Ethanol → Ethyl 4-trichloroacetamido-5-hexenoate

HRID 2259457Notes

Reaction equation

HRID 2259457 reaction equation
[H-].[Na+].O[CH2:4][CH:5]=[CH:6][CH2:7][CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[Cl:14][C:15]([Cl:19])([Cl:18])[C:16]#[N:17].C([OH:22])C>CCOCC>[Cl:14][C:15]([Cl:19])([Cl:18])[C:16]([NH:17][CH:6]([CH:5]=[CH2:4])[CH2:7][CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[O:22]

Participants

6

Reactant 4

HCID 702EthanolHCID 11011TrichloroacetonitrileHCID 24758Sodium hydrideHCID 53641333Ethyl 6-hydroxy-4-hexenoate

Product 1

HCID 11055787Ethyl 4-trichloroacetamido-5-hexenoateYield 727.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Sodium hydride (0.03 g of a 50% dispersion in oil, 0.5 mmol, was added to a solution of ethyl 6-hydroxy-4-hexenoate (0.7 g, 5 mmol) and trichloroacetonitrile (0.6 g, 5 mmol) in anhydrous ether (50 mL) under N2 at 0° C. After 1H, ethanol (0.5 mmol) was added and the solvent was removed in vacuo. The formation of the imidate was controled by NMR (NH, ~8.5 ppm). A solution of the crude imidate in xylene (30 mL) was heated at reflux 48H. Then the solvent was removed in vacuo and the residue was purified by flash chromatography on SiO2. (eluant AcOEt: hexane, 2:8) to give the title product (1.1 g, ~70%). 1H NMR (90 MHz) (CDCl3, TMS)δ ppm. 1.23 (t, 3H, CH3, J=6 Hz), 2.0 (t, 2H, CH2 --CH2 --CO2 , J=5 Hz), 2.36 (s, 2H, CH2CO2), 4.1 (q, 2H, CH3CH2, J=6 Hz), 4.4 (t, 1H, C---CH2, J=5 Hz), 5.1 (m, 2H, CH2), 5.76 (m, 1H, CH=CH2), 7.2 (s, 1H, NH).

Workup

  1. customthe solvent was removed in vacuo
  2. temperatureA solution of the crude imidate in xylene (30 mL) was heated
  3. temperatureat reflux 48H
  4. customThen the solvent was removed in vacuo
  5. customthe residue was purified by flash chromatography on SiO2

Sources & evidence

ORD record
ord-12a340738ed74545a3336952738deff3
Source dataset
uspto-grants-1995_12
Patent number
US05473099

Reaction notes

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