Acetic Acid → (E)-diethylphosphono(6-methoxy-6-methyl-2-hepten-4-ynyl)acetic acid ethyl ester

HRID 1757268Notes

Reaction equation

HRID 1757268 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[CH2:5][P:6]([O:11][CH2:12][CH3:13])([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].[H-].[Na+].[CH3:17][O:18][C:19]([CH3:27])([CH3:26])[C:20]#[C:21]/[CH:22]=[CH:23]/[CH2:24]Br.C(O)(=O)C>C(O)C>[CH2:1]([O:3][C:4](=[O:14])[CH:5]([P:6]([O:8][CH2:9][CH3:10])([O:11][CH2:12][CH3:13])=[O:7])[CH2:24]/[CH:23]=[CH:22]/[C:21]#[C:20][C:19]([O:18][CH3:17])([CH3:27])[CH3:26])[CH3:2]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 13647222(E)-6-methoxy-6-methyl-2-hepten-4-ynyl bromide

Product 1

HCID 86748935(E)-diethylphosphono(6-methoxy-6-methyl-2-hepten-4-ynyl)acetic acid ethyl esterYield 55.8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

3.36 g of diethylphosphonoacetic acid ethyl ester is dissolved in 40 ml of ethanol, 0.60 g of 60% oily sodium hydride is added under ice cooling and stirring, 1.09 g of (E)-6-methoxy-6-methyl-2-hepten-4-ynyl bromide is added dropwise, and the mixture is stirred under ice cooling for 1 hour and then at room temperature for 5 hours. 15 ml of acetic acid is added to the reaction solution, the solvent is distilled off under reduced pressure, and the residue is extracted with a system of water and ethyl acetate. The organic layer is post-treated in a conventional manner, and the product is purified by silica gel column chromatography [Wako gel C-200, 100 g; hexane/ethyl acetate=1/2] and medium pressure liquid chromatography [Lobar column, size B, Lichroprep Si 60F (produced by Merck Co.); hexane/ethyl acetate=1/1→1/2] to obtain 1.01 g of (E)-diethylphosphono(6-methoxy-6-methyl-2-hepten-4-ynyl)acetic acid ethyl ester as colorless oil.

Workup

  1. stirringthe mixture is stirred under ice cooling for 1 hour
  2. distillationthe solvent is distilled off under reduced pressure
  3. extractionthe residue is extracted with a system of water and ethyl acetate
  4. additionThe organic layer is post-treated in a conventional manner
  5. customthe product is purified by silica gel column chromatography [Wako gel C-200, 100 g; hexane/ethyl acetate=1/2] and medium pressure liquid chromatography [Lobar column, size B, Lichroprep Si 60F (produced by Merck Co.); hexane/ethyl acetate=1/1→1/2]

Sources & evidence

ORD record
ord-fe36d7807fd343479dc0c2a1fa416612
Source dataset
uspto-grants-1995_08
Patent number
US05444084

Reaction notes

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