Dichloromethane → Dimethyl 3-(2-bromoethylamino)-2-pentenedioate

HRID 2108214노트

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HRID 2108214 반응식
CS([CH2:5][CH2:6][NH:7][C:8]([CH2:14][C:15]([O:17][CH3:18])=[O:16])=[CH:9][C:10]([O:12][CH3:13])=[O:11])(=O)=O.ClCCl.S([O-])(=O)(=O)C.[Br-:27].[Li+]>O>[Br:27][CH2:5][CH2:6][NH:7][C:8]([CH2:14][C:15]([O:17][CH3:18])=[O:16])=[CH:9][C:10]([O:12][CH3:13])=[O:11]

참가 물질

6

반응물 4

HCID 6344DichloromethaneHCID 82050Lithium BromideHCID 85257MethanesulfonateHCID 74015715Dimethyl 3-(2-methanesulfonylethylamino)-2-pentenedioate

생성물 1

HCID 74015712Dimethyl 3-(2-bromoethylamino)-2-pentenedioate수율 86.7%

시약·촉매·용매 1

HCID 962Water용매

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온도
35 °C

실험 절차

Dimethyl 3-(2-methanesulfonylethylamino)-2-pentenedioate (156.3 g, 529 mmol) was added to a 2 L three-neck flask, which was fitted with a mechanical stirrer, thermometer, and reflux condenser. Dichloromethane (750 mL) was added and stirred until the mesylate had completely dissolved, anhydrous lithium bromide (69.0 g, 794 mmol) was added, and the mixture stirred at 35° C. for 19 hours. The mixture was cooled to 0° C. and water (250 mL) added, then stirred for 5 minutes and the phases separated. The organic phase was washed with water (3×250 mL) and brine (150 mL), and dried over anhydrous potassium carbonate for 15 minutes. Rotary evaporation of the solvent under reduced pressure (50° C.) gave 128.4 g of crude dimethyl 3-(2-bromoethylamino)-2-pentenedioate as a yellow oil, which quickly solidified to a yellow solid. The crude material was purified by extraction into boiling hexane (5×750 mL) and recrystallization from hexane, and the pot residues extracted and recrystallized, to give a total of 90.8 g (61.2% yield) of dimethyl 3-(2-bromoethylamino)-2-pentenedioate as white needles. An NMR spectrum in CDCl3 indicated an Z/E isomer ratio of 19:1, and remeasurement of the CDCl3 solution after three days indicated an Z/E ratio of 4:1. The two isomers were not separated.

후처리

  1. customwhich was fitted with a mechanical stirrer
  2. temperaturethermometer, and reflux condenser
  3. dissolutionhad completely dissolved
  4. temperatureThe mixture was cooled to 0° C.
  5. stirringstirred for 5 minutes
  6. customthe phases separated
  7. washThe organic phase was washed with water (3×250 mL) and brine (150 mL)
  8. dry with materialdried over anhydrous potassium carbonate for 15 minutes
  9. customRotary evaporation of the solvent under reduced pressure (50° C.)

출처 및 근거

ORD 기록
ord-cfdeed6340704e17914d4ec3770b5dec
출처 데이터셋
uspto-grants-1990_06
특허 번호
US04937368

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