Allyl phenyl ether → 1-(2-Ethyl-3,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-1-one

HRID 328664

Reaktionsgleichung

Reaktionsgleichung von HRID 328664
[Li].[C:2]1(OCC=C)[CH:7]=CC=C[CH:3]=1.C(O[C:15]([CH:17]1[C:22]([CH3:24])([CH3:23])[CH2:21][CH2:20][C:19]([CH3:25])=[C:18]1[CH2:26][CH3:27])=[O:16])C>O1CCCC1.CCOCC>[CH2:26]([C:18]1[CH:17]([C:15](=[O:16])[CH2:7][CH:2]=[CH2:3])[C:22]([CH3:23])([CH3:24])[CH2:21][CH2:20][C:19]=1[CH3:25])[CH3:27]

Komponenten

6

Edukt 3

HCID 74458Allyl phenyl etherHCID 3028194LithiumHCID 202363782-Cyclohexene-1-carboxylic acid, 2-ethyl-3,6,6-trimethyl-, ethyl ester

Produkt 1

HCID 214396681-(2-Ethyl-3,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-1-oneAusbeute 85,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A few crystals of diphenyl are added to a suspension, cooled to 5°-10° C and held under a nitrogen atmosphere, of 2.4 g (0.35 g-atoms) of finely cut lithium wire in 40 ml of absolute tetrahydrofuran. 2 ml of a solution of 9.4 g (70 mmol) of allyl phenyl ether in 10 ml of absolute ether are then added. After a greenish coloration sets in, the rest of the solution is added dropwise at -15° C. After completion of the addition, the mixture is stirred for 30 minutes at 0° C. The resulting allyl lithium solution is decanted off from excess lithium and transferred to a dropping funnel. This solution is added dropwise to a solution, cooled to -60° C and maintained under nitrogen, of 4.48 g (20 mmol) of 2-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid ethyl ester in 40 ml of absolute ether. After completion of the addition, the mixture is left to warm to room temperature, poured on to ice-water and extracted with three portions of hexane. The combined hexane extracts are washed neutral with three portions of water, dried over sodium sulphate and evaporated. By fractional distillation of the residue there are obtained 3.75 g (85%) of 2-ethyl-3,6,6-trimethyl-1-[but-3-enoyl]-2-cyclohexene; boiling point 57°-58° C/0.04 mm Hg; nD 20 = 1.4865.

Aufarbeitung

  1. additionA few crystals of diphenyl are added to a suspension
  2. temperaturecooled to 5°-10° C
  3. additionAfter a greenish coloration sets in, the rest of the solution is added dropwise at -15° C
  4. additionAfter completion of the addition
  5. customThe resulting allyl lithium solution is decanted off from excess lithium
  6. customtransferred to a dropping funnel
  7. additionThis solution is added dropwise to a solution
  8. temperaturecooled to -60° C
  9. additionAfter completion of the addition
  10. waitthe mixture is left
  11. temperatureto warm to room temperature
  12. extractionextracted with three portions of hexane
  13. washThe combined hexane extracts are washed neutral with three portions of water
  14. dry with materialdried over sodium sulphate
  15. customevaporated
  16. distillationBy fractional distillation of the residue there

Quellen und Nachweise

ORD-Eintrag
ord-e5ed5ceefbb5493c99b2369ee12c5c0e
Quelldatensatz
uspto-grants-1977_04
Patentnummer
US04018718

Verknüpfte Notizen

Wird geladen…