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2-Iodo-4-nitroaniline → HCID 53741589, Verbindung

HRID 1769636
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1769636
I[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[CH3:12][Si:13]([CH3:27])([CH3:26])[C:14]#[C:15][CH2:16][CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20].C([O-])(=O)C.[K+].[Cl-].[Li+]>CN(C=O)C.CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:9]([C:7]1[CH:8]=[C:2]2[C:3](=[CH:5][CH:6]=1)[NH:4][C:14]([Si:13]([CH3:12])([CH3:27])[CH3:26])=[C:15]2[CH2:16][CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:20])[CH3:21])([O-:11])=[O:10]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 2226292-Iodo-4-nitroanilineHCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 13679439tert-Butyl(dimethyl){[4-(trimethylsilyl)but-3-yn-1-yl]oxy}silane

Produkt 1

HCID 53741589HCID 53741589, VerbindungAusbeute 42,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845
palladium(II) acetate
Katalysator
HCID 3283Diethyl EtherLösungsmittel
HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

A mixture of 2-iodo-4-nitroaniline (7.92 g, 0.030 mol), 1-(trimethylsilyl)-4-(t-butyldimethylsiloxy)-1-butyne (15.36 g, 0.060 mol), potassium acetate (14.70 g, 0.15 mol), lithium chloride (1.27 g, 0.030 mol) and palladium (II) acetate (0.675 g, 0.003 mol) in 100 mL of dry DMF was heated at 70° C. (oil-bath temperature) under Ar for 2.5 h. The cooled reaction mixture was diluted with ether and the aqueous phase was separated and extracted with ethyl acetate. The combined organic phases were washed (H2O, brine), dried (Na2SO4) and evaporated. The resulting residue was chromatographed (SiO2 /hexane-ethyl acetate, 4:1) to give a dark orange solid which was rechromatographed (SiO2 /hexane-CH2Cl2, 4:1 to 6:4) to give the title compound (5.00 g, 42%) as a yellow solid: IR (neat) 3414, 1328, 1253, 845 cm-1 ; 1H NMR (CDCl3, 200 MHz) δ 8.63 (d, J=2.2 Hz, 1H), 8.21 (br s, 1H), 8.09 (dd, J=9.0, 2.2 Hz, 1H), 7.35 (d, J=9.0 Hz, 1H), 3.84 (t, J=7.2 Hz, 2H), 3.09 (t, J=7.2 Hz, 2H), 0.85 (s, 9H), 0.42 (s, 9H), -0.01 (s, 6H).

Aufarbeitung

  1. customThe cooled reaction mixture
  2. customthe aqueous phase was separated
  3. extractionextracted with ethyl acetate
  4. washThe combined organic phases were washed (H2O, brine)
  5. dry with materialdried (Na2SO4)
  6. customevaporated
  7. customThe resulting residue was chromatographed (SiO2 /hexane-ethyl acetate, 4:1)
  8. customto give a dark orange solid which
  9. customwas rechromatographed (SiO2 /hexane-CH2Cl2, 4:1 to 6:4)

Quellen und Nachweise

ORD-Eintrag
ord-46cbe4e017f2451bbba70f566988022a
Quelldatensatz
uspto-grants-1995_01
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05382592

Notizen zur Reaktion

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