Isobutyric Acid → Ethyl 6,6-dichloro-3,3-dimethyl-7,7,7-trifluorohept-4-enoate

HRID 1247

Reaktionsgleichung

Reaktionsgleichung von HRID 1247
[C:1]([O:9]CC)([O:6][CH2:7][CH3:8])(OCC)[CH3:2].[Cl:12][C:13]([Cl:24])([C:20]([F:23])([F:22])[F:21])[CH:14](O)[CH:15]=[C:16]([CH3:18])[CH3:17].C(O)(=O)C(C)C>>[Cl:12][C:13]([Cl:24])([C:20]([F:21])([F:22])[F:23])[CH:14]=[CH:15][C:16]([CH3:18])([CH3:17])[CH2:2][C:1]([O:6][CH2:7][CH3:8])=[O:9]

Komponenten

4

Edukt 3

HCID 6590Isobutyric AcidHCID 66221Triethyl orthoacetateHCID 136022405,5-Dichloro-4-hydroxy-2-methyl-6,6,6-trifluorohex-2-ene

Produkt 1

HCID 53946683Ethyl 6,6-dichloro-3,3-dimethyl-7,7,7-trifluorohept-4-enoate

Versuchsvorschrift

A mixture of triethyl orthoacetate (25 ml), 5,5-dichloro-4-hydroxy-2-methyl-6,6,6-trifluorohex-2-ene (3.5 g), and isobutyric acid (0.11 g) was heated at the reflux temperature. The refluxing volatiles were condensed and collected in a Dean & Stark apparatus containing molecular sieves (4A) to collect the by-product ethanol and separate it from the orthoacetate which was returned to the mixture. After 30 minutes the more volatile components were removed by evaporation under reduced pressure and the residual oil (consisting principally of 5,5-dichloro-4-(1,1-diethoxyethoxy)-2-methyl-6,6,6-trifluorohex-2-ene, 3.8 g) collected. This was then heated with isobutyric acid (10 μl) at the reflux temperature for 16 hours under a condenser containing molecular sieves (4A) to remove ethanol from the condensate. The residual oil was subjected to purification by column chromatography using a 15:1 (by volume) mixture of hexane:ethyl acetate as eluant and a silica gel column (230-400 mesh, 60 Å) to obtain ethyl 6,6-dichloro-3,3-dimethyl-7,7,7-trifluorohept-4-enoate, identified by nuclear magnetic resonance, and gas chromatographic mass-spectroscopy.

Aufarbeitung

  1. temperaturewas heated at the reflux temperature
  2. customcondensed
  3. customcollected in a Dean & Stark apparatus
  4. additioncontaining molecular sieves (4A)
  5. customto collect the by-product ethanol
  6. customseparate it from the orthoacetate which
  7. customAfter 30 minutes the more volatile components were removed by evaporation under reduced pressure
  8. customcollected
  9. temperatureThis was then heated with isobutyric acid (10 μl) at the reflux temperature for 16 hours under a condenser
  10. additioncontaining molecular sieves (4A)
  11. customto remove ethanol from the condensate
  12. customThe residual oil was subjected to purification by column chromatography
  13. additiona 15:1 (by volume) mixture of hexane

Quellen und Nachweise

ORD-Eintrag
ord-d42202fb4a7943b3bbc1a6d0fce478fe
Quelldatensatz
uspto-grants-1998_03
Patentnummer
US05723649

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