Hydrochloric Acid → HCID 15049560, compound

HRID 484549Notes

Reaction equation

HRID 484549 reaction equation
[CH2:1]=[CH:2][C:3](=[CH2:5])[CH3:4].[Mg].[Si:7](Cl)([CH3:10])([CH3:9])[CH3:8].[C:12]1(=[O:18])[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1.Cl>C1COCC1>[CH3:5][C:3](=[CH2:4])[CH:2]([C:12]1([OH:18])[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1)[CH2:1][Si:7]([CH3:10])([CH3:9])[CH3:8].[CH3:5][C:3]([C:12]1([OH:18])[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1)([CH2:4][Si:7]([CH3:10])([CH3:9])[CH3:8])[CH:2]=[CH2:1]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 6557IsopreneHCID 7967CyclohexanoneHCID 5462224Magnesium

Product 2

HCID 15049560HCID 15049560, compoundHCID 15049561HCID 15049561, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

In a typical regioselective reaction of an unsymmetrical (2-butene-1,4-diyl)magnesium complex, a THF solution of the complex (20 mL) prepared from isoprene (0.281 g, 2.06 mmol, technical grade) and activated magnesium (3.44 mmol) was cooled to -78° C. Me3SiCl (0.171 g, 1.57 mmol) was added via a disposable syringe. The reaction mixture was stirred at -78° C. for 1 hour, and then it was gradually warmed to 0° C. Excess cyclohexanone (0.278 g, 2.83 mmol) was added at 0° C. The reaction mixture was warmed to room temperature and stirred for 1 hour. An aqueous solution of HCl (1.5N, 10 mL) was added at 0° C. The mixture was washed with diethyl ether (20 mL), and the aqueous layer was extracted with diethyl ether (2×20 mL). The combined organic phases were washed with a saturated aqueous solution of NaHCO3 (2×15 mL) and brine (20 mL) and dried over MgSO4. Removal of solvents and flash column chromatography (eluted by hexanes/Et2O, 98:2) gave 1-(2-methyl-1-trimethylsilylmethyl-2-propenyl)cyclohexanol as the major isomer (0.372 g, 77%) and 1-( 1-methyl-1-trimethylsilylmethyl-2-propenyl)cyclohexanol as the minor isomer (0.025 g, 5%) the major isomer was eluted out before the minor isomer in 82% total yield.

Workup

  1. customIn a typical regioselective reaction of an unsymmetrical (2-butene-1,4-diyl)magnesium complex
  2. temperatureit was gradually warmed to 0° C
  3. temperatureThe reaction mixture was warmed to room temperature
  4. stirringstirred for 1 hour
  5. washThe mixture was washed with diethyl ether (20 mL)
  6. extractionthe aqueous layer was extracted with diethyl ether (2×20 mL)
  7. washThe combined organic phases were washed with a saturated aqueous solution of NaHCO3 (2×15 mL) and brine (20 mL)
  8. dry with materialdried over MgSO4
  9. customRemoval of solvents and flash column chromatography (eluted by hexanes/Et2O, 98:2)

Sources & evidence

ORD record
ord-5958c7565d0c4ed1a510b2858f3e8d70
Source dataset
uspto-grants-1993_07
Patent number
US05231205

Reaction notes

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