Stattic → 6-nitro-1-[2-(trimethyl-silanyl)ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole

HRID 2181528Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2181528
C1C2C=CS(=O)(=O)C=2C=C([N+]([O-])=O)C=1.CC(C)(C)COC([SiH3])N1C([C:29]2[N:33]([CH2:34][O:35][CH2:36][CH2:37][Si:38]([CH3:41])([CH3:40])[CH3:39])[C:32]3[CH:42]=[CH:43][CH:44]=[CH:45][C:31]=3[N:30]=2)C2C(=CC=CC=2)N1.[N+:49]([C:52]1[CH:60]=[C:59]2[C:55]([C:56]([Sn](C)(C)C)=[N:57][N:58]2[CH2:61][O:62][CH2:63][CH2:64][Si:65]([CH3:68])([CH3:67])[CH3:66])=[CH:54][CH:53]=1)([O-:51])=[O:50].IN1C2C=CC=CC=2N(COCC[Si](C)(C)C)C1>[Cu]I.C1COCC1>[N+:49]([C:52]1[CH:60]=[C:59]2[C:55]([C:56]([C:29]3[N:33]([CH2:34][O:35][CH2:36][CH2:37][Si:38]([CH3:40])([CH3:41])[CH3:39])[C:32]4[CH:42]=[CH:43][CH:44]=[CH:45][C:31]=4[N:30]=3)=[N:57][N:58]2[CH2:61][O:62][CH2:63][CH2:64][Si:65]([CH3:68])([CH3:67])[CH3:66])=[CH:54][CH:53]=1)([O-:51])=[O:50]

Komponenten

7

Edukt 4

HCID 2779853StatticHCID 218774146-Nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-(trimethyl-stannanyl)-1-H-indazoleHCID 218775973-iodo-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzimidazoleHCID 178447183HCID 178447183, Verbindung

Produkt 1

HCID 229806876-nitro-1-[2-(trimethyl-silanyl)ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazoleAusbeute 82 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Preparation of 6-nitro-1-[2-(trimethyl-silanyl-ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]1-H-benzoimidazol-2-yl}-1-H-indazole: 6-Nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-(trimethyl-stannanyl)-1-H-indazole (7.50 g, 16.4 mmol), 3-iodo-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzimidazole (6.50 g, 17.4 mmol), and copper(I) iodide (313 mg, 1.64 mmol) were combined with dry THF (150 mL) in a flask purged with argon. Tetrakis(triphenylphosphine)palladium(0) was added, and the reaction stirred at reflux under argon for 23 h. The reaction was cooled and adsorbed directly onto silica gel (˜16 g). Purification by silica gel chromatography (4% to 15% ethyl acetate/hexanes) gave 7.28 g (82%) of 6-nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole as a light yellow solid. 1H NMR (300 MHz, CDCl3) δ 8.91 (d, 1H, J=9.0 Hz), 8.59 (d, 1H, J=1.8 Hz), 8.22 (dd, 1H, J=8.7, 1.8 Hz), 7.92-7.89 (m, 1H), 7.66-7.62 (m, 1H), 7.40-7.36 (m, 2H), 6.24 (s, 2H), 5.90 (s, 2H), 3.68-3.59 (m, 4H), 0.94 (t, 2H, J=8.1 Hz), 0.86 (t, 2H, J=8.1 Hz), −0.04 (s, 9H), −0.15 (s, 9H). Anal. (C26H37N5O4Si2) C, H, N. Calculated: C, 57.85; H, 6.91; N, 12.97. Found: C, 57.60; H, 6.81; N, 12.82.

Aufarbeitung

  1. custompurged with argon
  2. additionTetrakis(triphenylphosphine)palladium(0) was added
  3. temperatureat reflux under argon for 23 h
  4. temperatureThe reaction was cooled
  5. customPurification by silica gel chromatography (4% to 15% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-fff8df8e233442bbbf82233aaaa4fea4
Quelldatensatz
uspto-grants-2005_05
Patentnummer
US06891044B2

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