Acetonitrile → 3-(Naphthalen-1-yl)-3-oxopropanenitrile

HRID 928242Notes

Reaction equation

HRID 928242 reaction equation
C([Li])CCC.CCCCCC.[C:12](#[N:14])[CH3:13].[C:15]1([C:25](OCC)=[O:26])[C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH:18]=[CH:17][CH:16]=1>O1CCCC1>[C:15]1([C:25]([CH2:13][C:12]#[N:14])=[O:26])[C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 8058HexaneHCID 76364Ethyl 1-naphthoateHCID 178418339Butyllithium

Product 1

HCID 219434673-(Naphthalen-1-yl)-3-oxopropanenitrileYield 72%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2.50 M of n-butyllithium in hexane (49.9 mL, 125 mmol) in tetrahydrofuran (49.9 mL) cooled to −78° C. is added acetonitrile (6.52 mL, 125 mmol) drop-wise. The resulting cloudy mixture is stirred for 30 min. Ethyl α-napthoate (8.87 mL, 49.9 mmol) is added drop-wise and the reaction mixture is stirred at −78° C. for 2 hr. The reaction is warmed to room temperature, quenched with acetic acid (50 ml) and partitioned between ethyl acetate and water. The organic layer is dried over Na2SO4, filtered and concentrated in vacuo. The crude material is purified by column chromatography (eluent: 5-15% CH2Cl2/methanol) to provide 1-naphthoylacetonitrile (6.99 g, yield 72%). 1H NMR (400 MHz, CDCl3) δ 8.82 (d, J=8.7 Hz, 1H), 8.11 (d, J=8.3 Hz, 1H), 7.90 (t, J=8.1 Hz, 2H), 7.71-7.64 (m, 1H), 7.57 (dt, J=15.5, 7.2 Hz, 2H), 4.21 (s, 2H).

Workup

  1. stirringthe reaction mixture is stirred at −78° C. for 2 hr
  2. customquenched with acetic acid (50 ml)
  3. custompartitioned between ethyl acetate and water
  4. dry with materialThe organic layer is dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude material is purified by column chromatography (eluent: 5-15% CH2Cl2/methanol)

Sources & evidence

ORD record
ord-7a0ccae401454707b989490608e1fc1f
Source dataset
uspto-grants-2016_03
Patent number
US09290500B2

Reaction notes

Loading…