Sodium Cyanide → [3-(t-Butyldiphenylsiloxymethyl)phenyl]acetonitrile

HRID 1648684Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1648684
[C-:1]#[N:2].[Na+].[O:4]([CH2:22][C:23]1[CH:24]=[C:25]([CH:28]=[CH:29][CH:30]=1)[CH2:26]Cl)[Si:5]([C:18]([CH3:21])([CH3:20])[CH3:19])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Cl-].[NH4+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C>[O:4]([CH2:22][C:23]1[CH:24]=[C:25]([CH2:26][C:1]#[N:2])[CH:28]=[CH:29][CH:30]=1)[Si:5]([C:18]([CH3:21])([CH3:20])[CH3:19])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Komponenten

6

Edukt 3

HCID 8929Sodium CyanideHCID 25517Ammonium ChlorideHCID 220737533-(t-Butyldiphenylsiloxymethy)benzyl chloride

Produkt 1

HCID 19920606[3-(t-Butyldiphenylsiloxymethyl)phenyl]acetonitrileAusbeute 73 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 67553Tetrabutylammonium IodideKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

Sodium cyanide (1.57 g, 32.0 mmol) and tetrabutylammonium iodide (0.11 g, 0.30 mmol) were added to a stirred solution of 24 (11.8 g, 29.9 mmol) in anhydrous DMF (90 mL) at room temperature under argon. The reaction mixture was heated to 80° C. for 2 h. The solution was allowed to cool to room temperature and was poured into saturated ammonium chloride solution and extracted twice with diethyl ether. The organic layers were combined, washed with saturated sodium chloride, dried over anhydrous magnesium sulfate, filtered, and concentrated to give 11.0 g of a clear, brown oil. Purification by column chromatography (20:1 ratio silica gel/crude product; gradient elution with 1% to 10% ethyl acetate/hexanes) provided 8.39 g (73%) of 25 as a pale yellow, clear oil. 1H NMR (300 MHz, CDCl3) δ7.64-7.67 (m, 4H, ArH), 7.19-7.41 (m, 10H, ArH), 4.74 (s, 2H, CH2OSi), 3.70 (s, 2H, CH2CN), and 1.08 (s, 9H, SiC(CH3)3); 13C NMR (75 MHz, CDCl3) δ142.24, 135.57, 133.31, 129.81, 129.04, 127.78, 126.41, 125.69, 125.54, 117.87 (CN), 65.13 (CH2OSi), 26.85 (SiC(CH3)3), 23.65 (CH2CN), and 19.31 (SiC(CH3)3); IR (film) 2960, 2930, 2890, 2860, 2250 (CN), 1470, 1430, 1150, 1110, and 1080 cm-1 ; MS (DCI) m/e 386 (MH+).

Aufarbeitung

  1. temperatureto cool to room temperature
  2. extractionextracted twice with diethyl ether
  3. washwashed with saturated sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give 11.0 g of a clear, brown oil
  8. customPurification
  9. washby column chromatography (20:1 ratio silica gel/crude product; gradient elution with 1% to 10% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-0ecc60a934ea497ebaf391b8efa4cac0
Quelldatensatz
uspto-grants-1995_07
Patentnummer
US05436369

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