Hydrochloric Acid → Uniconazole

HRID 1165370

Reaktionsgleichung

Reaktionsgleichung von HRID 1165370
Cl.N[C@@H](CC(C)C)C(C1C=CC=CC=1)(C1C=CC=CC=1)O.[BH4-].[Na+].[Cl:24][C:25]1[CH:30]=[CH:29][C:28](/[CH:31]=[C:32](/[N:39]2[CH:43]=[N:42][CH:41]=[N:40]2)\[C:33](=[O:38])[C:34]([CH3:37])([CH3:36])[CH3:35])=[CH:27][CH:26]=1.Cl>ClCCCl.CN(C)C=O>[Cl:24][C:25]1[CH:30]=[CH:29][C:28](/[CH:31]=[C:32](/[N:39]2[CH:43]=[N:42][CH:41]=[N:40]2)\[CH:33]([OH:38])[C:34]([CH3:37])([CH3:36])[CH3:35])=[CH:27][CH:26]=1

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 10913254(E)-1-(4-chlorophenyl)-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

Produkt 1

HCID 6436604UniconazoleAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 111,2-DichloroethaneLösungsmittel2×HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
-20 °C

Versuchsvorschrift

In a nitrogen atmosphere, 0.551 g (1.8 mmoles) 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 0.0681 g (1.8 mmoles) of sodium borohydride in 1 ml of dimethylformamide was added. The temperature of the suspension was raised from -20° C. to room temperature over 2 hours. Thereafter, a solution of 0.348 g (1.2 mmoles) of (E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one in 4 ml of 1,2-dichloroethane was added to this suspension at room temperature, and stirring was carried out for 48 hours. Thereafter, 6 ml of 2N hydrochloric acid was added and stirring was carried out for 2 hours. After removing the intermediate layer by filtration, the organic layer was washed with water and concentrated under reduced pressure, and the residue was purified on a column packed with 2 g of silica gel with chloroform as a developing solvent to obtain 0.35 g of (+)-(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3 -ol as a crystal. By gas-chromatographic analysis, it was found that the conversion was 96.3%, and the composition of the product was: E-form alcohol, 78.9%; Z-form alcohol, 20.3%; and saturated alcohol, 0.8% (said alcohol means a product obtained by hydrogenation of both the carbonyl group and the double bond contained in the α,β-unsaturated ketone used as a material). By high-performance liquid-chromatographic analysis using an optically active column, it was found that the enantiomer ratio of the produced E-form alcohol was: (+)-isomer, 86.1% and (-)-isomer, 13.9%. The optical yield was 72.2%.

Aufarbeitung

  1. temperatureThe temperature of the suspension was raised from -20° C. to room temperature over 2 hours
  2. stirringstirring
  3. waitwas carried out for 2 hours
  4. customAfter removing the intermediate layer
  5. filtrationby filtration
  6. washthe organic layer was washed with water
  7. concentrationconcentrated under reduced pressure
  8. customthe residue was purified on a column

Quellen und Nachweise

ORD-Eintrag
ord-5fe71a184fca4ce5b15b86569ece71a1
Quelldatensatz
uspto-grants-1990_03
Patentnummer
US04908455

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