Boron Trichloride → Methyl 3-cyano-5-hydroxybenzoate

HRID 431866Notes

Reaction equation

HRID 431866 reaction equation
C([O:4][C:5]1[CH:6]=[C:7]([CH:12]=[C:13]([C:15]#[N:16])[CH:14]=1)[C:8]([O:10][CH3:11])=[O:9])C=C.B(Cl)(Cl)Cl>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl>[C:15]([C:13]1[CH:12]=[C:7]([CH:6]=[C:5]([OH:4])[CH:14]=1)[C:8]([O:10][CH3:11])=[O:9])#[N:16]

Participants

5

Reactant 2

HCID 25135Boron TrichlorideHCID 21942395Methyl 3-(allyloxy)-5-cyanobenzoate

Product 1

HCID 21942421Methyl 3-cyano-5-hydroxybenzoateYield 67%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A mixture of methyl 3-allyloxy-5-cyanobenzoate (1.5 g, 6.9 mmol) and tetrabutylammonium iodide (2.8 g, 7.6 mmol) in dichloromethane (38 mL) at −78° C., under argon, was treated with a solution of 1M boron trichloride in dichloromethane (24 mL, 24 mmol). After 5 minutes at −78° C., the reaction mixture was stirred at ambient temperature for 1 hour. The reaction was then quenched with ice water and stirred for an additional 30 minutes. The organic layer was washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, filtered and concentrated. Silica gel chromatography using a gradient of 20-30% ethyl acetate/hexanes afforded 811 mg (67%) of methyl 3-cyano-5-hydroxybenzoate as a light yellow solid.

Workup

  1. customThe reaction was then quenched with ice water
  2. stirringstirred for an additional 30 minutes
  3. washThe organic layer was washed with saturated sodium bicarbonate
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-6ae0c2f14a0741a59f29d02fc98375c3
Source dataset
uspto-grants-2003_12
Patent number
US06660753B2

Reaction notes

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