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Cesium carbonate → 9-(8-Aza-bicyclo[3.2.1]oct-3-ylidene)-5-phenyl-9H-xanthene-3-carboxylic acid diethylamide

HRID 733066
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 733066
[CH2:1]([N:3]([CH2:29][CH3:30])[C:4]([C:6]1[CH:7]=[CH:8][C:9]2[C:10](=[C:21]3[CH2:27][CH:26]4[NH:28][CH:23]([CH2:24][CH2:25]4)[CH2:22]3)[C:11]3[C:16]([O:17][C:18]=2[CH:19]=1)=[C:15](Br)[CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2].[C:31]1(B(O)O)[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C(O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:1]([N:3]([CH2:29][CH3:30])[C:4]([C:6]1[CH:7]=[CH:8][C:9]2[C:10](=[C:21]3[CH2:27][CH:26]4[NH:28][CH:23]([CH2:24][CH2:25]4)[CH2:22]3)[C:11]3[C:16]([O:17][C:18]=2[CH:19]=1)=[C:15]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2]
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Komponenten

7

Edukt 3

HCID 10796Cesium carbonateHCID 66827Phenylboronic AcidHCID 469179409-(8-Aza-bicyclo[3.2.1]oct-3-ylidene)-5-bromo-9H-xanthene-3-carboxylic acid diethylamide

Produkt 1

HCID 469179959-(8-Aza-bicyclo[3.2.1]oct-3-ylidene)-5-phenyl-9H-xanthene-3-carboxylic acid diethylamideAusbeute 90,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 44119782
Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)
Katalysator
HCID 702EthanolLösungsmittel
HCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

A mixture of 9-(8-aza-bicyclo[3.2.1]oct-3-ylidene)-5-bromo-9H-xanthene-3-carboxylic acid diethylamide (0.170, 0.363 mmol), phenylboronic acid (0.049 g, 0.40 mmol) and cesium carbonate (0.236 g, 0.726 mmol) in dioxane (4 mL) and ethanol (1 mL) was treated with dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct (13 mg), and the resulting mixture was heated at reflux for 2 h. The reaction mixture was cooled to room temperature, and the inorganics removed by filtration and washed successively with dioxane, ethanol and dichloromethane. The solvents were evaporated in vacuo. The residue was purified by reverse phase (C18) preparative HPLC, using a gradient of acetonitrile (10% to 90%) in water with trifluoroacetate (0.1%) as the eluant to give the title compound (0.153 g) as a colorless solid. MS: m/z 465.3 (MH+). 1H NMR (DMSO-d6): δ 1.05-1.20 (br m, 6 H0, 1.31 d, 2 H, J=8.2 Hz), 1.75-1.85 (br m, 2 H), 2.90-3.10 (m, 4 H), 3.15-3.50 (br m, 4 H), 4.03 br s, 2 H), 7.10 (d, 1 H, J=1.5 Hz), 7.20 (d of d, 1 H, J=1.5 & 7.9 Hz), 7.32 (t, 1 H, J=7.5 Hz), 7.40-7.63 (m, 8 H), 8.83 (br s, 1 H0 and 9.16 (br d, 1 H).

Aufarbeitung

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux for 2 h
  3. customthe inorganics removed by filtration
  4. washwashed successively with dioxane, ethanol and dichloromethane
  5. customThe solvents were evaporated in vacuo
  6. customThe residue was purified by reverse phase (C18) preparative HPLC

Quellen und Nachweise

ORD-Eintrag
ord-692ed06fd5dd4552ad240132f16026cd
Quelldatensatz
uspto-grants-2009_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07589103B2

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