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

HRID 1478397

Reaktionsgleichung

Reaktionsgleichung von HRID 1478397
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

Komponenten

8

Edukt 3

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

Produkt 1

HCID 903861371-tert-butyl 2-methyl 3-phenyl-1H-pyrrole-1,2-dicarboxylateAusbeute 65,9 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-d0cc616d177942f88b47f003bb49788b
Quelldatensatz
uspto-grants-2016_08
Patentnummer
US09403834B2

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