Iodine → 4,4-Dimethyl-1-iodo-trans-1-octen-3-ol

HRID 1448248Notes

Reaction equation

HRID 1448248 reaction equation
C(BC(C(C)C)C)(C(C)C)C.[CH3:12][C:13]([CH3:28])([CH2:24][CH2:25][CH2:26][CH3:27])[CH:14]([O:17]C1CCCCO1)[C:15]#[CH:16].C([N+]([O-])(CC)CC)C.[OH-].[Na+].[I:39]I.S([O-])([O-])(=O)=S.[Na+].[Na+]>O.O1CCCC1>[CH3:12][C:13]([CH3:28])([CH2:24][CH2:25][CH2:26][CH3:27])[CH:14]([OH:17])/[CH:15]=[CH:16]/[I:39]

Participants

9

Reactant 6

HCID 807IodineHCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 123168Ethanamine, N,N-diethyl-, N-oxideHCID 192733Bis(1,2-dimethylpropyl)boraneHCID 145163702-[(4,4-Dimethyloct-1-YN-3-YL)oxy]oxane

Product 1

HCID 204657234,4-Dimethyl-1-iodo-trans-1-octen-3-ol

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To 233 ml. of a 0.43% solution of disiamylborane in diglyne cooled to 0° C. under an inert atmosphere is added 23.8 g. (0.100 mole) 4,4-dimethyl-3-tetrahydropyramyloxy-1-octyne (Example 995). The mixture is allowed to come to room temperature and is stirred at ambient temperature for 3 hours. The solution is cooled to 0° C. and 22.5 g. (0.30 mole) of triethylamine oxide is added portionwise such that the temperature is maintained at 0°-5° C. The mixture is stirred at 0° C. for 1 hour and is then poured into 150 ml. of 1 N sodium hydroxide followed immediately by a solution of 25.4 g. (0.100 mole) of iodine in 60 ml. of tetrahydrofuran. The mixture is stirred at ambient temperatures for 0.5 hour and poured into 500 ml. of water. The mixture is decolorized by addition of sodium thiosulfate solution and is extracted into ether. The organic phase is washed with water and the solvent is removed in vacuo. The residue is stirred at room temperature for 20 hours with 900 ml. 3:1:1 tetrahydrofuran-acetate acid-water. The solution is evaporated in vacuo and the residue is chromatographed on silica gel in benzene using 10-20% ethylacetate in benzene.

Workup

  1. additionis added 23.8 g
  2. customto come to room temperature
  3. temperatureThe solution is cooled to 0° C.
  4. temperatureis maintained at 0°-5° C
  5. stirringThe mixture is stirred at 0° C. for 1 hour
  6. additionis then poured into 150 ml
  7. stirringThe mixture is stirred at ambient temperatures for 0.5 hour
  8. additionpoured into 500 ml
  9. extractionis extracted into ether
  10. washThe organic phase is washed with water
  11. customthe solvent is removed in vacuo
  12. stirringThe residue is stirred at room temperature for 20 hours with 900 ml
  13. customThe solution is evaporated in vacuo
  14. customthe residue is chromatographed on silica gel in benzene using 10-20% ethylacetate in benzene

Sources & evidence

ORD record
ord-45d400dd8a42431da292cf7ade2d90f8
Source dataset
uspto-grants-1979_12
Patent number
US04179574

Reaction notes

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