Sodium Carbonate → 2-[Bis(tert-butoxycarbonyl)amino]-5-(2'-methylthiophenyl)pyrimidine

HRID 394784Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 394784
[C:1]([O:5][C:6]([N:8]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[C:9]1[N:14]=[CH:13][C:12](Br)=[CH:11][N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:23][S:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC=CC=1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:1]([O:5][C:6]([N:8]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[C:9]1[N:14]=[CH:13][C:12]([C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[S:24][CH3:23])=[CH:11][N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Komponenten

7

Edukt 3

HCID 10340Sodium CarbonateHCID 27735432-(Methylthio)benzeneboronic acidHCID 11977091tert-butyl N-(5-bromopyrimidin-2-yl)-N-((tert-butoxy)carbonyl)carbamate

Produkt 1

HCID 181773202-[Bis(tert-butoxycarbonyl)amino]-5-(2'-methylthiophenyl)pyrimidineAusbeute 96,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysatorHCID 241BenzeneLösungsmittel

Versuchsvorschrift

2-[Bis(tert-butoxycarbonyl)amino]-5-bromopyrimidine (2.00 g, 5.3 mmol) was dissolved in benzene (130 mL). 2-methylthiophenylboronic acid (2.24 g, 13.3 mmol), aq. sodium carbonate (13 mL, 2.0 M, 26 mmol), tetrabutyl ammonium bromide (86 mg, 0.26 mmol), and bis(triphenylphosphine)palladium(II)chloride (190 mg, 0.27 mmol) were added, and the resulting mixture was first purged with vacuum and argon, then refluxed 17 hours. The cooled mixture was diluted with EtOAc and water. The layers were separated, and the organic was dried over Na2SO4, filtered, and evaporated. The crude product was chromatographed on silica gel (50% EtOAc/hexanes), evaporated, and chromatographed a second time on silica gel (30-50% EtOAc/hexanes) to yield the desired product (2.13 g, 96%). 1H NMR (CDCl3): δ 8.81 (s, 2H), 7.41 (m, 2H), 7.25 (m, 2H), 2.39 (s, 3H), 1.49 (s, 18H).

Aufarbeitung

  1. customthe resulting mixture was first purged with vacuum and argon
  2. temperaturerefluxed 17 hours
  3. additionThe cooled mixture was diluted with EtOAc and water
  4. customThe layers were separated
  5. dry with materialthe organic was dried over Na2SO4
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was chromatographed on silica gel (50% EtOAc/hexanes)
  9. customevaporated
  10. customchromatographed a second time on silica gel (30-50% EtOAc/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-199091ef605e418ab7f06aa043e60a83
Quelldatensatz
uspto-grants-2003_08
Patentnummer
US06602895B2

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