Bromine → ethyl 4-bromo-3,5-dimethyl-1H-pyrrole-2-carboxylate

HRID 383755노트

반응식

HRID 383755 반응식
[CH3:1][C:2]1[CH:6]=[C:5]([CH3:7])[NH:4][C:3]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].[Br:13]Br>C(Cl)(Cl)(Cl)Cl.C(Cl)Cl>[Br:13][C:6]1[C:2]([CH3:1])=[C:3]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[NH:4][C:5]=1[CH3:7]

참가 물질

5

반응물 2

HCID 24408BromineHCID 1374771H-Pyrrole-2-carboxylic acid, 3,5-dimethyl-, ethyl ester

생성물 1

HCID 138486ethyl 4-bromo-3,5-dimethyl-1H-pyrrole-2-carboxylate

시약·촉매·용매 2

HCID 5943Carbon Tetrachloride용매2회HCID 6344Dichloromethane용매

실험 절차

To a solution of ethyl 3,5-dimethyl-1H-pyrrole-2-carboxylate (3.42 g, 20 mmol) in carbon tetrachloride (40 mL) was added a solution of bromine in carbon tetrachloride (10 mL) dropwise at 20° C. After the addition was complete, stirring was continued for 2 h. The reaction mixture was diluted with DCM, washed with aqueous NaHCO3 and water, and then dried over Na2SO4. Evaporation of solvent gave ethyl 4-bromo-3,5-dimethyl-1H-pyrrole-2-carboxylate as a solid (4.8 g), which was used in the next step without purification. 1H-NMR (CDCl3): δ 9.36 (1H, s), 4.30 (2H, q), 228 (3H, s), 2.26 (3H, s), 1.36 (3H, t). To a solution of ethyl 4-bromo-3,5-dimethyl-1H-pyrrole-2-carboxylate (2.4 g, 10 mmol) in DMF (25 mL) was added tetrakis(triphenylphosphine)palladium (2.3 g, 1 mmol). After stirring 15 min, the reaction mixture was charged with 2-(trifluoromethyl)-benzeneboronic acid (2.4 g, 12.5 mmol) and sodium carbonate (in 5 mL of water). The reaction mixture was heated to reflux overnight with stirring. After cooling, the reaction mixture was then diluted with water and extracted with DCM. The combined extracts were washed with water and dried over Na2SO4. Evaporation of solvent gave a crude material, which was purified by chromatography on silica gel column eluting with EtOAc-hexane (1:1) to give the title compound (1.5 g). MS (ES): 312 (MH+);

후처리

  1. additionAfter the addition
  2. washwashed with aqueous NaHCO3 and water
  3. dry with materialdried over Na2SO4
  4. customEvaporation of solvent

출처 및 근거

ORD 기록
ord-1107e7e9ecc04d43af6b7f834d16a10f
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08367667B2

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