Pyrrolidine → 2-(Pyrrolidin-1-yl)-4-amino-m-xylene

HRID 1182266Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1182266
Br[C:2]1[C:3]([CH3:10])=[C:4]([NH2:9])[CH:5]=[CH:6][C:7]=1[CH3:8].[NH:11]1[CH2:15][CH2:14][CH2:13][CH2:12]1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[N:11]1([C:2]2[C:3]([CH3:10])=[C:4]([NH2:9])[CH:5]=[CH:6][C:7]=2[CH3:8])[CH2:15][CH2:14][CH2:13][CH2:12]1

Komponenten

5

Edukt 3

HCID 31268PyrrolidineHCID 123959063-Bromo-2,4-dimethylanilineHCID 23676156Sodium t-butoxide

Produkt 1

HCID 204949532-(Pyrrolidin-1-yl)-4-amino-m-xylene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a solution of the 3-bromo-2,4-dimethylphenylamine (0.6 g, 3.0 mmol) in toluene (10 mL) and pyrrolidine (1.25 mL, 15 mmol) was added sodium-t-butoxide (0.86 g, 9 mmol, 3eq). The suspension was deoxygenated by passing a stream of N2 gas through the mixture for approximately 5–10 minutes before introducing the tris(dibenzilidene)dipalladium(0) (Pd2(dba)3) (27 mg) and rac-2,2′Bis(diphenylphosphino)-1,1′binaphthyl (BINAP) (25 mg). The nitrogen stream continued 10 minutes before heating at 100° C. overnight. The reaction mixture was cooled, acidified with HCl (2N) and extracted with diethyl ether. The aqueous layer was adjusted basic and re-extracted with ethyl acetate. The organic layer was dried over sodium sulfate, decanted and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, gradient elution with 6:1 to 4:1 hexanes to ethyl acetate) to give the desired 2-(pyrrolidin-1-yl)-4-amino-m-xylene.

Aufarbeitung

  1. customThe suspension was deoxygenated
  2. customfor approximately 5–10 minutes
  3. additionbefore introducing the tris(dibenzilidene)dipalladium(0) (Pd2(dba)3) (27 mg) and rac-2,2′Bis(diphenylphosphino)-1,1′binaphthyl (BINAP) (25 mg)
  4. temperatureThe reaction mixture was cooled
  5. extractionextracted with diethyl ether
  6. extractionre-extracted with ethyl acetate
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. customdecanted
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by flash chromatography (silica gel, gradient elution with 6:1 to 4:1 hexanes to ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-760f60a7e9f14de4be0929e705825a2b
Quelldatensatz
uspto-grants-2007_10
Patentnummer
US07288538B2

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