Cesium carbonate → Di-tert-butyl 1-[6-(2-methoxy-5-methylphenyl)-4-nitropyridin-2-yl]hydrazine-1,2-dicarboxylate

HRID 1255201Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1255201
Cl[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([C:11]2[CH:16]=[C:15]([CH3:17])[CH:14]=[CH:13][C:12]=2[O:18][CH3:19])[N:3]=1.[NH:20]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23].C([O-])([O-])=O.[Cs+].[Cs+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[CH3:19][O:18][C:12]1[CH:13]=[CH:14][C:15]([CH3:17])=[CH:16][C:11]=1[C:4]1[N:3]=[C:2]([N:20]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[NH:21][C:22]([O:24][C:25]([CH3:26])([CH3:27])[CH3:28])=[O:23])[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=1

Komponenten

7

Edukt 3

HCID 10796Cesium carbonateHCID 85431Di-tert-butyl bicarbamateHCID 866334942-Chloro-6-(2-methoxy-5-methylphenyl)-4-nitropyridine

Produkt 1

HCID 67158740Di-tert-butyl 1-[6-(2-methoxy-5-methylphenyl)-4-nitropyridin-2-yl]hydrazine-1,2-dicarboxylate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A mixture of the title compound from Example 19 Step A (1.5 g, 5.4 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (1.375 g, 5.92 mmol), DPPF (360 mg, 0.65 mmol), Pd2 dba3 (0.4 g, 0.43 mmol), Cs2CO3 (1.90 g, 5.83 mmol) and 12 mL toluene was stirred at 100° C. After 20 h, the mixture was allowed to cool to ambient temperature, then purification by flash chromatography on silica gel using hexane-EtOAc (20:1 to 4:1 v/v) as mobile phase provided the title compound: LCMS m/z 375.6 (observed [M+H]+ for the ion corresponding to loss of one Boc group); 1H NMR (400 MHz, acetone-d6) δ 7.86 (d, J=2.1 Hz, 1H), 7.26 (dd, J=8.4, 2.1 Hz, 1H), 7.07 (d, J=8.4, 2.1 Hz, 1H), 3.93 (s, 3H), 2.31 (s, 3H), 1.54 (s, 9H), 1.47 (s, 9H).

Aufarbeitung

  1. temperatureto cool to ambient temperature
  2. custompurification by flash chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-6d9ca54d3ad94644a7ff75360075ce41
Quelldatensatz
uspto-grants-2013_06
Patentnummer
US08455638B2

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