3,3-Dimethyl-1-butyne → 2-(3,3-Dimethyl-but-1-ynyl)-6-fluoro-4-nitro-phenylamine

HRID 468344Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 468344
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([F:11])[C:3]=1[NH2:12].[CH3:13][C:14]([CH3:18])([CH3:17])[C:15]#[CH:16]>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>[CH3:13][C:14]([CH3:18])([CH3:17])[C:15]#[C:16][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([F:11])[C:3]=1[NH2:12]

Komponenten

6

Edukt 2

HCID 135123,3-Dimethyl-1-butyneHCID 143001412-Bromo-6-fluoro-4-nitroaniline

Produkt 1

HCID 591292912-(3,3-Dimethyl-but-1-ynyl)-6-fluoro-4-nitro-phenylamineAusbeute 36 %

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 solution of 2-bromo-6-fluoro-4-nitro-phenylamine (11 g, 47 mmol) in dry Et3N (100 mL) was added CuI (445 mg, 5% mol), Pd(PPh3)2Cl2 (550 mg, 5% mol) and 3,3-dimethyl-but-1-yne (9.6 g, 120 mmol) under N2 protection. The mixture was stirred at 80° C. for 10 h. The reaction mixture was filtered, poured into ice (100 g), and extracted with EtOAc (50 mL×3). The combined organic extracts were dried over anhydrous Na2SO4 and evaporated under vacuum to give the crude product, which was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 50:1) to give 2-(3,3-dimethyl-but-1-ynyl)-6-fluoro-4-nitro-phenylamine (4.0 g, 36%). 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J=1.2 Hz, 1H), 7.84 (dd, =2.4, 10.8 Hz, 1H), 4.85 (brs, 2H), 1.36 (s, 9H).

Aufarbeitung

  1. filtrationThe reaction mixture was filtered
  2. additionpoured into ice (100 g)
  3. extractionextracted with EtOAc (50 mL×3)
  4. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  5. customevaporated under vacuum
  6. customto give the crude product, which
  7. customwas purified by column chromatography on silica gel (petroleum ether/ethyl acetate 50:1)

Quellen und Nachweise

ORD-Eintrag
ord-c151f78058054ff391c11a41a12e91d9
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08623905B2

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