Toluene → (3-nitro-phenyl)-{3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-yl}-amine

HRID 1816799Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1816799
[CH:1]([C:9]1[C:17]2[C:12](=[CH:13][C:14]([NH2:18])=[CH:15][CH:16]=2)[N:11]([CH2:19][O:20][CH2:21][CH2:22][Si:23]([CH3:26])([CH3:25])[CH3:24])[N:10]=1)=[CH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[N+:27]([C:30]1[CH:31]=[C:32](I)[CH:33]=[CH:34][CH:35]=1)([O-:29])=[O:28].C([O-])([O-])=O.[Cs+].[Cs+].C1(C)C=CC=CC=1>C(OCC)(=O)C.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].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[N+:27]([C:30]1[CH:35]=[C:34]([NH:18][C:14]2[CH:13]=[C:12]3[C:17]([C:9]([CH:1]=[CH:2][C:3]4[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=4)=[N:10][N:11]3[CH2:19][O:20][CH2:21][CH2:22][Si:23]([CH3:24])([CH3:26])[CH3:25])=[CH:16][CH:15]=2)[CH:33]=[CH:32][CH:31]=1)([O-:29])=[O:28]

Komponenten

8

Edukt 4

HCID 1140TolueneHCID 10796Cesium carbonateHCID 125741-Iodo-3-nitrobenzeneHCID 693709803-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-ylamine

Produkt 1

HCID 69371523(3-nitro-phenyl)-{3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-yl}-amineAusbeute 74 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 634876Binap, (A+-)-KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To 3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-ylamine (1.1 g, 3 mmol, m-nitro-iodobenzene (0.9 g, 3.6 mmol), BINAP (0.07 g, 0.133 mmol), Pd2(dba)3 (34 mg, 0.0375 mmol) and Cs2CO3 (1.37 g, 4.2 mmol) under an atmosphere of argon was added toluene (6 mL). The resulting heterogeneous mixture was heated to 80° C. After 46 h the reaction was cooled to 23° C. diluted with ethyl acetate (EtOAc) (20 mL) and filtered. Water (5 mL) was added, the phases were separated, and the organic was extracted 2×50 mL EtOAc. The pooled organic material was washed with brine, then dried with Na2SO4, filtered and concentrated under reduced pressure. The crude reaction was purified by silica gel chromatography (eluting with 9:1 hexane:EtOAc) to give (3-nitro-phenyl)-{3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-yl}-amine as a yellow solid (7.65 g, 74%): TLC (Hexane:EtOAc 7:3) Rf sm 0.16, Rf p 0.30 (ethyl acetate:hexane 3:7); FTIR (KBr) 3391, 3059, 2952, 2894, 1614, 1530, 1483, 1346, 1248, 1076, 836, 734 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.86 (s, 1H), 7.83 (s. 1H), 7.65 (dt, 1H, J=2.21, 5.13 Hz), 7.15-7.41 (m, 5H), 6.93 (dd, 1H, J=1.87, 8.67 Hz), 5.56 (s, 2H), 3.51 (t, 2H, J=8.17 Hz), 0.81 (t, 2H, J=7.96 Hz), −0.15 (s, 9H); 13C NMR (75 MHz, CDCl3) δ 149.6, 144.8, 143.5, 142.4, 140.9, 137.3, 131.8, 130.3, 129.0, 128.2, 126.7, 122.8, 122.6, 120.1, 119.3, 116.1, 115.6, 111.4, 98.5, 77.9, 66.7, 18.0, −1.2; MS (ESI) [M+H]/z Calc'd 487, found 487. Anal. Calc'd: C, 66.64; H, 6.21; N, 11.51. Found: C, 66.91; H, 6.21; N, 11.44.

Aufarbeitung

  1. temperatureAfter 46 h the reaction was cooled to 23° C.
  2. filtrationfiltered
  3. additionWater (5 mL) was added
  4. customthe phases were separated
  5. extractionthe organic was extracted 2×50 mL EtOAc
  6. washThe pooled organic material was washed with brine
  7. dry with materialdried with Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe crude reaction
  11. customwas purified by silica gel chromatography (eluting with 9:1 hexane:EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-c0f3e914819c4b9ba86e978f0e596a90
Quelldatensatz
uspto-grants-2005_04
Patentnummer
US06884890B2

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