Dimethyl methylphosphonate → HCID 14302184, compound

HRID 867783Notes

Reaction equation

HRID 867783 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[CH:13]1([CH2:19][CH2:20][C:21](OC)=[O:22])[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1>C1COCC1.C(O)(=O)C.O>[CH:13]1([CH2:19][CH2:20][C:21](=[O:22])[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9])[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1

Participants

7

Reactant 3

HCID 12958Dimethyl methylphosphonateHCID 88651Methyl cyclohexanepropionateHCID 178418339Butyllithium

Product 1

HCID 14302184HCID 14302184, compoundYield 81.7%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

n-Butyl lithium (1.63N, 45.1 ml, 73 mmol) was added dropwise to a stirred solution of dimethyl methylphosphonate (9.05 g, 73 mmol) in 100 ml of anhydrous THF at -78° C. under argon atmosphere. After 30 minutes, a solution of methyl 3-cyclohexylpropionate (5.0 g, 29.4 mmol) in 10 ml of anhydrous THF was further added dropwise and the mixture was stirred for 30 minutes. This reaction solution was allowed to warm to 0° C., diluted with 4.4 ml of acetic acid and 10 ml of water, and concentrated. 30 ml of water was added to the residue 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 a colorless transparent oil of dimethyl 4-cyclohexyl-2-oxobutylphosphonate (6.3 g, 24 mmol, yield 81.7%, b.p. 138°-142° C./0.05 mmHg), which was assigned the structure by the following data:

Workup

  1. concentrationconcentrated
  2. addition30 ml of water was added to the residue
  3. extractionthe mixture was extracted with ethyl acetate (50 ml ×2)
  4. washThe combined ethyl acetate layers were washed with water (20 ml×1) and brine (20 ml×1)
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. distillationThe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-e296ba3258004aa4b70f672ca7321ff9
Source dataset
uspto-grants-1988_10
Patent number
US04775692

Reaction notes

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