Benzeneacetonitrile, 4-bromo- → HCID 20100170, compound

HRID 1480564Notes

Reaction equation

HRID 1480564 reaction equation
[CH:1]1([Mg]Br)[CH2:3][CH2:2]1.Br[C:7]1[CH:12]=[CH:11][C:10]([CH2:13][C:14]#[N:15])=[CH:9][CH:8]=1>C1COCC1.[Cl-].[Zn+2].[Cl-]>[CH:1]1([C:7]2[CH:12]=[CH:11][C:10]([CH2:13][C:14]#[N:15])=[CH:9][CH:8]=2)[CH2:3][CH2:2]1

Participants

5

Reactant 2

HCID 27914Benzeneacetonitrile, 4-bromo-HCID 178418630HCID 178418630, compound

Product 1

HCID 20100170HCID 20100170, compoundYield 66%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

Cyclopropylmagnesium bromide (64.0 mL, 32.00 mmol) in THF was treated with a solution of zinc (II) chloride (64.00 mL, 32.00 mmol) in THF. The mixture was stirred at ambient temperature for 20 minutes. 2-(4-Bromophenyl)acetonitrile (5.228 g, 26.67 mmol) and bis[tri-t-butyl phosphine]palladium (0.6814 g, 1.333 mmol) were added as a solution in THF (2 mL). The reaction was stirred at ambient temperature under nitrogen for 12 hours. The reaction was quenched with saturated NH4Cl, diluted with methylene chloride and separated. The aqueous layer was washed with methylene chloride (2×), and then the combined organic layers were washed with water (3×), dried over Na2SO4 and concentrated in vacuo. The crude product was subjected to chromatography on SiO2 eluting with 25:1 hexanes/ethyl acetate to yield 2-(4-cyclopropylphenyl)acetonitrile (2.76 g, 66%). 1H NMR (CDCl3, 400 MHz) δ 7.20 (d, J=8.2, 2H), 7.07 (d, J=8.2, 2H), 3.70 (s, 2H), 1.94-1.85 (m, 1H), 1.01-0.95 (m, 2H), 0.71-0.66 (m, 2H).

Workup

  1. stirringThe reaction was stirred at ambient temperature under nitrogen for 12 hours
  2. customThe reaction was quenched with saturated NH4Cl
  3. additiondiluted with methylene chloride
  4. customseparated
  5. washThe aqueous layer was washed with methylene chloride (2×)
  6. washthe combined organic layers were washed with water (3×)
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-81dd5dcccb5042809bd05d08cda69420
Source dataset
uspto-grants-2016_08
Patent number
US09409886B2

Reaction notes

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