Dimethyl methylphosphonate → Dimethyl 2-o-methylphenyl-2-oxoethylphosphonate
Reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[CH3:13][C:14]1[CH:23]=[CH:22][CH:21]=[CH:20][C:15]=1[C:16](OC)=[O:17]>C1COCC1.C(O)(=O)C.O>[CH3:13][C:14]1[CH:23]=[CH:22][CH:21]=[CH:20][C:15]=1[C:16](=[O:17])[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9]Participants
Conditions
- Temperature
- 0 °C
Procedure
n-Butyl lithium (1.58N, 52.5 ml, 83 mmol) was added dropwise to a stirred solution of dimethyl methylphosphonate (10.3 g, 83 mmol) in 100 ml of anhydrous THF at -78° C. under argon atmosphere. After 30 minutes, methyl o-methylbenzoate (5.0 g, 33 mmol) in 10 ml of anhydrous THF was added dropwise. After being stirred for 30 minutes, this reaction mixture was allowed to warm to 0° C., diluted with 5 ml of acetic acid and 10 ml of water, and concentrated. 20 ml of water was added and the mixture was extracted with ethyl acetate (50 ml×2). The combined ethyl acetate layers were washed with water (20 ml×1) and brine (20 ml×1), dried over anhydrous sodium sulfate, and concentrated. The residue was distilled under reduced pressure to give an oil of dimethyl 2-o-methylphenyl-2-oxoethylphosphonate (68 g, 28.1 mmol, yield 85.1%, b.p. 134°-136° C./0.21 mmHg), which was assigned the structure by the following data:
Workup
- concentrationconcentrated
- addition20 ml of water was added
- extractionthe mixture was extracted with ethyl acetate (50 ml×2)
- washThe combined ethyl acetate layers were washed with water (20 ml×1) and brine (20 ml×1)
- dry with materialdried over anhydrous sodium sulfate
- concentrationconcentrated
- distillationThe residue was distilled under reduced pressure
Sources & evidence
- ORD record
- ord-33b55cead9254810b5431902b8587d9a
- Source dataset
- uspto-grants-1988_10
- Patent number
- US04775692
Reaction notes
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