Sodium Carbonate → 2-Cyano-4'-methylbiphenyl

HRID 248618Notes

Reaction equation

HRID 248618 reaction equation
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].C(=O)([O-])[O-].[Na+].[Na+].B(O)(O)[C:17]1[CH:18]=[CH:19][C:20]([CH3:23])=[CH:21][CH:22]=1>C(COC)OC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[C:4]([C:3]1[CH:6]=[CH:7][CH:8]=[CH:9][C:2]=1[C:17]1[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=1)#[N:5]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 162722-BromobenzonitrileHCID 79799Tolylboronic acid

Product 1

HCID 1455122-Cyano-4'-methylbiphenylYield 98.9%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Nitrogen was bubbled through a solution of 2-bromobenzonitrile (309.4 g, 1.70 mol) in dimethoxyethane (4.2 L) for 30 minutes then the following reagents added in succession: tetrakis(triphenylphosphine)palladium(O), (95 g, 0.082 mol); 2M aqueous sodium carbonate solution (1785 mL, 3.57 mol); and p-tolylboronic acid (239.1 g, 1.76 mol). The reaction mixture was heated under an atmosphere of nitrogen at 70° to 78° C. for 19 hours. The two-phase mixture was cooled to room temperature and the layers separated. The organic layer was evaporated to dryness under reduced pressure. The aqueous layer was extracted with ether (3×1.2 L) and the extracts added to the organic residue. The insoluble material was filtered off and washed with ether. The filtrate was dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. The oily residue was filtered to remove the solids and the filtrate distilled under high vacuum (0.1-0.2 torr) collecting the fraction boiling between 135° to 140° C. to afford 325 g of 2-cyano-4'-methylbiphenyl. MS (DEI) 193 (M+).

Workup

  1. additionthe following reagents added in succession
  2. temperatureThe reaction mixture was heated under an atmosphere of nitrogen at 70° to 78° C. for 19 hours
  3. customthe layers separated
  4. customThe organic layer was evaporated to dryness under reduced pressure
  5. extractionThe aqueous layer was extracted with ether (3×1.2 L)
  6. additionthe extracts added to the organic residue
  7. filtrationThe insoluble material was filtered off
  8. washwashed with ether
  9. dry with materialThe filtrate was dried over anhydrous magnesium sulfate
  10. customevaporated to dryness under reduced pressure
  11. filtrationThe oily residue was filtered
  12. customto remove the solids
  13. distillationthe filtrate distilled under high vacuum (0.1-0.2 torr)
  14. customcollecting the fraction
  15. customboiling between 135° to 140° C.

Sources & evidence

ORD record
ord-8e2f36ad352f436696347ebe1bfc044a
Source dataset
uspto-grants-1993_05
Patent number
US05210211

Reaction notes

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