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Toluene → N-(Diphenylmethylene)-5-(2-fluoro-4-nitrophenoxy)-1-methyl-1H-indazol-6-amine

HRID 2195502
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2195502
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][N:8]2[CH3:11])=[CH:4][C:3]=1[O:12][C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][C:14]=1[F:22].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C1(C)C=CC=CC=1.[C:72](=[NH:85])([C:79]1[CH:84]=[CH:83][CH:82]=[CH:81][CH:80]=1)[C:73]1[CH:78]=[CH:77][CH:76]=[CH:75][CH:74]=1.CC(C)([O-])C.[Na+]>C(Cl)Cl.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].CCOC(C)=O>[C:79]1([C:72]([C:73]2[CH:74]=[CH:75][CH:76]=[CH:77][CH:78]=2)=[N:85][C:2]2[CH:10]=[C:9]3[C:5]([CH:6]=[N:7][N:8]3[CH3:11])=[CH:4][C:3]=2[O:12][C:13]2[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][C:14]=2[F:22])[CH:80]=[CH:81][CH:82]=[CH:83][CH:84]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

9

Edukt 5

HCID 1140TolueneHCID 136809Benzophenone imineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23676156Sodium t-butoxideHCID 667668536-Bromo-5-(2-fluoro-4-nitrophenoxy)-1-methyl-1H-indazole

Produkt 1

HCID 86638473
N-(Diphenylmethylene)-5-(2-fluoro-4-nitrophenoxy)-1-methyl-1H-indazol-6-amine
Ausbeute 90,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 6344DichloromethaneLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel2×

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

To a 10 mL microwave vial is added 6-bromo-5-(2-fluoro-4-nitrophenoxy)-1-methyl-1H-indazole (500 mg, 1.37 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (73 mg, 123 μmol) and Pd2(dba)3 (38 mg, 41 μmol). The mixture is suspended in toluene (5 mL, 47 mmol) and benzophenone imine (272 mg, 1.5 mmol) and sodium tert-butoxide (203 mg, 2.05 mmol) are added. The mixture is heated at 150° C. for 20 min in a microwave reactor. After cooling, the reaction solution is concentrated to give a brown oil which is dissolved in DCM (150 mL) and washed with saturated aqueous sodium chloride (2×50 mL). The aqueous layers are combined and extracted with DCM (1×50 mL), dried with Na2SO4, filtered and concentrated to give a brown residue. The residue is purified on a silica gel column eluting with hexanes (A) and EtOAc (B), gradient from 85%(A): 15%(B) to 50%(A):50%(B) over 50 min to give a yellow solid material as the title compound (574 mg, 90.1% yield). MS (m/z): 467.2 (M+H).

Aufarbeitung

  1. temperatureAfter cooling
  2. concentrationthe reaction solution is concentrated
  3. customto give a brown oil which
  4. washwashed with saturated aqueous sodium chloride (2×50 mL)
  5. extractionextracted with DCM (1×50 mL)
  6. dry with materialdried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give a brown residue
  10. customThe residue is purified on a silica gel column
  11. washeluting with hexanes (A) and EtOAc (B), gradient from 85%(A)

Quellen und Nachweise

ORD-Eintrag
ord-adadd962d4b141ce93636812ebfd692d
Quelldatensatz
uspto-grants-2012_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
USRE043878E1

Notizen zur Reaktion

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