Diethyl methylmalonate → 1-(3-bromophenyl)-5-hydroxy-4-methyl-1,2-dihydro-3H-pyrazol-3-one

HRID 432115

反応式

HRID 432115 の反応式
Cl.[Br:2][C:3]1[CH:4]=[C:5]([NH:9][NH2:10])[CH:6]=[CH:7][CH:8]=1.[O-]CC.[Na+].[CH3:15][CH:16]([C:22](OCC)=[O:23])[C:17](OCC)=[O:18]>C(O)C>[Br:2][C:3]1[CH:4]=[C:5]([N:9]2[C:22]([OH:23])=[C:16]([CH3:15])[C:17](=[O:18])[NH:10]2)[CH:6]=[CH:7][CH:8]=1

参加物

5

反応物 3

HCID 11857Diethyl methylmalonateHCID 337573-Bromophenylhydrazine hydrochlorideHCID 2723922Sodium ethoxide

生成物 1

HCID 223514471-(3-bromophenyl)-5-hydroxy-4-methyl-1,2-dihydro-3H-pyrazol-3-one収率 10.4%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒2 回

反応条件

温度
90 °C

実験手順

To a suspension of 1-(3-bromophenyl)hydrazine hydrochloride (1.0 g, 4.47 mmol) in ethanol (8.9 mL) was added dropwise 2.0 M sodium ethoxide in ethanol (0.77 mL, 9.84 mmol, 2.2 eq.). Diethyl 2-methylmalonate (0.85 mL, 4.92 mmol, 1.1 eq.) was then added. The reaction mixture was stirred at 90° C. for 16 hours and then quenched with 2 N aqueous hydrochloric acid (50 mL). The reaction was extracted with ethyl acetate (3×50 mL), and the combined organic layers were dried (MgSO4), filtered, and evaporated under reduced pressure. Purification using MPLC (Biotage) eluted with 3:1 v/v ethyl acetate-hexane gave the desired product as a white solid (125 mg, 0.46 mmol, 10.4% yield). MS LC-MS (ES MH+=269/271); TLC (Rf=0.10, 50% ethyl acetate-hexane).

後処理

  1. customquenched with 2 N aqueous hydrochloric acid (50 mL)
  2. extractionThe reaction was extracted with ethyl acetate (3×50 mL)
  3. dry with materialthe combined organic layers were dried (MgSO4)
  4. filtrationfiltered
  5. customevaporated under reduced pressure
  6. customPurification
  7. washeluted with 3:1 v/v ethyl acetate-hexane

出典と根拠

ORDレコード
ord-c0a2637b7cfc4f828ad4965f769c119f
出典データセット
uspto-grants-2003_12
特許番号
US06660752B2

関連ノート

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