Hydrochloric Acid → (E)-diethylphosphono-(6,6-dimethyl-2-hepten-4-ynyl)acetic acid ethyl ester

HRID 1757267Notes

Reaction equation

HRID 1757267 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][C:18]([CH3:26])([CH3:25])[C:19]#[C:20]/[CH:21]=[CH:22]/[CH2:23]Br.Cl>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])[CH2:23]/[CH:22]=[CH:21]/[C:20]#[C:19][C:18]([CH3:26])([CH3:25])[CH3:17])[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 110744282-Hepten-4-yne, 1-bromo-6,6-dimethyl-

Product 1

HCID 86748934(E)-diethylphosphono-(6,6-dimethyl-2-hepten-4-ynyl)acetic acid ethyl esterYield 66.8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

3.34 g of diethylphosphonoacetic acid ethyl ester is dissolved in 40 ml of ethanol, 594 mg of 60% oily sodium hydride is added under ice cooling and stirring, and ethanol solution (10 ml) of 600 mg of (E)-6,6-dimethyl-2-hepten-4-ynyl bromide is added dropwise, and the mixture is stirred for 5 hours. The reaction solution is neutralized with 1N hydrochloric acid and then concentrated under reduced pressure, the residue is dissolved in a mixture of water with ethyl acetate, the organic layer is taken and post-treated in a conventional manner, and the product is purified by silica gel column chromatography [Wako gel C-200, 140 g; hexane/ethyl acetate=3/1→1/1] to obtain 686 mg of (E)-diethylphosphono-(6,6-dimethyl-2-hepten-4-ynyl)acetic acid ethyl ester as colorless oil.

Workup

  1. stirringthe mixture is stirred for 5 hours
  2. concentrationconcentrated under reduced pressure
  3. dissolutionthe residue is dissolved in a mixture of water with ethyl acetate
  4. additionpost-treated in a conventional manner
  5. customthe product is purified by silica gel column chromatography [Wako gel C-200, 140 g; hexane/ethyl acetate=3/1→1/1]

Sources & evidence

ORD record
ord-eadec35c878543cebd2d8a64493f2f8e
Source dataset
uspto-grants-1995_08
Patent number
US05444084

Reaction notes

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