Hexane → Dimethyl 2-oxo-3-phenoxypropylphosphonate

Temperature

-78 °C

Dimethyl methylphosphonate (18 ml, 0.166 mol) was addded to anhydrous THF (150 ml) under argon atmosphere and cooled to -78° C. After 20 min. a solution of n-butyl lithium in hexane (1.59N, 108.8 ml, 0.173 mmol) was added to the mixture. After being stirred for 30 min. a solution of methyl phenoxyacetate (10 ml, 0.069 mmol) in 10 ml of anhydrous THF was added, and the reaction mixture was stirred successively for 30 min. at -78° C. and for 30 min. at room temperature, and acidified with acetic acid. After confirming a weakly acidic pH of the solution thus obtained, THF was distilled out. Water (50 ml) was added to the residue, and the resulting mixture was extracted with ethyl acetate (150 ml×3). The combined organic layers were washed with 100 ml of water and with 100 ml of brine, dried over anhydrous sodium sulfate, and concentrated. The oily product was distilled under reduced pressure to afford dimethyl 2-oxo-3-phenoxypropylphosphonate (14.65 g, 0.057 mol, yield: 82.3%). B.p.: 145°-147° C./0.1 mmHg. The product was identified by the following data.

1. additionwas added
2. customthus obtained
3. distillationTHF was distilled out
4. additionWater (50 ml) was added to the residue
5. extractionthe resulting mixture was extracted with ethyl acetate (150 ml×3)
6. washThe combined organic layers were washed with 100 ml of water and with 100 ml of brine
7. dry with materialdried over anhydrous sodium sulfate
8. concentrationconcentrated
9. distillationThe oily product was distilled under reduced pressure

ORD record

ord-e1b8dd12fa6041a9931dca27c82ca1e7

Source dataset

uspto-grants-1988_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04775692