Lithium iodide → 3-Chloro-5-hydroxybenzonitrile

HRID 457543Notes

Reaction equation

HRID 457543 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:10]C)[CH:9]=1)[C:5]#[N:6].[I-].[Li+]>N1C(C)=CC(C)=CC=1C>[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([OH:10])[CH:9]=1)[C:5]#[N:6]

Participants

4

Reactant 2

HCID 66321Lithium iodideHCID 219499213-Chloro-5-methoxybenzonitrile

Product 1

HCID 219498783-Chloro-5-hydroxybenzonitrileYield 91%

Reagents, catalysts & solvents 1

HCID 79532,4,6-TrimethylpyridineSolvent

Conditions

Temperature
175 °C

Procedure

A 250 mL round bottom flask was charged 3-chloro-5-methoxybenzonitrile (4.2 g; 25.05 mmol) and 2,4,6-collidine (60 mL) was added. The mixture was stirred under an argon atmosphere until the solution was homogeneous. Anhydrous lithium iodide (10.06 g; 75.18 mmol) was added and the mixture was heated to 175° C. for 3 h. The reaction mixture was cooled to RT and partitioned between 10% HCl and EtOAc. The EtOAc phase was washed sequentially with 10% HCl and brine, dried (Na2SO4), filtered and evaporated in vacuo to afford a oil which was crystallized from hexanes to afford 3-chloro-5-hydroxybenzonitrile (130c, 3.5 g, 91% theory).

Workup

  1. additionwas added
  2. temperatureThe reaction mixture was cooled to RT
  3. custompartitioned between 10% HCl and EtOAc
  4. washThe EtOAc phase was washed sequentially with 10% HCl and brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated in vacuo
  8. customto afford a oil which
  9. customwas crystallized from hexanes

Sources & evidence

ORD record
ord-0318f21247d6452f94b7be96e238e15a
Source dataset
uspto-grants-2007_03
Patent number
US07189718B2

Reaction notes

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