1-Octyn-3-ol → HCID 22150762, compound

HRID 703637Notes

Reaction equation

HRID 703637 reaction equation
C([Li])CCC.O1CCCCC1OC1CCCCO1.[CH:19]#[C:20][CH:21]([OH:27])[CH2:22][CH2:23][CH2:24][CH2:25][CH3:26].C[Si](C)(C)[O:30][C:31]1([CH3:45])[CH2:36][CH:35]([O:37][Si](C)(C)C)[CH2:34][C:33]([CH3:43])([CH3:42])[C:32]1=[O:44].[Cl-].[NH4+]>C1COCC1.CCCCCC>[OH:44][C:32]1([C:19]#[C:20][CH:21]([OH:27])[CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[C:33]([CH3:43])([CH3:42])[CH2:34][CH:35]([OH:37])[CH2:36][C:31]1([OH:30])[CH3:45]

Participants

8

Reactant 5

HCID 131661-Octyn-3-olHCID 25517Ammonium ChlorideHCID 263182Tetrahydropyranyl etherHCID 22150761HCID 22150761, compoundHCID 178418339Butyllithium

Product 1

HCID 22150762HCID 22150762, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To 2.8 ml of a 1.6M n-hexane solution of n-butyl lithium was added 10 ml of anhydrous THF at -78° C. (bath temperature) in a nitrogen atmosphere, and 1.1 g of a tetrahydropyranyl ether of 1-octyn-3-ol was added dropwise thereto under the same conditions. After the addition, the mixture was stirred for 30 minutes. Then, 15 ml of an anhydrous THF solution containing 1.4 g of 2,4-bis(trimethylsiloxy)-2,6,6-trimethylcyclohexanone was added dropwise to the mixture under the same conditions over 20 minutes. After the dropwise addition, the mixture was stirred for 5 hours. A saturated ammonium chloride aqueous solution was added to the reaction mixture, and the mixture was extracted with diethyl ether. The diethyl ether was removed from the extract by distillation, and a 1N hydrochloric acid aqueous solution and methanol were added to the residue, followed by stirring at room temperature for 6 hours. The methanol was removed by distillation under reduced pressure, and the residue was extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, and the solvent, etc. were removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.1 g (yield: 85%) of 1-(1,2,4-trihydroxy-2,6,6-trimethylcyclohexyl)oct-1-yn-3-ol.

Workup

  1. additionwas added dropwise
  2. additionAfter the addition
  3. additionwas added dropwise to the mixture under the same conditions over 20 minutes
  4. additionAfter the dropwise addition
  5. stirringthe mixture was stirred for 5 hours
  6. extractionthe mixture was extracted with diethyl ether
  7. customThe diethyl ether was removed from the
  8. extractionextract by distillation
  9. additiona 1N hydrochloric acid aqueous solution and methanol were added to the residue
  10. stirringby stirring at room temperature for 6 hours
  11. customThe methanol was removed by distillation under reduced pressure
  12. extractionthe residue was extracted with diethyl ether
  13. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  14. customthe solvent, etc. were removed by distillation under reduced pressure
  15. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-0ac385af4fa345b991a645b01d2704ce
Source dataset
uspto-grants-1991_01
Patent number
US04983723

Reaction notes

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