Dimethylformamide → 1-[({[(4R,5R)-4,5-bis(nitrooxy)hexyl]oxy}carbonyl)oxy]ethyl 2-ethoxy-1-{[2'-(1-trityl-1H-tetrazol-5-yl)biphenyl-4-yl]methyl}-1H-benzimidazole-7-carboxylate

HRID 889520

Reaktionsgleichung

Reaktionsgleichung von HRID 889520
CN(C)C=O.[C:6](=[O:26])([O:22][CH:23](Cl)[CH3:24])[O:7][CH2:8][CH2:9][CH2:10][C@@H:11]([O:18][N+:19]([O-:21])=[O:20])[C@H:12]([O:14][N+:15]([O-:17])=[O:16])[CH3:13].[CH2:27]([O:29][C:30]1[N:34]([CH2:35][C:36]2[CH:41]=[CH:40][C:39]([C:42]3[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=3[C:48]3[N:52]([C:53]([C:66]4[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=4)([C:60]4[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=4)[C:54]4[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=4)[N:51]=[N:50][N:49]=3)=[CH:38][CH:37]=2)[C:33]2[C:72]([C:76]([OH:78])=[O:77])=[CH:73][CH:74]=[CH:75][C:32]=2[N:31]=1)[CH3:28].C(=O)([O-])[O-].[Cs+].[Cs+]>O>[CH2:27]([O:29][C:30]1[N:34]([CH2:35][C:36]2[CH:37]=[CH:38][C:39]([C:42]3[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=3[C:48]3[N:52]([C:53]([C:60]4[CH:61]=[CH:62][CH:63]=[CH:64][CH:65]=4)([C:54]4[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=4)[C:66]4[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=4)[N:51]=[N:50][N:49]=3)=[CH:40][CH:41]=2)[C:33]2[C:72]([C:76]([O:78][CH:23]([O:22][C:6]([O:7][CH2:8][CH2:9][CH2:10][C@@H:11]([O:18][N+:19]([O-:21])=[O:20])[C@H:12]([O:14][N+:15]([O-:17])=[O:16])[CH3:13])=[O:26])[CH3:24])=[O:77])=[CH:73][CH:74]=[CH:75][C:32]=2[N:31]=1)[CH3:28]

Komponenten

6

Edukt 4

HCID 6228Dimethylformamide2×HCID 10796Cesium carbonateHCID 103125632-Ethoxy-1-((2'-(1-(triphenylmethyl)-1H-tetrazol-5-yl)(1,1'-biphenyl)-4-yl)methyl)-1H-benzimidazole-7-carboxylic acidHCID 86647015(4R,5R)-4,5-bis(nitrooxy)hexyl 1-chloroethyl carbonate

Produkt 1

HCID 866470171-[({[(4R,5R)-4,5-bis(nitrooxy)hexyl]oxy}carbonyl)oxy]ethyl 2-ethoxy-1-{[2'-(1-trityl-1H-tetrazol-5-yl)biphenyl-4-yl]methyl}-1H-benzimidazole-7-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

A N,N-dimethylformamide (20 mL) solution of (4R,5R)-4,5-bis(nitrooxy)hexyl 1-chloroethyl carbonate (2.94 g, 8.89 mmol) was added to a stirred N,N-dimethylformamide (20 mL) suspension of 2-ethoxy-1-{[2′-(1-trityl-1H-tetrazol-5-yl)biphenyl-4-yl]methyl}-1H-benzimidazole-7-carboxylic acid (7.46 g, 10.9 mmol) and cesium carbonate (3.95 g, 12.1 mmol). The solution was stirred at 70° C. for 2 hours. Water (100 mL) was added, and the solution was extracted with ethyl acetate (3×100 mL). The combined organic layers were dried (magnesium sulfate), filtered, and concentrated in vacuo. The residue was purified by column chromatography on silica gel, eluting with 20-60% ethyl acetate/hexanes to give the title compound as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.84 (dd, J=1.6, 7.3 Hz, 1H), 7.76 (dd, J=1.0, 7.9 Hz, 1H), 7.58 (dd, J=1.0, 7.9 Hz, 1H), 7.45 (dt, J=1.7, 7.4 Hz, 1H), 7.42 (dt, J=1.7, 7.4 Hz, 1H), 7.32 (t, J=7.4 Hz, 3H), 7.29 (dd, J=1.5, 7.4 Hz, 1H), 7.24 (t, J=7.8 Hz, 6H), 7.17 (t, J=7.9 Hz, 1H), 6.98 (d, J=8.2 Hz, 2H), 6.92 (d, J=8.2 Hz, 6H), 6.85 (q, J=5.4 Hz, 1H), 6.78 (d, J=8.2 Hz, 2H), 5.56 (s, 2H), 5.12-5.22 (m, 2H), 4.58-4.68 (m, 2H), 4.06-4.20 (m, 2H), 1.64-1.94 (m, 4H), 1.41-1.46 (m, 6H), 1.33 (d, J=6.4 Hz, 3H); LC-MS: m/z 999.5 (M+Na).

Aufarbeitung

  1. extractionthe solution was extracted with ethyl acetate (3×100 mL)
  2. dry with materialThe combined organic layers were dried (magnesium sulfate)
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by column chromatography on silica gel
  6. washeluting with 20-60% ethyl acetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-2dac838d4af54667aca4735a8211cad2
Quelldatensatz
uspto-grants-2012_08
Patentnummer
US08252825B2

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