Dimethylformamide → Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate

HRID 648794노트

반응식

HRID 648794 반응식
O=C[CH2:3][C:4]([O-])=O.C(=O)([O-])[O-].[K+].[K+].[CH3:13][N:14](C)[CH:15]=[O:16].[Br:18]CCBr.[CH3:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27].[C:28]([O:31][CH2:32][CH3:33])(=[O:30])[CH3:29]>C(Cl)Cl>[Br:18][C:24]1[CH:23]=[CH:22][C:13]([NH:14][C:15]([C:29]2([C:28]([O:31][CH2:32][CH3:33])=[O:30])[CH2:4][CH2:3]2)=[O:16])=[C:26]([CH3:27])[CH:25]=1

참가 물질

7

반응물 5

HCID 6228DimethylformamideHCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 95431423-OxopropanoateHCID 21226206Ethyl acetate hexane

생성물 1

HCID 14150215Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate수율 81%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

Into a 500 milliliter three-necked Morton flask equipped with a mechanical stirrer, thermometer and nitrogen inlet and outlet was added 30.0 grams (0.10 mol) of ethyl 3-[4-bromo-2-methylphenyl)amino]-3-oxopropanoate prepared as in Example A, 34.5 grams (0.25 mol) of finely ground anhydrous potassium carbonate, 100 milliliters of dry dimethylformamide and 8.60 milliliters (0.10 mol) of 1,2-dibromoethane. The resulting mixture was stirred vigorously at ambient temperature under a nitrogen atmosphere for a period of 55 hours. During the first hour, the reaction exothermed from a temperature of 24° C. to 37° C. and, after 2 hours, high pressure liquid chromatographic analysis showed the reaction to be about 70 percent complete. The product was isolated by diluting with methylene chloride, filtering off the solids and concentrating under reduced pressure to give a yellow solid. Chromatography on silica gel with a 3:1 volume/volume hexane-ethyl acetate eluent provided ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate in two portions: 0.6 grams (1.8 mmol) of a pale yellow solid having a melting point of 89.5° C.-90.0° C. and 24.8 grams (0.076 mol) of a colorless solid having a melting point of 90.0° C.-90.5° C. The total yield was 81.0 percent based on a 96.7 weight percent assay of the starting ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate. NMR analysis of the product indicated the following:

후처리

  1. customInto a 500 milliliter three-necked Morton flask equipped with a mechanical stirrer
  2. additionthermometer and nitrogen inlet and outlet was added 30.0 grams (0.10 mol) of ethyl 3-[4-bromo-2-methylphenyl)amino]-
  3. waitDuring the first hour, the reaction exothermed from a temperature of 24° C. to 37° C. and, after 2 hours
  4. customthe reaction
  5. customThe product was isolated
  6. filtrationfiltering off the solids
  7. concentrationconcentrating under reduced pressure
  8. customto give a yellow solid

출처 및 근거

ORD 기록
ord-ab5038fa667c40fd8b9c779b396e508c
출처 데이터셋
uspto-grants-1988_04
특허 번호
US04736056

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