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

HRID 1648684ノート

反応式

HRID 1648684 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 67553Tetrabutylammonium Iodide触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

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+).

後処理

  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)

出典と根拠

ORDレコード
ord-0ecc60a934ea497ebaf391b8efa4cac0
出典データセット
uspto-grants-1995_07
特許番号
US05436369

反応ノート

読み込み中…