Acetic Acid → Uniconazole

HRID 845850

反応式

HRID 845850 の反応式
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

参加物

9

反応物 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

生成物 1

HCID 6436604Uniconazole収率 96%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 7964Chlorobenzene溶媒2 回

実験手順

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%.

後処理

  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

出典と根拠

ORDレコード
ord-9b64605f688a4633accbec8b36330e67
出典データセット
uspto-grants-1988_07
特許番号
US04760149

関連ノート

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