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

HRID 1648684Notes

Reaction equation

HRID 1648684 reaction equation
[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

Participants

6

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

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+).

Workup

  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)

Sources & evidence

ORD record
ord-0ecc60a934ea497ebaf391b8efa4cac0
Source dataset
uspto-grants-1995_07
Patent number
US05436369

Reaction notes

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