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

HRID 648795ノート

反応式

HRID 648795 の反応式
[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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 21226206Ethyl acetate hexane溶媒

実験手順

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:

後処理

  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

出典と根拠

ORDレコード
ord-75ad6df0c4184526acaee96973ff59aa
出典データセット
uspto-grants-1988_04
特許番号
US04736056

反応ノート

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