Acetaldehyde → HCID 23443043, compound

HRID 842252Notes

Reaction equation

HRID 842252 reaction equation
C(NC(C)C)(C)C.[C:8]12([CH3:18])[C:15]([CH3:17])([CH3:16])[CH:12]([CH2:13][CH2:14]1)[CH2:11][C:9]2=[O:10].[CH:19](=[O:21])[CH3:20].C(=O)([O-])O.[Na+]>C1COCC1.CCCCCC>[OH:21][CH:19]([CH:11]1[CH:12]2[C:15]([CH3:17])([CH3:16])[C:8]([CH3:18])([CH2:14][CH2:13]2)[C:9]1=[O:10])[CH3:20].[OH:21][CH:19]([CH:11]1[CH:12]2[C:15]([CH3:17])([CH3:16])[C:8]([CH3:18])([CH2:14][CH2:13]2)[CH:9]1[OH:10])[CH3:20]

Participants

8

Reactant 4

HCID 177AcetaldehydeHCID 2537CamphorHCID 7912DiisopropylamineHCID 516892Sodium Bicarbonate

Product 2

HCID 147599003-(1-Hydroxyethyl)-camphorHCID 23443043HCID 23443043, compoundYield 126.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

2.50 ml of 2.5M n-butylithium hexane solution was added dropwise to a tetrahydrofuran solution comprising 4 ml THF and 1.00 ml diisopropylamine at −78° C. and the mixture was stirred for 15 minutes. Then, a solution comprising 4 ml THF with 0.91 g camphor dissolved therein was added dropwise to the above solution at −78° C., then, 0.27 g of acetaldehyde was further added and the mixture was stirred for 15 minutes. Thus, 3-(1-hydroxyethyl)-camphor was synthesized. This reaction solution was admixed with 50 ml of saturated sodium hydrogen carbonate aqueous solution and restored to room temperature. The reaction product was extracted with diethylether. 5 ml of the above 3-(1-hydroxyethyl)-camphor diethylether solution was gradually added dropwise to 10 ml of a diethylether solution comprising 10 ml diethylether and 0.11 g lithium aluminum hydride and the mixture was stirred at room temperature for 30 minutes. 0.5 ml of water and 0.5 ml of 2N-NaOH were added to the reaction solution to separate the solids out. The separated-out solids were filtered off and the solvent was removed under vacuum. The residue was purified by means of silica gel column chromatography (eluent: hexane/ethylacetate=7/3) and 0.75 g of 3-(1-hydroxyethyl)-borneol was obtained (yield: 95%).

Workup

  1. customat −78° C.
  2. dissolutiondissolved
  3. additiontherein was added dropwise to the above solution at −78° C.
  4. stirringthe mixture was stirred for 15 minutes
  5. customrestored to room temperature
  6. extractionThe reaction product was extracted with diethylether
  7. addition5 ml of the above 3-(1-hydroxyethyl)-camphor diethylether solution was gradually added dropwise to 10 ml of a diethylether solution
  8. stirringthe mixture was stirred at room temperature for 30 minutes
  9. addition0.5 ml of water and 0.5 ml of 2N-NaOH were added to the reaction solution
  10. customto separate the solids out
  11. filtrationThe separated-out solids were filtered off
  12. customthe solvent was removed under vacuum
  13. customThe residue was purified by means of silica gel column chromatography (eluent: hexane/ethylacetate=7/3)

Sources & evidence

ORD record
ord-691aa418c359422ba2b567727f23bbd4
Source dataset
uspto-grants-2002_04
Patent number
US06372804B1

Reaction notes

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