2-Methyl-2-butene → 1-Bromo-4,4-dimethyl-3-tetrahydropyranyloxy-trans-1-octene

HRID 67018Notes

Reaction equation

HRID 67018 reaction equation
CC(=CC)C.B#B.[CH3:8][C:9]([CH3:24])([CH2:20][CH2:21][CH2:22][CH3:23])[CH:10]([O:13][CH:14]1[CH2:19][CH2:18][CH2:17][CH2:16][O:15]1)[C:11]#[CH:12].[Br:25]Br>O1CCCC1.C(Cl)(Cl)(Cl)Cl>[Br:25]/[CH:12]=[CH:11]/[CH:10]([O:13][CH:14]1[CH2:19][CH2:18][CH2:17][CH2:16][O:15]1)[C:9]([CH3:24])([CH3:8])[CH2:20][CH2:21][CH2:22][CH3:23]

Participants

7

Reactant 4

HCID 105532-Methyl-2-buteneHCID 24408BromineHCID 6328200DiboronHCID 145163702-[(4,4-Dimethyloct-1-YN-3-YL)oxy]oxane

Product 1

HCID 867329711-Bromo-4,4-dimethyl-3-tetrahydropyranyloxy-trans-1-octene

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To an ice cooled solution of 3.5 g. (50 moles) of 2-methyl-2-butene in 25 ml. of tetrahydrofuran under an inert atmosphere is added 25 ml. of 1 M diborane in tetrahydrofuran dropwise over 10 minutes. The mixture is stirred at 0°-5° C. for 2 hours and then the solvent is removed under vacuum. The residue is dissolved in 20 ml. of carbon tetrachloride and to the resulting solution cooled to 0° C. is added a solution of 5.25 g. (22 mole) of 4,4-dimethyl-3-tetrahydropyranyloxy-1-octyne (Example 995) in 10 ml. of carbon tetrachloride over 10 minutes. The cooling bath is removed and the mixture is allowed to stir at ambient temperature for 1.5 hours. The mixture is cooled to 0° C. and a solution of 3.52 g. (22 moles) of bromine in 15 ml. of carbon tetrachloride is added over 10 minutes. The cooling bath is removed and the mixture is refluxed for 6 hours under an inert atmosphere. The mixture is cooled and poured into dilute sodium hydroxide solution. The organic phase is washed with water and saturated brine, dried (Na2SO4), and evaporated. The residue is chromatographed upon silica gel and the title compound is isolated with 5% ethyl acetate in benzene.

Workup

  1. customthe solvent is removed under vacuum
  2. dissolutionThe residue is dissolved in 20 ml
  3. additionis added a solution of 5.25 g
  4. customThe cooling bath is removed
  5. stirringto stir at ambient temperature for 1.5 hours
  6. temperatureThe mixture is cooled to 0° C.
  7. customThe cooling bath is removed
  8. temperaturethe mixture is refluxed for 6 hours under an inert atmosphere
  9. temperatureThe mixture is cooled
  10. additionpoured into dilute sodium hydroxide solution
  11. washThe organic phase is washed with water and saturated brine
  12. dry with materialdried (Na2SO4)
  13. customevaporated
  14. customThe residue is chromatographed upon silica gel

Sources & evidence

ORD record
ord-55bc0c317f18466394a28c44f3fe2b9e
Source dataset
uspto-grants-1982_08
Patent number
US04343949

Reaction notes

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