Acetonitrile → Benzoylacetonitrile

HRID 1594025Notes

Reaction equation

HRID 1594025 reaction equation
[Li]CCCC.[C:6](#[N:8])[CH3:7].[C:9](OC)(=[O:16])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.C(#N)C.C(=O)=O>C1COCC1>[O:16]=[C:9]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH2:7][C:6]#[N:8]

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 7150Methyl BenzoateHCID 86587134Acetonitrile dry iceHCID 178418339Butyllithium

Product 1

HCID 64799Benzoylacetonitrile

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 50 mL of THF at −78° C. was added n-BuLi (58.8 mL, 147.0 mmol, 2.5 M in hexanes). After the reaction temperature equilibrated (˜15 min), a solution of acetonitrile (7.7 mL, 147.0 mmol in 100 mL of THF) was added dropwise via an addition funnel over a 20 min period. The resulting milky-white slurry was allowed to stir for 1 hr before a solution of methyl benzoate (10.0 g, 73.5 mmol in 20 mL of THF) was added down the inside of the flask over a 15 min period. After 1 hr, the reaction was warmed to −45° C. (acetonitrile/CO2) and allowed to stir for 2 hr. The reaction was quenched cold by the dropwise addition of 2 N HCl, pH=7 and then diluted with EtOAc. The layers were separated and the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure to give the title compound (quantitative yield) as a colorless solid that was used without further purification. LRMS m/z (APCl) 144 (M−1); 500 MHz 1H NMR (CDCl3) δ 7.92 (dd, J=8.4, 1.2 Hz, 2H), 7.66-7.64 (m, 1H), 7.55-7.50 (m, 2H), 4.09 (s, 2H).

Workup

  1. custom(˜15 min)
  2. additionwas added down the inside of the flask over a 15 min period
  3. customThe reaction was quenched cold by the dropwise addition of 2 N HCl, pH=7
  4. additiondiluted with EtOAc
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with CH2Cl2
  7. dry with materialThe combined organic layers were dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-51d3392e6d88475d9f88e8e2d205c77f
Source dataset
uspto-grants-2007_11
Patent number
US07300943B2

Reaction notes

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