Iodine → 1-Iodo-trans-1-octene-3-ol

Temperature

55 °C

To 1.26 g. (0.01 moles) of 1-octyn-3-ol in 8 ml. in dry heptane was added dropwise 6.18 ml. (0.03 moles) of triisobutylaluminum at 10°-15°C.; 1.82 ml. (0.01 moles) of diisobutylaluminum hydride was then added and the reaction mixture was heated at 50°14 55° C. for 2 hours. The solution was then cooled and the heptane removed under reduced pressure. The residue obtained was diluted with 12 ml. of dry tetrahydrofuran. After cooling the solution to -50° C., 10.26 g. (0.04 moles) of iodine in 16 ml. of dry tetrahydrofuran was added dropwise. The dark solution was warmed to room temperature and the alane was decomposed at 20°-30° C. with 20% H2SO4. After the isobutane evolution had diminished, the reaction mixture was poured into ice and extracted four times with pentane. The pentane extract was washed successively with saturated NaHCO3, sodium thiosulfate, saturated NaHCO3 and saturated NaCl solutions. After drying the pentane over MgSO4, it was evaporated to given a dark oil. To remove the iodo-3-hydroxyoctane, the mixture was heated for 16 hours at 90° C. with 0.005 moles of triethylamine. The excess triethylamine was evaporated off and water was added to the residue. Most of the dark oily residue dissolved in the aqueous layer and the total mixture was extracted with pentane. The pentane extract was washed with dilute hydrochloric acid, saturated sodium bicarbonate and saturated sodium chloride solutions and dried over magnesium sulfate. After evaporation of the pentane, the residue was distilled in vacuo to yield pure 3-hydroxy-1-iodo-1-trans-octene (40-50% molar basis). Some 1-octyn-3-ol was recovered.

1. customat 10°-15°C.
2. temperatureThe solution was then cooled
3. customthe heptane removed under reduced pressure
4. customThe residue obtained
5. additionwas diluted with 12 ml
6. temperatureAfter cooling the solution to -50° C.
7. temperatureThe dark solution was warmed to room temperature
8. additionthe reaction mixture was poured into ice
9. extractionextracted four times with pentane
10. extractionThe pentane extract
11. washwas washed successively with saturated NaHCO3, sodium thiosulfate, saturated NaHCO3 and saturated NaCl solutions
12. dry with materialAfter drying the pentane over MgSO4, it
13. customwas evaporated
14. customTo remove the iodo-3-hydroxyoctane
15. customThe excess triethylamine was evaporated off
16. additionwater was added to the residue
17. dissolutionMost of the dark oily residue dissolved in the aqueous layer
18. extractionthe total mixture was extracted with pentane
19. extractionThe pentane extract
20. washwas washed with dilute hydrochloric acid, saturated sodium bicarbonate and saturated sodium chloride solutions
21. dry with materialdried over magnesium sulfate
22. customAfter evaporation of the pentane
23. distillationthe residue was distilled in vacuo

ORD record

ord-4d7b93eae86c42eea09edf810d683058

Source dataset

uspto-grants-1976_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US03962352