Cesium carbonate → (2-Bromo-6-{4,4-dimethyl-9-oxo-7-thia-10-azatricyclo[6.4.0.02,6]dodeca-1(8),2(6)-dien-10-yl}-4-fluorophenyl)methyl Acetate

HRID 1919044Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1919044
[CH3:1][C:2]1([CH3:15])[CH2:14][C:5]2[C:6]3[CH2:11][CH2:10][NH:9][C:8](=[O:12])[C:7]=3[S:13][C:4]=2[CH2:3]1.[C:16]([O:19][CH2:20][C:21]1[C:26]([Br:27])=[CH:25][C:24]([F:28])=[CH:23][C:22]=1Br)(=[O:18])[CH3:17].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:16]([O:19][CH2:20][C:21]1[C:22]([N:9]2[CH2:10][CH2:11][C:6]3[C:5]4[CH2:14][C:2]([CH3:15])([CH3:1])[CH2:3][C:4]=4[S:13][C:7]=3[C:8]2=[O:12])=[CH:23][C:24]([F:28])=[CH:25][C:26]=1[Br:27])(=[O:18])[CH3:17]

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 580438956,6-Dimethyl-2,3,4,5,6,7-hexahydro-1H-cyclopenta[4,5]thieno[2,3-c]pyridin-1-oneHCID 670165932,6-Dibromo-4-fluorobenzyl acetate

Produkt 1

HCID 58044256(2-Bromo-6-{4,4-dimethyl-9-oxo-7-thia-10-azatricyclo[6.4.0.02,6]dodeca-1(8),2(6)-dien-10-yl}-4-fluorophenyl)methyl AcetateAusbeute 71,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A mixture of 4,4-dimethyl-7-thia-10-azatricyclo[6.4.0.02,6]dodeca-1(8),2(6)-dien-9-one (105h) (2 g, 9.05 mmol), 2,6-dibromo-4-fluorobenzyl acetate (197c) (8.8 g, 27.15 mmol), XantPhos (524 mg, 0.9 mmol), Pd2(dba)3 (828 mg, 0.9 mmol) and Cs2CO3 (5.9 g, 18 mmol) in dioxane (200 mL) was heated at 100° C. for 15 h under nitrogen. The reaction mixture was filtered and the filtrated was evaporated in vacuo. The residue was purified by silical-gel column eluting with 1:1 ethyl acetate/petroleum ether to give 247a as a yellow solid (3 g, 71%). MS: (M+H)+ 466.

Aufarbeitung

  1. filtrationThe reaction mixture was filtered
  2. customthe filtrated was evaporated in vacuo
  3. customThe residue was purified by silical-gel column
  4. washeluting with 1:1 ethyl acetate/petroleum ether

Quellen und Nachweise

ORD-Eintrag
ord-b6fa6f0ec8f6418f87e77c569565babc
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08618107B2

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