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

HRID 1397366Notes

Reaction equation

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]

Participants

Conditions

Temperature: -70 °C

Procedure

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).

Workup

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

Sources & evidence

ORD record: ord-41127b54704a41b98d393ef681799325
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08901156B2

Reaction notes

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