Hydrochloric Acid → Methyl 4,5-dichloro-6-((1-ethoxymethyl-pyrazol-5-yl)-hydroxymethyl)-1,3-benzodioxole-2-carboxylate

HRID 1074176노트

반응식

HRID 1074176 반응식
[CH2:1]([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:24]2[O:23][CH:22]([C:25]([O-:27])=[O:26])[O:21][C:20]=2[CH:19]=[C:18]([CH:28]=[O:29])[C:17]=1[Cl:30].[Li+].[Cl-].[NH4+].Cl>CCCCCC.O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[Cl:15][C:16]1[C:24]2[O:23][CH:22]([C:25]([O:27][CH3:1])=[O:26])[O:21][C:20]=2[CH:19]=[C:18]([CH:28]([C:14]2[N:10]([CH2:9][O:8][CH2:6][CH3:7])[N:11]=[CH:12][CH:13]=2)[OH:29])[C:17]=1[Cl:30]

참가 물질

9

반응물 5

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 157143991-(ethoxymethyl)-1H-pyrazoleHCID 23683076Lithium 4,5-dichloro-6-formyl-1,3-benzodioxole-2-carboxylateHCID 178418339Butyllithium

생성물 1

HCID 15714401Methyl 4,5-dichloro-6-((1-ethoxymethyl-pyrazol-5-yl)-hydroxymethyl)-1,3-benzodioxole-2-carboxylate수율 75%

시약·촉매·용매 3

HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매HCID 12679Hexamethylphosphoramide용매

실험 절차

A solution of 12.2 ml of 1.6M n-butyl lithium in hexane is added dropwise to a solution of 2.45 g of 1-ethoxymethyl-pyrazole in 50 ml of tetrahydrofuran at -60° to -50° C. under argon gas atmosphere and the mixture is stirred at the same temperature for 40 minutes. A solution of 5.23 g of lithium 4,5-dichloro-6-formyl-1,3-benzodioxole-2-carboxylate in 40 ml of hexamethylphosphoric triamide is added dropwise to the reaction mixture at -60° to -50° C. and the mixture is stirred at the same temperature for 30 minutes. An aqeous saturated ammonium chloride solution and 1N hydrochloric acid are added to the reaction mixture, and the mixture is extracted with ethyl acetate. An excess amount of a solution of diazomethane in ether is added to the extract (the extract contains 4,5-dichloro-6-[(1-ethoxymethylpyrazol-5-yl)-hydroxymethyl]-1,3-benzodioxole-2-carboxylic acid) and the mixture is stirred for 10 minutes. The mixture is evaporated to remove solvent and the residue is purified by silica gel column chromatography (solvent: chloroform-acetone-ethanol) to give 5.9 g of methyl 4,5-dichloro-6-[(1-ethoxymethyl-pyrazol-5-yl)-hydroxymethyl]-1,3-benzodioxole-2-carboxylate (a mixture of diastereoisomers thereof) as an oil. Yield: 75%

후처리

  1. stirringthe mixture is stirred at the same temperature for 30 minutes
  2. extractionthe mixture is extracted with ethyl acetate
  3. additionAn excess amount of a solution of diazomethane in ether is added to the
  4. extractionextract (the extract
  5. stirringis stirred for 10 minutes
  6. customThe mixture is evaporated
  7. customto remove solvent
  8. customthe residue is purified by silica gel column chromatography (solvent: chloroform-acetone-ethanol)

출처 및 근거

ORD 기록
ord-2df3542ebb9c4b66ac37d4a3fe4d559f
출처 데이터셋
uspto-grants-1990_11
특허 번호
US04973600

반응 노트

불러오는 중…