Trimethyl phosphite → 1-[2-(Dimethoxy-phosphoryl)-acetyl]-cyclopropanecarboxylic acid n-butyl ester

HRID 605487Notes

Reaction equation

HRID 605487 reaction equation
[CH2:1]([O:5][C:6]([C:8]1([C:11](=[O:14])[CH2:12]Br)[CH2:10][CH2:9]1)=[O:7])[CH2:2][CH2:3][CH3:4].[CH3:15][O:16][P:17]([O:20]C)[O:18][CH3:19]>C1(C)C=CC=CC=1>[CH2:1]([O:5][C:6]([C:8]1([C:11](=[O:14])[CH2:12][P:17]([O:18][CH3:19])([O:16][CH3:15])=[O:20])[CH2:10][CH2:9]1)=[O:7])[CH2:2][CH2:3][CH3:4]

Participants

4

Reactant 2

HCID 8472Trimethyl phosphite2×HCID 57429591HCID 57429591, compound

Product 1

HCID 600281941-[2-(Dimethoxy-phosphoryl)-acetyl]-cyclopropanecarboxylic acid n-butyl esterYield 59%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 16 3.42 g (13.0 mmol) and trimethylphosphite (1.95 mL, 2.05 g, 16.5 mmol) in toluene (45 mL) was refluxed for 15 hours. The solvent and remaining trimethyl phosphite were then distilled off, and the residue was purified by column chromatography (2-10% isopropanol/hexane) to give 2.26 g (7.74 mmol; 59% yield) of 17. 1H NMR (500 MHz, CDCl3) δ 0.95 (3H, t, J=7.3 Hz), 1.39 (2H, m), 1.57-1.67 (6H, m), 3.75 (2H, d, JH-P=22.1 Hz), 3.78 (6H, d, JH-P=11.1 Hz), 4.15 (2H, t, J=6.7 Hz). 13C NMR (125 MHz, CDCl3) δ 13.7, 19.2, 20.6, 30.5, 35.3, 39.8, 40.8, 52.9 (d, JC-P=6.0 Hz), 170.8, 197.0 (d, JC-P=6.3 Hz). MS (EI) m/z 292 (15, M+), 264 (17), 236 (21), 218 ((45), 191 (18), 163 (22), 150 (59), 126 (100); exact mass (ESI) calculated for C12H21O6PNa ([M+Na]+) 315.0973, found 315.0963.

Workup

  1. distillationwere then distilled off
  2. customthe residue was purified by column chromatography (2-10% isopropanol/hexane)

Sources & evidence

ORD record
ord-fa938ac63f194b4ab2996dd16f99f14c
Source dataset
uspto-grants-2011_03
Patent number
US07915242B2

Reaction notes

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