Ammonium Chloride → alpha-(1-Ethoxymethyl-5-pyrazolyl)-2,3-dichloro-4-hydroxybenzylalcohol

HRID 1721943ノート

反応式

HRID 1721943 の反応式
C([Li])CCC.[CH2:6]([O:8][CH2:9][N:10]1[CH:14]=[CH:13][CH:12]=[N:11]1)[CH3:7].[Cl:15][C:16]1[C:23]([Cl:24])=[C:22]([OH:25])[CH:21]=[CH:20][C:17]=1[CH:18]=[O:19].[Cl-].[NH4+]>CCCCCC.O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH2:6]([O:8][CH2:9][N:10]1[C:14]([CH:18]([OH:19])[C:17]2[CH:20]=[CH:21][C:22]([OH:25])=[C:23]([Cl:24])[C:16]=2[Cl:15])=[CH:13][CH:12]=[N:11]1)[CH3:7]

参加物

8

反応物 4

HCID 25517Ammonium ChlorideHCID 5283802,3-Dichloro-4-hydroxybenzaldehydeHCID 157143991-(ethoxymethyl)-1H-pyrazoleHCID 178418339Butyllithium

生成物 1

HCID 14622794alpha-(1-Ethoxymethyl-5-pyrazolyl)-2,3-dichloro-4-hydroxybenzylalcohol収率 66.1%

試薬・触媒・溶媒 3

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒HCID 12679Hexamethylphosphoramide溶媒

実験手順

18.1 ml of 1.6M n-butyl lithium in hexane are added to a tetrahydrofuran solution of 3.56 g of 1-ethoxymethylpyrazole at -55° to -53° C. under argon gas atmosphere and the mixture is stirred at the same temperature for 1 hour. A solution of 2.45 g of 2,3-dichloro-4-hydroxybenzaldehyde in tetrahydrofuran is added to the above mixture, and the reaction mixture is stirred at -55° to -60° C. for 3 hours. 4.9 ml of hexamethylphosphoric triamide are then added and the whole mixture is stirred at room temperature for 16 hours. An aqueous saturated ammonium chloride solution is added and the mixture is extracted with ethyl acetate. The extract is washed with water, dried and evaporated to remove solvent. The residue is purified by silica gel column chromatography and crystallized with a mixture of ethyl acetate and isopropyl ether to give 2.69 g of α-(1-ethoxymethyl-5-pyrazolyl)-2,3-dichloro-4-hydroxybenzylalcohol.

後処理

  1. stirringthe reaction mixture is stirred at -55° to -60° C. for 3 hours
  2. stirringthe whole mixture is stirred at room temperature for 16 hours
  3. extractionthe mixture is extracted with ethyl acetate
  4. washThe extract is washed with water
  5. customdried
  6. customevaporated
  7. customto remove solvent
  8. customThe residue is purified by silica gel column chromatography
  9. customcrystallized with a mixture of ethyl acetate and isopropyl ether

出典と根拠

ORDレコード
ord-4f8be800e3444e22a13b2dd6b1ad84df
出典データセット
uspto-grants-1989_08
特許番号
US04853404

反応ノート

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