Methanol → 3-(1,1-Dimethoxy-methyl)-6-[2-methoxy4-(2-trimethylsilanyl-ethoxymethoxy)-phenyl]-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole

HRID 724415Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 724415
[CH3:1][O:2][CH:3]([C:6]1[C:14]2[C:9](=[CH:10][C:11](I)=[CH:12][CH:13]=2)[N:8]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[N:7]=1)[O:4][CH3:5].[CH3:24][O:25][C:26]1[CH:31]=[C:30]([O:32][CH:33]([Si](C)(C)C)[O:34][CH2:35][CH3:36])[CH:29]=[CH:28][C:27]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+].CO>C1C=CC=CC=1.CCOCC.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.O>[CH3:1][O:2][CH:3]([C:6]1[C:14]2[C:9](=[CH:10][C:11]([C:27]3[CH:28]=[CH:29][C:30]([O:32][CH2:33][O:34][CH2:35][CH2:36][Si:20]([CH3:22])([CH3:21])[CH3:19])=[CH:31][C:26]=3[O:25][CH3:24])=[CH:12][CH:13]=2)[N:8]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[N:7]=1)[O:4][CH3:5]

Komponenten

9

Edukt 4

HCID 887MethanolHCID 10340Sodium CarbonateHCID 218772983-(1,1-dimethoxy-methyl)-6-iodo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazoleHCID 218774492-Methoxy4-(trimethylsilanyl-ethoxymethoxy)-phenylboronic acid

Produkt 1

HCID 218774213-(1,1-Dimethoxy-methyl)-6-[2-methoxy4-(2-trimethylsilanyl-ethoxymethoxy)-phenyl]-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazoleAusbeute 164,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 241BenzeneLösungsmittelHCID 962WaterLösungsmittelHCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

3-(1,1-Dimethoxy-methyl)-6-iodo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole (1.06 g, 2.37 mmol), 2-methoxy-4-(trimethylsilanyl-ethoxymethoxy)-phenylboronic acid (0.99 g, 3.32 mmol), and sodium carbonate (352 mg, 1.4 mmol) were stirred in a mixture of benzene (15 mL), MeOH (3 mL), and water (1 mL) in a flask purged with argon. Tetrakis(triphenylphosphine)palladium(0) (220 mg, 0.19 mmol) was added, and the reaction stirred at reflux for 16 h. The reaction was allowed to cool and was diluted with ether (70 mL). Organics were washed with H2O and brine (30 mL each), dried (Na2SO4), and concentrated in vacuo. Purification by silica gel chromatography (15% EtOAc/hexanes) gave 1.12 g (82%) of 3-(1,1-dimethoxy-methyl)-6-[2-methoxy-4-(2-trimethylsilanyl-ethoxymethoxy)-phenyl]-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole as a faintly yellow oil. 1H NMR (300 MHz, CDCl3) δ 7.91 (d, 1H, J=8.4 Hz), 7.64 (s, 1H), 7.37 (dd, 1H, J=8.4, 1.2 Hz), 7.29 (d, 1H, J=8.4 Hz), 6.71–6.77 (m, 2H), 5.82 (s, 1H), 5.75 (s, 2H), 5.28 (s, 2H), 3.77–3.83 (m, 5H), 3.57 (t, 2H, J=8.4 Hz), 3.46 (s, 6H), 1.00 (t, 2H, J=8.4 Hz), 0.88 (t, 2H, J=8.4 Hz), 0.03 (s, 9H), −0.05 (s, 9H).

Aufarbeitung

  1. custompurged with argon
  2. temperatureat reflux for 16 h
  3. temperatureto cool
  4. washOrganics were washed with H2O and brine (30 mL each)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customPurification by silica gel chromatography (15% EtOAc/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-864934a05a12446eaf20107135964030
Quelldatensatz
uspto-grants-2006_11
Patentnummer
US07141587B2

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