Hydrochloric Acid → 2,4,4-Trimethyl-3-(15-hydroxypentadecyl)-2-cyclohexen-1-one

HRID 1768450Notes

Reaction equation

HRID 1768450 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][O:17][Si](C(C)(C)C)(C)C.[Mg].C([O:28][C:29]1[CH2:34][CH2:33][C:32]([CH3:36])([CH3:35])[C:31](=O)[C:30]=1[CH3:38])C.Cl.C(=O)([O-])O.[Na+]>C(OCC)C.O1CCCC1>[OH:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:31]1[C:32]([CH3:36])([CH3:35])[CH2:33][CH2:34][C:29](=[O:28])[C:30]=1[CH3:38]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 516892Sodium BicarbonateHCID 5462224MagnesiumHCID 205455943-Ethoxy-2,6,6-trimethyl-2-cyclohexen-1-oneHCID 23615174[(15-Bromopentadecyl)oxy](tert-butyl)dimethylsilane

Product 1

HCID 97991882,4,4-Trimethyl-3-(15-hydroxypentadecyl)-2-cyclohexen-1-oneYield 39%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

15-Bromo-1-(t-butyldimethylsiloxy)pentadecane (1 g, 2.36 mmol) dissolved in absolute ethyl ether (3 mL) and magnesium (0.115 g) were mixed, and the mixture was refluxed for 40 minutes. Subsequently, 3-ethoxy-2,6,6-trimethyl-2-cyclohexen-1-one (287.5 mg, 1.57 mmol) dissolved in tetrahydrofuran (2 mL) was added thereto. After stirring the mixture for four hours, 10% hydrochloric acid (3 mL) was added, and the reaction was allowed to continue for a further 17 hours under stirring. The reaction mixture was neutralized with sodium hydrogencarbonate, followed by extraction with ethyl ether three times. The organic layers were combined, washed with aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by means of silica gel column chromatography (hexane/ethyl acetate=9/1-6/4; concentration gradient=5%), to thereby afford 222.7 mg (0.61 mmol) of 3-(15-hydroxypentadecyl)-2,4,4-trimethyl-2-cyclohexen-1-one.

Workup

  1. temperaturethe mixture was refluxed for 40 minutes
  2. additionwas added
  3. waitto continue for a further 17 hours
  4. stirringunder stirring
  5. extractionfollowed by extraction with ethyl ether three times
  6. washwashed with aqueous sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe crude product was purified by means of silica gel column chromatography (hexane/ethyl acetate=9/1-6/4; concentration gradient=5%)

Sources & evidence

ORD record
ord-8bbd00907f1c45f0877f2cd092d91d2d
Source dataset
uspto-grants-2007_06
Patent number
US07235700B2

Reaction notes

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