Hydrochloric Acid → Triapenthenol

HRID 1165376

Reaction equation

HRID 1165376 reaction equation
Cl.N[C@@H](CC(C)C)C(C1C=CC=CC=1)(C1C=CC=CC=1)O.[BH4-].[Na+].[CH:24]1(/[CH:30]=[C:31](/[N:38]2[CH:42]=[N:41][CH:40]=[N:39]2)\[C:32](=[O:37])[C:33]([CH3:36])([CH3:35])[CH3:34])[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]1.Cl>ClCCCl.CN(C)C=O>[CH:24]1(/[CH:30]=[C:31](/[N:38]2[CH:42]=[N:41][CH:40]=[N:39]2)\[CH:32]([OH:37])[C:33]([CH3:36])([CH3:35])[CH3:34])[CH2:25][CH2:26][CH2:27][CH2:28][CH2:29]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 12763477(E)-1-cyclohexyl-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-oneHCID 13036360(S)-2-amino-1,1-diphenyl4-methylpentan-1-ol hydrochloride

Product 1

HCID 6437842TriapenthenolYield 100%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolvent2×HCID 6228DimethylformamideSolvent

Conditions

Temperature
-20 °C

Procedure

In a nitrogen atmosphere, 0.275 g (0.90 mmole) of (S)-2-amino-1,1-diphenyl-4-methylpentan-1-ol hydrochloride was suspended in 5 ml of 1,2-dichloroethane, and after cooling to -20° C., a solution of 0.034 g (0.90 mmole) of sodium borohydride in 0.5 ml of dimethylformamide was added. The temperature of the suspension was then raised from -20° C. to room temperature over 2 hours. Thereafter, a solution of 157 mg (0.60 mmole) of (E)-1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one in 2 ml of 1,2-dichloroethane was added dropwise to this suspension at room temperature, and stirring was carried out for 24 hours. To this reaction solution was added 6 ml of 2N hydrochloric acid, and after removing liberated (S)-2-amino-1,1-diphenyl-4-methylpentan-1-ol hydrochloride by filtration, the organic layer was washed with water and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to obtain 0.158 g of (-)-(E)-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-ol. The conversion was 93.7%, and the composition of the product was: E-form alcohol, 95.7% and Z-form alcohol, 4.3%. The enantiomer ratio of the E-form alcohol was: (+)-isomer, 18.8% and (-)-isomer, 81.2%.

Workup

  1. temperatureThe temperature of the suspension was then raised from -20° C. to room temperature over 2 hours
  2. customafter removing liberated (S)-2-amino-1,1-diphenyl-4-methylpentan-1-ol hydrochloride
  3. filtrationby filtration
  4. washthe organic layer was washed with water
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-d5ad35a7830d4cbdb1a3b32a30730a5b
Source dataset
uspto-grants-1990_03
Patent number
US04908455

Linked notes

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