3,3-Dimethyl-1-butyne → 2-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile

HRID 503343Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 503343
[NH2:1][C:2]1[C:9](Br)=[CH:8][C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5].[CH3:14][C:15]([CH3:19])([CH3:18])[C:16]#[CH:17]>CCN(CC)CC.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[C:9]([C:17]#[C:16][C:15]([CH3:19])([CH3:18])[CH3:14])=[CH:8][C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5]

Komponenten

6

Edukt 2

HCID 135123,3-Dimethyl-1-butyneHCID 871732-Amino-3-bromo-5-nitrobenzonitrile

Produkt 1

HCID 591292522-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrileAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a stirred solution of 2-amino-3-bromo-5-nitrobenzonitrile (2.4 g, 10 mmol) in dry Et3N (60 mL) was added CuI (380 mg, 5% mol) and Pd(PPh3)2Cl2 (470 mg, 5% mol) at room temperature. 3,3-dimethyl-but-1-yne (2.1 g, 25 mmol) was added dropwise to the mixture at room temperature. The reaction mixture was stirred at 80° C. for 10 h. The reaction mixture was filtered and the filtrate was poured into ice (60 g), extracted with ethyl acetate. The phases were separated and the organic phase was dried over Na2SO4. The solvent was removed under vacuum to obtain the crude product, which was purified by column chromatography (2-10% EtOAc in petroleum ether) to obtain 2-amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile (1.7 g, 71%). 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J=2.7 Hz, 1H), 8.27 (d, J=2.7 Hz, 1H), 5.56 (br s, 2H), 1.37 (s, 9H).

Aufarbeitung

  1. filtrationThe reaction mixture was filtered
  2. additionthe filtrate was poured into ice (60 g)
  3. extractionextracted with ethyl acetate
  4. customThe phases were separated
  5. dry with materialthe organic phase was dried over Na2SO4
  6. customThe solvent was removed under vacuum
  7. customto obtain the crude product, which
  8. customwas purified by column chromatography (2-10% EtOAc in petroleum ether)

Quellen und Nachweise

ORD-Eintrag
ord-366fe5b4c98c48cc9644fa9defb101c4
Quelldatensatz
uspto-grants-2010_08
Patentnummer
US07776905B2

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