Cyanocyclobutane → 1-(4-Bromopyridin-2-yl)cyclobutane-1-carbonitrile

HRID 1430158Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1430158
[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[Br:11][C:12]1[CH:17]=[CH:16][N:15]=[C:14](F)[CH:13]=1.[CH:19]1([C:23]#[N:24])[CH2:22][CH2:21][CH2:20]1>C1(C)C=CC=CC=1>[Br:11][C:12]1[CH:17]=[CH:16][N:15]=[C:14]([C:19]2([C:23]#[N:24])[CH2:22][CH2:21][CH2:20]2)[CH:13]=1

Komponenten

5

Edukt 3

HCID 78148CyanocyclobutaneHCID 2733832Lithium HexamethyldisilazideHCID 27628514-Bromo-2-fluoropyridine

Produkt 1

HCID 574170941-(4-Bromopyridin-2-yl)cyclobutane-1-carbonitrileAusbeute 69 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

LiHMDS (1M in toluene, 17.7 mL, 17.7 mmol, 3.1 eq) is added dropwise to a cold (−5° C.) solution of 4-bromo-2-fluoro-pyridine [Marsais, F. et al, Journal of Organic Chemistry, (1992), 57, 565-573] (1 g, 5.7 mmol) and cyclobutanecarbonitrile (1.39 g, 17.1 mmol, 3 eq) in toluene (20 mL). The reaction mixture is allowed to warm to rt, stirred for 5 h, quenched by addition of a saturated solution of NaHCO3 and filtered through a pad of celite. The filtrate is extracted with EtOAc. The organic phase is washed with a saturated solution of NaHCO3, dried (Na2SO4), filtered and concentrated. The residue is purified by silica gel column chromatography (Hex/EtOAc, 1:0→95:5) to afford 933 mg of the title compound as a yellow oil: ESI-MS: 237.0/239.0 [M+H]+; tR=4.27 min (System 1); TLC: Rf=0.30 (Hex/EtOAc, 9:1).

Aufarbeitung

  1. customquenched by addition of a saturated solution of NaHCO3
  2. filtrationfiltered through a pad of celite
  3. extractionThe filtrate is extracted with EtOAc
  4. washThe organic phase is washed with a saturated solution of NaHCO3
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue is purified by silica gel column chromatography (Hex/EtOAc, 1:0→95:5)

Quellen und Nachweise

ORD-Eintrag
ord-47e8f06a5e91462dae91a429ecdfe30d
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08940771B2

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