Hexane → Dimethyl (3-methyl-2-oxo-3-phenylbutyl)phosphonate

HRID 867802Notes

Reaction equation

HRID 867802 reaction equation
C([Li])CCC.CCCCCC.[CH3:12][P:13](=[O:18])([O:16][CH3:17])[O:14][CH3:15].[CH3:19][C:20]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)([CH3:25])[C:21](OC)=[O:22]>C1COCC1.O.C(O)(=O)C>[CH3:25][C:20]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)([CH3:19])[C:21](=[O:22])[CH2:12][P:13](=[O:18])([O:16][CH3:17])[O:14][CH3:15]

Participants

8

Reactant 4

HCID 8058HexaneHCID 12958Dimethyl methylphosphonateHCID 143498Methyl 2-methyl-2-phenylpropanoateHCID 178418339Butyllithium

Product 1

HCID 13345715Dimethyl (3-methyl-2-oxo-3-phenylbutyl)phosphonate

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of n-butyl lithium in hexane (1.59N, 44.0 ml, 70.0 mmol) was added to a solution of dimethyl methylphosphonate (8.74 g, 70.0 mmol) in anhydrous THF (130 ml) cooled at -78° C. under argon atmosphere, and the mixture was stirred for 30 minutes. To this reaction mixture was added a solution of methyl 2-methyl-2-phenylpropionate (5.00 g, 28.0 mmol) in anhydrous THF (15 ml) at -78° C. The mixture was stirred for 2 hours, allowed to warm to room temperature and neutralized with acetic acid. The reaction mixture was diluted with water (10 ml), and concentrated. The residue was combined with ethyl acetate (100 ml) and water (30 ml). The separated organic layer was washed with water (30 ml) and brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was distilled (b.p. 135°-141° C./0.05 mmHg) to give an oil of dimethyl 3-methyl-2-oxo-3-phenylbuthylphosphonate (5.73 g, 21.2 mmol, 75.7%). This compound was assigned the structure by the following data:

Workup

  1. stirringThe mixture was stirred for 2 hours
  2. concentrationconcentrated
  3. washThe separated organic layer was washed with water (30 ml) and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. distillationThe residue was distilled (b.p. 135°-141° C./0.05 mmHg)
  7. customto give an oil of dimethyl 3-methyl-2-oxo-3-phenylbuthylphosphonate (5.73 g, 21.2 mmol, 75.7%)

Sources & evidence

ORD record
ord-4550a02ad73f4300922ba7669972b16e
Source dataset
uspto-grants-1988_10
Patent number
US04775692

Reaction notes

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