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

HRID 1721943노트

반응식

HRID 1721943 반응식
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]

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매HCID 12679Hexamethylphosphoramide용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-4f8be800e3444e22a13b2dd6b1ad84df
출처 데이터셋
uspto-grants-1989_08
특허 번호
US04853404

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