Acetic Acid → Uniconazole

HRID 2249019

Reaktionsgleichung

Reaktionsgleichung von HRID 2249019
C(O)(=O)C.C[C@H](N)[C@H](O)C1C=CC=CC=1.Cl.[BH4-].[Na+].[Cl:19][C:20]1[CH:25]=[CH:24][C:23](/[CH:26]=[C:27](/[N:34]2[CH:38]=[N:37][CH:36]=[N:35]2)\[C:28](=[O:33])[C:29]([CH3:32])([CH3:31])[CH3:30])=[CH:22][CH:21]=1.Cl>ClC1C=CC=CC=1.CN(C)C=O.O>[Cl:19][C:20]1[CH:25]=[CH:24][C:23](/[CH:26]=[C:27](/[N:34]2[CH:38]=[N:37][CH:36]=[N:35]2)\[CH:28]([OH:33])[C:29]([CH3:32])([CH3:31])[CH3:30])=[CH:22][CH:21]=1

Komponenten

9

Edukt 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 62943Phenylpropanolamine HydrochlorideHCID 4311764Sodium borohydrideHCID 10913254(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one

Produkt 1

HCID 6436604UniconazoleAusbeute 96 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 7964ChlorobenzeneLösungsmittel2×

Versuchsvorschrift

In a nitrogen atmosphere, 0.393 g (0.0065 mole) of acetic acid was added to a suspension of 8.18 g (0.0436 mole) of (-)-norephedrine hydrochloride in 62.17 g of chlorobenzene, and then a solution of 1.815 g (0.0480 mole) of sodium borohydride in 9.35 g of dimethylformamide was added dropwise to this suspension at 5° to 10° C. for 1.5 hours. Thereafter, the resulting mixture was stirred at room temperature for 1 hour, and then a solution of 8.42 g (0.0291 mole; E/Z=99.8/0.2) of (E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one in 49.7 g of chlorobenzene was added at room temperature. The resulting mixture was stirred at the same temperature for 18 hours. The reaction solution was decomposed with addition of 17.50 g of 10% hydrochloric acid and 5 g of water, and the organic layer was separated, washed with water and concentrated under reduced pressure to obtain 8.15 g (+)-(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol as a crystal. The conversion was 99.8%, and the composition of the product obtained was: E-form alcohol, 90.8%; saturated alcohol, 2.3%; and Z-form alcohol, 6.9%. The enantiomer ratio of the E-form alcohol was: (+)-isomer, 81.0% and (-)-isomer, 19.0%. The optical yield was 62.0%.

Aufarbeitung

  1. stirringThe resulting mixture was stirred at the same temperature for 18 hours
  2. customthe organic layer was separated
  3. washwashed with water
  4. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-f80e51ff994c46d6b20bdad93123b7fe
Quelldatensatz
uspto-grants-1991_08
Patentnummer
US05041651

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