Potassium bis(trimethylsilyl)amide → 4-(4-Cyano-3-methylphenyl)tetrahydro-2H-thiopyran-4-carbonitrile

HRID 419952

Reaktionsgleichung

Reaktionsgleichung von HRID 419952
[S:1]1[CH2:6][CH2:5][CH:4]([C:7]#[N:8])[CH2:3][CH2:2]1.C[Si]([N-][Si](C)(C)C)(C)C.[K+].F[C:20]1[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[C:22]([CH3:28])[CH:21]=1>C1COCC1>[C:24]([C:23]1[CH:26]=[CH:27][C:20]([C:4]2([C:7]#[N:8])[CH2:5][CH2:6][S:1][CH2:2][CH2:3]2)=[CH:21][C:22]=1[CH3:28])#[N:25]

Komponenten

5

Edukt 3

HCID 3251421Potassium bis(trimethylsilyl)amideHCID 38260554-Fluoro-2-methylbenzonitrileHCID 21598641Thiane-4-carbonitrile

Produkt 1

HCID 582984424-(4-Cyano-3-methylphenyl)tetrahydro-2H-thiopyran-4-carbonitrileAusbeute 67,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A solution of tetrahydro-2H-thiopyran-4-carbonitrile (197 mg, 1.55 mmol) and THF (2.0 mL) is slowly added via syringe to a mixture of KHMDS (324 mg, 1.63 mmol) in THF (3.0 mL), stirring at −78° C. under nitrogen. The temperature is maintained at −78° C. for 30 min. before a mixture of 4-fluoro-2-methylbenzonitrile (222 mg, 1.64 mmol) in THF (1.0 mL) is slowly added to the vessel. The mixture is allowed to warm to room temperature and is stirred for 3 hours before being quenched with saturated aqueous NH4Cl. The solvent is removed by rotary evaporator and EtOAc (10.0 mL) and water (10.0 mL) are added. The phases are partitioned and the organic is washed with brine, dried with Na2SO4 and concentrated to yield the product (252 mg, 1.04 mmol, 67%). 1H NMR (400 MHz, DMSO-D6) δ ppm 1.84-1.95 (m, 2H), 2.03-2.14 (m, 2H), 2.51 (s, 3H), 2.57-2.72 (m, 4H), 7.23-7.31 (m, 1H), 7.41 (dd, J=9.96, 1.76 Hz, 1H), 7.89 (dd, J=8.59, 5.86 Hz, 1H).

Aufarbeitung

  1. additionis slowly added to the vessel
  2. temperatureto warm to room temperature
  3. stirringis stirred for 3 hours
  4. custombefore being quenched with saturated aqueous NH4Cl
  5. customThe solvent is removed by rotary evaporator and EtOAc (10.0 mL) and water (10.0 mL)
  6. additionare added
  7. customThe phases are partitioned
  8. washthe organic is washed with brine
  9. dry with materialdried with Na2SO4
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-294cf2cad1814cd8b0ac3b130c83bbff
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08093402B2

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