Potassium Carbonate → 1-tert-butyl 2-methyl 3-phenyl-1H-pyrrole-1,2-dicarboxylate

HRID 1478397

반응식

HRID 1478397 반응식
Br[C:2]1[CH:6]=[CH:5][N:4]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[C:3]=1[C:14]([O:16][CH3:17])=[O:15].C(=O)([O-])[O-].[K+].[K+].[C:24]1(B(O)O)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>C1(C)C=CC=CC=1.O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:24]1([C:2]2[CH:6]=[CH:5][N:4]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[C:3]=2[C:14]([O:16][CH3:17])=[O:15])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

참가 물질

8

반응물 3

HCID 11430Potassium CarbonateHCID 66827Phenylboronic AcidHCID 441898031-tert-butyl 2-methyl 3-bromo-1H-pyrrole-1,2-dicarboxylate

생성물 1

HCID 903861371-tert-butyl 2-methyl 3-phenyl-1H-pyrrole-1,2-dicarboxylate수율 65.9%

시약·촉매·용매 4

HCID 74236Tetrabutylammonium Bromide촉매HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 1140Toluene용매

실험 절차

To a solution of 1-tert-butyl 2-methyl 3-bromo-1H-pyrrole-1,2-dicarboxylate (17.6 g, 57.9 mmol) in toluene (200 mL) and water (200 mL) was added potassium carbonate (64.0 g, 463 mmol), followed by phenylboronic acid (10.6 g, 87.0 mmol) and tetrabutylammonium bromide (1.68 g, 5.21 mmol). The reaction mixture degassed for 10 min with nitrogen and then tetrakis(triphenylphosphine)palladium (1.34 g, 1.16 mmol) was added. The resulting slurry was degassed with nitrogen for 30 min and then heated to reflux for 16 h. The reaction mixture was concentrated under reduced pressure to remove water and toluene. Water was then added to the residue and the mixture extracted by ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography using CombiFlash (REDISEP®, silica gel, 80 g, 20% EtOAc/hexanes) to obtain 1-tert-butyl 2-methyl 3-phenyl-1H-pyrrole-1,2-dicarboxylate (11.5 g, 65.9%) as a tan solid. 1H NMR (400 MHz, CD3OD) δ ppm: 1.60 (s, 9H), 3.79 (s, 3H), 6.40 (d, J=3.4 Hz, 1H), 7.37 (m, 6H).

후처리

  1. customThe reaction mixture degassed for 10 min with nitrogen
  2. customThe resulting slurry was degassed with nitrogen for 30 min
  3. temperatureheated
  4. temperatureto reflux for 16 h
  5. concentrationThe reaction mixture was concentrated under reduced pressure
  6. customto remove water and toluene
  7. additionWater was then added to the residue
  8. extractionthe mixture extracted by ethyl acetate
  9. dry with materialThe combined organic layers were dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified by column chromatography

출처 및 근거

ORD 기록
ord-d0cc616d177942f88b47f003bb49788b
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09403834B2

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