Sodium bis(trimethylsilyl)amide → 3-(But-3-yn-1-yl)benzonitrile

HRID 1397366노트

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HRID 1397366 반응식
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Br[C:12](Br)=[CH:13][CH2:14][CH2:15][C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][CH:23]=1)[C:19]#[N:20].[Li]CCCC>C1COCC1>[CH2:15]([C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][CH:23]=1)[C:19]#[N:20])[CH2:14][C:13]#[CH:12]

참가 물질

5

반응물 3

HCID 2724254Sodium bis(trimethylsilyl)amideHCID 866775953-(4,4-Dibromobut-3-en-1-yl)benzonitrileHCID 178418339Butyllithium

생성물 1

HCID 541923053-(But-3-yn-1-yl)benzonitrile수율 54.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

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온도
-70 °C

실험 절차

Sodium bis(trimethylsilyl)amide (10.7 mL, 10.7 mmol, 1 M in THF) was added dropwise to a solution of 3-(4,4-dibromobut-3-en-1-yl)benzonitrile (2.25 g, 7.14 mmol) in dry THF (45 mL) at −60° C. The reaction mixture was stirred for another 0.5 h maintaining the same temperature. The mixture was then cooled to −70° C. and n-BuLi (8.9 mL, 14.3 mmol, 1.6 M in hexane) was added dropwise. The reaction mixture was stirred for 0.5 h, quenched with saturated NH4Cl solution, and extracted with EtOAc. The combined extracts were concentrated under reduced pressure to obtain the 3-(but-3-yn-1-yl)benzonitrile (600 mg, yield 54%). 1H NMR (300 MHz, CDCl3) δ 7.55 (m, 1H), 7.53-7.51 (m, 1H), 7.48-7.39 (m, 2H), 2.90-2.85 (m, 2H), 2.54-2.48 (td, J=7.2 Hz, 2.6 Hz, 2H), 2.01-1.99 (t, J=2.6 Hz, 1H).

후처리

  1. temperaturemaintaining the same temperature
  2. stirringThe reaction mixture was stirred for 0.5 h
  3. customquenched with saturated NH4Cl solution
  4. extractionextracted with EtOAc
  5. concentrationThe combined extracts were concentrated under reduced pressure

출처 및 근거

ORD 기록
ord-41127b54704a41b98d393ef681799325
출처 데이터셋
uspto-grants-2014_12
특허 번호
US08901156B2

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