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Triphosgene → HCID 178522047, Verbindung

HRID 1023890
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1023890
C([N:20]1[CH:24]=[C:23]([C:25]2[CH:40]=[CH:39][CH:38]=[CH:37][C:26]=2[O:27][CH2:28][CH2:29][C:30]2[CH:36]=[CH:35][C:33]([NH2:34])=[CH:32][CH:31]=2)[N:22]=[CH:21]1)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.Cl[C:42](Cl)([O:44]C(=O)OC(Cl)(Cl)Cl)Cl.[O:53]1[CH2:58][CH2:57][CH:56]([NH2:59])[CH2:55][CH2:54]1.C(=O)(O)[O-].[Na+]>ClCCl.C(N(CC)CC)C>[NH:20]1[CH:24]=[C:23]([C:25]2[CH:40]=[CH:39][CH:38]=[CH:37][C:26]=2[O:27][CH2:28][CH2:29][C:30]2[CH:31]=[CH:32][C:33]([NH:34][C:42]([NH:59][CH:56]3[CH2:57][CH2:58][O:53][CH2:54][CH2:55]3)=[O:44])=[CH:35][CH:36]=2)[N:22]=[CH:21]1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 4

HCID 94429TriphosgeneHCID 4192234-AminotetrahydropyranHCID 516892Sodium BicarbonateHCID 672072114-(2-(2-(1-Trityl-1H-imidazol-4-yl)phenoxy)ethyl)aniline

Produkt 1

HCID 178522047HCID 178522047, VerbindungAusbeute 78 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344
Dichloromethane
Lösungsmittel
2×
HCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

4-(2-(2-(1-trityl-1H-imidazol-4-yl)phenoxy)ethyl)aniline (50.0 mg. 0.096 mmol) was dissolved in dichloromethane (DCM, 5 ml) and triethylamine (1 ml), and a solution of triphosgene (0.105 mmol) in DCM (5 ml) was then added to the solution at 0° C. The mixture was stirred at room temperature under N2 for 2 h. Next, tetrahydro-2H-pyran-4-amine (20.0 mg, 0.192 mmol) was added to the reaction solution, and the mixture was stirred at room temperature under N2 for overnight. A saturated aqueous sodium bicarbonate solution was added to the reaction solution, followed by extraction with DCM (3×15 ml). The DCM layer was dried over Na2SO4. The solvent was removed by distillation under the reduced pressure. The residue was dissolved in MeOH/AcOH (4:1, 4 mL) and heated at 80° C. for 2 h. The reaction mixture was basified with aqueous 10% NaOH and the aqueous layer extracted with ethyl acetate (2×30 mL). The combined organic extracts were washed with brine (15 mL), dried over Na2SO4 and concentrated. The residue was purified by flash column chromatography. Yield=78%. 1H NMR (MeOH-d4): 1.40-1.54 (m, 2H), 1.81-1.92 (m, 2H), 3.11-3.15 (m, 2H), 3.46-3.53 (m, 2H), 3.55-3.80 (m, 1H), 3.85-3.95 (m, 2H), 4.35 (t, 2H, J=6.6 Hz), 6.95-7.00 (m, 1H), 7.05-7.13 (m, 2H), 7.19-7.30 (m, 5H), 7.70 (s, 1H), 7.78 (d, 1H, J=7.8 Hz).

Aufarbeitung

  1. stirringthe mixture was stirred at room temperature under N2 for overnight
  2. extractionfollowed by extraction with DCM (3×15 ml)
  3. dry with materialThe DCM layer was dried over Na2SO4
  4. customThe solvent was removed by distillation under the reduced pressure
  5. dissolutionThe residue was dissolved in MeOH/AcOH (4:1, 4 mL)
  6. temperatureheated at 80° C. for 2 h
  7. extractionthe aqueous layer extracted with ethyl acetate (2×30 mL)
  8. washThe combined organic extracts were washed with brine (15 mL)
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated
  11. customThe residue was purified by flash column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-6ac2db0779ef40e3816afd56722a89a0
Quelldatensatz
uspto-grants-2014_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08722720B2

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