Ammonium Chloride → 3-(4-Methylphenyl)pyridine-2-carbonitrile

HRID 373127Notes

Reaction equation

HRID 373127 reaction equation
[C:1]1([CH3:9])[CH:6]=[CH:5][C:4]([Mg]Br)=[CH:3][CH:2]=1.Br[C:11]1[C:12]([C:17]#[N:18])=[N:13][CH:14]=[CH:15][CH:16]=1.[NH4+].[Cl-]>CCOCC.C1COCC1.[Cl-].[Cl-].[Zn+2].Cl[Ni](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:17]([C:12]1[C:11]([C:4]2[CH:5]=[CH:6][C:1]([CH3:9])=[CH:2][CH:3]=2)=[CH:16][CH:15]=[CH:14][N:13]=1)#[N:18]

Participants

8

Reactant 3

HCID 25517Ammonium ChlorideHCID 8176943-Bromopyridine-2-carbonitrileHCID 178418370HCID 178418370, compound

Product 1

HCID 153301703-(4-Methylphenyl)pyridine-2-carbonitrile

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 178418751HCID 178418751, compoundCatalystHCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of p-tolylmagnesium bromide (9.3 mL of a 1M solution in Et2O, 9.28 mmol) in THF (17 mL) at -78° C. was added ZnCl2 (9.3 mL of a 1M solution in Et2O, 9.28 mmol). The resulting slurry was warmed to rt for 20 min then cooled to 0° C. Bis-(triphenylphosphine)nickle(II) chloride (178 mg, 0.27 mmol) and 3-bromo-2-cyanopyridine (1.0 g, 5.5 mmol); (prepared as reported: Chem. Pharm Bull., 1985, vol. 33, p 565) were added in one portion. After 1 h, saturated aqueous NH4Cl (50 mL) was added and the mixture was extracted with EtOAc (2×50 mL). Purification by flash chromatography (40% EtOAc/hexanes) gave the above titled compound as a white solid.

Workup

  1. temperaturethen cooled to 0° C
  2. custom(prepared as reported: Chem. Pharm Bull., 1985, vol. 33, p 565)
  3. additionwere added in one portion
  4. extractionthe mixture was extracted with EtOAc (2×50 mL)
  5. customPurification by flash chromatography (40% EtOAc/hexanes)

Sources & evidence

ORD record
ord-86d26a7a7ca842bea4047e489570e1ce
Source dataset
uspto-grants-1992_11
Patent number
US05162325

Reaction notes

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