washed with saturated aqueous solution of sodium chloride, dried and concentrated. Purification of crude material by flash column chromatography (40% ethyl acetate in hexane) gives methyl 2-methanesulfonyloxy-3-phenyl-propionate (1.6 g, 93%).

Workup

  1. customUpon completion of reaction
  2. washwashed with saturated aqueous solution of sodium chloride
  3. customdried
  4. concentrationconcentrated
  5. customPurification of crude material by flash column chromatography (40% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-1c70f6cd3edd4e6d8252623e4454642a
Source dataset
uspto-grants-1993_10
Patent number
US05254682

Reaction notes

Loading…