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

HRID 648795노트

반응식

HRID 648795 반응식
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:16])[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:4]([CH3:17])[CH:3]=1.C(=O)([O-])[O-].[K+].[K+].CN(C)C=O.Br[CH2:30][CH2:31]Br>C(Cl)Cl.CCCCCC.C(OCC)(=O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]([C:10]2([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:31][CH2:30]2)=[O:16])=[C:4]([CH3:17])[CH:3]=1

참가 물질

7

반응물 4

HCID 6228DimethylformamideHCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate

생성물 1

HCID 14150215Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate수율 87%

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 21226206Ethyl acetate hexane용매

실험 절차

Into a 250 milliliter three-necked round-bottom reaction flask equipped with a mechanical stirrer, thermometer and nitrogen inlet and outlet was added 5.0 grams (17.0 mmol) of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate prepared as in Example A, 5.73 grams (42.0 mmol) of anhydrous potassium carbonate, 20 milliliters of anhydrous dimethylformamide and 1.7 milliliters (20.0 mol) of 1,2-dibromoethane. The resulting mixture was stirred at ambient temperature under a nitrogen atmosphere and irradiated with ultra sound waves using a Bransonic 52 ultrasonic cleaning bath for a period of 4.25 hours. Ice was added to maintain the temperature of the bath between 26° C. and 31° C. After this period, high pressure liquid chromatographic analysis showed the reaction to be 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 4.58 grams (14.0 mmol) of ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate as a pale yellow solid having a melting point of 87° C.-89° C. The total yield was 87 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 250 milliliter three-necked round-bottom reaction flask equipped with a mechanical stirrer
  2. additionthermometer and nitrogen inlet and outlet was added
  3. customirradiated with ultra sound waves
  4. customof 4.25 hours
  5. additionIce was added
  6. temperatureto maintain the temperature of the bath between 26° C. and 31° C
  7. waitAfter this period
  8. customthe reaction
  9. customThe product was isolated
  10. filtrationfiltering off the solids
  11. concentrationconcentrating under reduced pressure
  12. customto give a yellow solid

출처 및 근거

ORD 기록
ord-75ad6df0c4184526acaee96973ff59aa
출처 데이터셋
uspto-grants-1988_04
특허 번호
US04736056

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