Hydrochloric Acid → Triapenthenol

HRID 1165376

反応式

HRID 1165376 の反応式
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

参加物

7

反応物 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

生成物 1

HCID 6437842Triapenthenol収率 100%

試薬・触媒・溶媒 2

HCID 111,2-Dichloroethane溶媒2 回HCID 6228Dimethylformamide溶媒

反応条件

温度
-20 °C

実験手順

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%.

後処理

  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

出典と根拠

ORDレコード
ord-d5ad35a7830d4cbdb1a3b32a30730a5b
出典データセット
uspto-grants-1990_03
特許番号
US04908455

関連ノート

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