1-Octyn-3-ol → HCID 14229047, compound

HRID 703635Notes

Reaction equation

HRID 703635 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([CH3:40])[CH2:36][CH2:35][CH2:34][C:33]([CH3:38])([CH3:37])[C:32]1=[O:39].[Cl-].[NH4+]>C1COCC1.CCCCCC>[OH:39][C:32]1([C:19]#[C:20][CH:21]([OH:27])[CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[C:33]([CH3:38])([CH3:37])[CH2:34][CH2:35][CH2:36][C:31]1([OH:30])[CH3:40]

Participants

8

Reactant 5

HCID 131661-Octyn-3-olHCID 25517Ammonium ChlorideHCID 263182Tetrahydropyranyl etherHCID 14229046HCID 14229046, compoundHCID 178418339Butyllithium

Product 1

HCID 14229047HCID 14229047, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To 6.5 ml of a 1.6M n-hexane solution of n-butyl lithium was added 20 ml of anhydrous THF at -78° C. (bath temperature) in a nitrogen atmosphere, and 2.2 g of a tetrahydropyranyl ether of 1-octyn-3-ol was added dropwise thereto under the same conditions over 10 minutes. After the addition, the mixture was stirred for 30 minutes. Then, 30 ml of an anhydrous THF solution containing 2.0 g of 2-trimethylsiloxy-2,6,6-trimethylcyclohexanone was added dropwise to the mixture under the same conditions over 35 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, a 1N hydrochloric acid aqueous solution and methanol were added to the residue, followed by stirring at room temperature for 5 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 1.8 g (yield: 70%) of 1-(1,2-dihydroxy-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 35 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 5 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-b0f89d7beeef4a59bcfb036a70724669
Source dataset
uspto-grants-1991_01
Patent number
US04983723

Reaction notes

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