Methyl Acrylate → Methyl 3-(dimethoxyphosphinoyl)propionate

HRID 2259459Notes

Reaction equation

HRID 2259459 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[CH:2]=[CH2:3].[CH3:7][O:8][P:9]([O-:12])[O:10][CH3:11].C[O-].[Na+]>CO>[CH3:7][O:8][P:9]([CH2:3][CH2:2][C:1]([O:5][CH3:6])=[O:4])(=[O:12])[O:10][CH3:11]

Participants

5

Reactant 3

HCID 7294Methyl AcrylateHCID 10942334Sodium Methoxide2×HCID 21884954Dimethylphosphite

Product 1

HCID 87769Methyl 3-(dimethoxyphosphinoyl)propionateYield 70.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

This procedure was reported by; Kreutzkamp, N.; Mengel, W. Chem. Ber., 1967, 100, 709-714. ##STR8## A mixture of methyl acrylate (30 mL, 28.7 g, 0.33 mol) and dimethylphosphite (36.7 g, 0.33 mol) was cooled to 0° C. and treated with a solution of sodium methoxide (1M) in methanol (5 mL). After a few min a vigorous exothermic reaction took place. When the reaction subsided, an additional portion of sodium methoxide was added. This procedure was repeated for a total of four times. The reaction was then allowed to stir at room temperature for 16 h and then the methanol removed by distillation. The residue was then vacuum distilled, bp 95° C. @ 0.15mm, to provide 45.6 g, 70% of pure product. 1H NMR (CDCI3 /TMS/300 MHz) δ3.71(d, J=11.1 Hz, 6H), 3.67 (s, 3H), 2.57 (td, J=8.4, 12.5 Hz, 2H), 2.06(td, J=8.4 12.5 Hz, 2H); 31P NMR (CDCI3) 33.3 (s); 13C NMR (CDCI3) 172.3, 52.3(d, J=6.5 Hz), 51.8, 27.0(d, J=4.1 Hz), 20.8, 18.9.

Workup

  1. customAfter a few min a vigorous exothermic reaction
  2. customthe methanol removed by distillation
  3. distillationvacuum distilled

Sources & evidence

ORD record
ord-05924debe7cb4db5a5ea42a3493dd0f3
Source dataset
uspto-grants-1995_12
Patent number
US05473092

Reaction notes

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