Cyclohexene oxide → HCID 18653088, compound

HRID 484545Notes

Reaction equation

HRID 484545 reaction equation
[Mg].Br[C:3]([O:16][C:17](C1C=CC=CC=1)(Br)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)([C:10]1C=CC=C[CH:11]=1)[C:4]1C=CC=[CH:6][CH:5]=1.[CH:31]12[O:37][CH:32]1[CH2:33][CH2:34][CH2:35][CH2:36]2>C1COCC1.C(OCC)(=O)C.[Cu]Cl>[CH2:17]([O:16][C:3]1[CH:4]=[CH:5][CH:6]=[CH:11][C:10]=1[C@@H:31]1[CH2:36][CH2:35][CH2:34][CH2:33][C@H:32]1[OH:37])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 3

HCID 9246Cyclohexene oxideHCID 5462224MagnesiumHCID 70628552HCID 70628552, compound

Product 1

HCID 18653088HCID 18653088, compoundYield 86.9%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-30 °C

Procedure

A 1 L round bottom flask equipped with a mechanical stirrer, addition funnel, condenser, and nitrogen inlet is charged with 6.6 g (0.27 mol) of magnesium turnings and 25 ml of dry tetrahydrofuran. To this stirred mixture a solution of 50 g (0.27 mol) of bromophenyl benzylether in 50 ml of dry THF is added dropwise. The reaction needs to be heated (30°-40° C.) at first to initiate it but then the heating mantel is removed and the temperature maintained by the rate of addition. Once the addition is complete the reaction is held at 45°-50° C. for 2 hours, then 300 ml of dry THF is added. The solution is cooled to -30° C. and 1.2 g (0.012 mol) of copper (I) chloride is added. The resulting mixture is stirred for 10 minutes and then a solution of 26 g (0.265 mol) of cyclohexene oxide in 30 ml of THF is added dropwise over 1 hour. Upon completion of the addition the reaction is allowed to warm to 0° C. and stirred for 2 hours, then diluted with 300 ml of ethyl acetate and quenched by addition of 150 ml of saturated aqueous ammonium sulfate solution. The organic phase is separated and washed with another 75 ml of ammonium sulfate solution. The combined aqueous phases are extracted with 100 ml of ethyl acetate. The organic phases are combined, dried with magnesium sulfate, and evaporated under reduced pressure to yield 65 g of trans-2-(2'-benzyloxyphenyl)cyclohexanol as an amber oil, which is used directly in the next step.

Workup

  1. customA 1 L round bottom flask equipped with a mechanical stirrer, addition funnel, condenser, and nitrogen inlet
  2. temperatureto be heated (30°-40° C.) at first
  3. customthe heating mantel is removed
  4. temperaturethe temperature maintained by the rate of addition
  5. additionOnce the addition
  6. addition300 ml of dry THF is added
  7. additionUpon completion of the addition the reaction
  8. temperatureto warm to 0° C.
  9. stirringstirred for 2 hours
  10. customquenched by addition of 150 ml of saturated aqueous ammonium sulfate solution
  11. customThe organic phase is separated
  12. washwashed with another 75 ml of ammonium sulfate solution
  13. extractionThe combined aqueous phases are extracted with 100 ml of ethyl acetate
  14. dry with materialdried with magnesium sulfate
  15. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-f347e9f71f304e019b5553baefa20cfd
Source dataset
uspto-grants-1993_07
Patent number
US05231198

Reaction notes

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