1-Ethynyl-3,5-difluorobenzene → 2-Tert-butoxycarbonylamino-5-{4-[4-(4-pentylphenyl)-[1,2,3]triazol-1-yl]phenyl}imidazole-1-carboxylic acid tert-butyl ester

HRID 1468572Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1468572
[C:1]([O:5][C:6]([N:8]1[C:12]([C:13]2[CH:18]=[CH:17][C:16]([N:19]=[N+:20]=[N-:21])=[CH:15][CH:14]=2)=[CH:11][N:10]=[C:9]1[NH:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:30]([C:32]1[CH:37]=[C:36](F)[CH:35]=[C:34](F)[CH:33]=1)#[CH:31].O=[C:41]1O[C@H:46]([C@H:48](CO)O)[C:44]([O-])=[C:42]1O.[Na+]>O.CCO.C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[C:12]([C:13]2[CH:14]=[CH:15][C:16]([N:19]3[CH:31]=[C:30]([C:32]4[CH:37]=[CH:36][C:35]([CH2:41][CH2:42][CH2:44][CH2:46][CH3:48])=[CH:34][CH:33]=4)[N:21]=[N:20]3)=[CH:17][CH:18]=2)=[CH:11][N:10]=[C:9]1[NH:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Komponenten

7

Edukt 3

HCID 42068061-Ethynyl-3,5-difluorobenzeneHCID 23667548Sodium AscorbateHCID 579314105-(4-Azidophenyl)-2-tert-butoxycarbonylaminoimidazole-1-carboxylic acid tert-butyl ester

Produkt 1

HCID 579314242-Tert-butoxycarbonylamino-5-{4-[4-(4-pentylphenyl)-[1,2,3]triazol-1-yl]phenyl}imidazole-1-carboxylic acid tert-butyl esterAusbeute 593,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

5-(4-azidophenyl)-2-tert-butoxycarbonylaminoimidazole-1-carboxylic acid tert-butyl ester (0.080 g, 0.200 mmol), 1-ethynyl-3,5-difluorobenzene (0.035 g, 0.26 mmol), CuSO4.5H2O (0.097 g, 0.040 mmol), and sodium ascorbate (0.004 g, 0.020 mmol) were all charged in a reaction vessel and dissolved in a 1:1:1 mixture of H2O (0.75 mL), EtOH 0.75 mL), and CH2Cl2 (0.75 mL). The reaction was stirred at ambient temperature for 16 h. After the reaction was quenched with sat. NaHCO3 and diluted with EtOAc (50 mL). The organic layer was washed with sat. NaHCO3 (3×20 mL) before being dried (Na2SO4), filtered and evaporated to dryness. The crude product was purified by column chromatography (10%-30% EtOAc/Hexanes) to afford 0.068 g (44%) of 2-tert-butoxycarbonylamino-5-{4-[4-(4-pentylphenyl)-[1,2,3]triazol-1-yl]phenyl}imidazole-1-carboxylic acid tert-butyl ester as a white solid: 1H NMR (300 MHz, DMSO-d6) δ 9.60 (s, 1H), 9.29 (s, 1H), 8.01 (m, 3H), 7.98 (d, 2H, J=6.0 Hz), 7.85 (d, 2H, J=5.6 Hz), 7.32 (d, 2H, J=5.4 Hz), 2.62 (t, 2H, J=5.1 Hz), 1.59 (s, 9H), 1.47 (m, 2H), 1.45 (s, 9H), 1.30 (m, 4H), 0.87 (m, 3H); 13C NMR (75 MHz, DMSO-d6) δ 152.8, 147.2, 142.3, 139.9, 135.5, 128.9, 127.8, 127.6, 125.9, 120.1, 118.9, 113.5, 85.5, 80.0, 38.7, 31.3, 30.8, 27.9, 27.3, 21.9, 13.9; HRMS (ESI) calcd for C32H40N6O4 (M+) 572.3111. found 572.3113.

Aufarbeitung

  1. additionall charged in a reaction vessel
  2. customAfter the reaction was quenched with sat. NaHCO3
  3. additiondiluted with EtOAc (50 mL)
  4. washThe organic layer was washed with sat. NaHCO3 (3×20 mL)
  5. dry with materialbefore being dried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated to dryness
  8. customThe crude product was purified by column chromatography (10%-30% EtOAc/Hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-7c4cb4536e8e40ad8b70b9f0957d0ed1
Quelldatensatz
uspto-grants-2015_04
Patentnummer
US09005643B2

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