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

HRID 1648684노트

반응식

HRID 1648684 반응식
[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

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 67553Tetrabutylammonium Iodide촉매HCID 6228Dimethylformamide용매

반응 조건

온도
80 °C

실험 절차

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+).

후처리

  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)

출처 및 근거

ORD 기록
ord-0ecc60a934ea497ebaf391b8efa4cac0
출처 데이터셋
uspto-grants-1995_07
특허 번호
US05436369

반응 노트

불러오는 중…