Magnesium → Trans-3-[2-Benzyloxy-4-(1,1-dimethylheptyl)phenyl]-4-(2-propenyl)cyclohexanone

HRID 1762227

Reaktionsgleichung

Reaktionsgleichung von HRID 1762227
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([CH3:16])([CH3:15])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])=[CH:4][C:3]=1[O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[Mg].[CH2:26]([CH:29]1[CH2:34][CH2:33][C:32](=[O:35])[CH:31]=[CH:30]1)[CH:27]=[CH2:28]>O1CCCC1>[CH2:18]([O:17][C:3]1[CH:4]=[C:5]([C:8]([CH3:16])([CH3:15])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])[CH:6]=[CH:7][C:2]=1[C@H:30]1[C@H:29]([CH2:26][CH:27]=[CH2:28])[CH2:34][CH2:33][C:32](=[O:35])[CH2:31]1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Komponenten

5

Edukt 3

HCID 5462224MagnesiumHCID 109535714-(2-Propenyl)-2-cyclohexen-1-one2×HCID 128821642-(Benzyloxy)-1-bromo-4-(2-methyloctan-2-YL)benzene

Produkt 1

HCID 13105165Trans-3-[2-Benzyloxy-4-(1,1-dimethylheptyl)phenyl]-4-(2-propenyl)cyclohexanoneAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

A solution of 73.0 g. (0.188 mole) of 1-bromo-2-benzyloxy-4-(1,1-dimethylheptyl)benzene (BrZ') in 350 ml. of tetrahydrofuran was slowly added to 9.0 g. (0.375 mole) of 70-80 mesh magnesium metal. After a 5 minute initiation period the rate of addition was adjusted so as to just maintain reflux. The reaction was stirred 1.5 hours longer following completion of addition while cooling to 25° C. The reaction was cooled to -20° C. and 1.78 g. (9.38 mmoles) of cuprous iodide added. The resultant mixture was stirred 5 minutes and then a solution of 25.5 g. (0.188 mole) of 4-(2-propenyl)-2-cyclohexen-1-one (enone) in 30 ml. of tetrahydrofuran added dropwise while the reaction temperature was maintained at about -18° C. Additional 1.78 g. (9.38 mmoles) portions of cuprous iodide were added following addition of 1/3 and 2/3 of the enone reactant. The reaction was stirred 5 minutes longer at -20° C. and then added to 1000 ml. of ice cold saturated ammonium chloride. The quenched mixture was extracted with 1000 ml. of ether and the organic extract washed twice with 500 ml. of saturated ammonium chloride, once with 500 ml. of saturated sodium chloride, dried over magnesium sulfate and evaporated (aspirator) to an oil. The crude oil was purified via column chromatography on 1 kg. of silica gel eluted with 20% etherhexane to yield 58.3 g. (70%) of the title compound as an oil.

Aufarbeitung

  1. additionAfter a 5 minute initiation period the rate of addition
  2. temperatureto just maintain
  3. temperaturereflux
  4. additioncompletion of addition
  5. temperatureThe reaction was cooled to -20° C.
  6. temperaturewas maintained at about -18° C
  7. stirringThe reaction was stirred 5 minutes longer at -20° C.
  8. additionadded to 1000 ml
  9. extractionThe quenched mixture was extracted with 1000 ml
  10. extractionof ether and the organic extract
  11. washwashed twice with 500 ml
  12. dry with materialof saturated sodium chloride, dried over magnesium sulfate
  13. customevaporated (aspirator) to an oil
  14. customThe crude oil was purified via column chromatography on 1 kg
  15. washof silica gel eluted with 20% etherhexane
  16. customto yield 58.3 g

Quellen und Nachweise

ORD-Eintrag
ord-a1bc342440ca461394ac558ae1e08e18
Quelldatensatz
uspto-grants-1989_05
Patentnummer
US04831059

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