Diethyl Ether → 2-Chloro-4-iodobenzonitrile

HRID 1348904Notes

Reaction equation

HRID 1348904 reaction equation
N[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([Cl:10])[CH:3]=1.C(OCC)C.N([O-])=O.[Na+].[I-:20].[K+]>O>[Cl:10][C:4]1[CH:3]=[C:2]([I:20])[CH:9]=[CH:8][C:5]=1[C:6]#[N:7]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 4875Potassium IodideHCID 887284-Amino-2-chlorobenzonitrileHCID 23668193Sodium Nitrite

Product 1

HCID 179660212-Chloro-4-iodobenzonitrile

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A solution of 4-amino-2-chlorobenzonitrile (30.5 g, 0.2 mol) in 1:1 diethyl ether/3M HCl (600 mL) at 0° C. was treated dropwise over 15 minutes with a solution of sodium nitrite (18 g, 0.26 mol) in water (100 mL), stirred 15 minutes, then treated with a solution of potassium iodide (50 g, 0.3 mol) in water (50 mL) dropwise over 45 minutes, warmed to room temperature, and stirred for 1.5 hours. The organic phase was washed with water (3×100 mL) and the combined aqueous layers were extracted with diethyl ether. The combined organic layers were combined, washed sequentially with saturated NaHCO3, 25% Na2S2O3, and brine, dried (MgSO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 19:1/hexanes:ethyl acetate, triturated in hexanes, filtered, and dried to provide the desired product.

Workup

  1. stirringstirred for 1.5 hours
  2. washThe organic phase was washed with water (3×100 mL)
  3. extractionthe combined aqueous layers were extracted with diethyl ether
  4. washwashed sequentially with saturated NaHCO3, 25% Na2S2O3, and brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe concentrate was purified by flash column chromatography on silica gel with 19:1/hexanes
  9. customethyl acetate, triturated in hexanes
  10. filtrationfiltered
  11. customdried

Sources & evidence

ORD record
ord-a817e9abea0f4b0186560cc2d16ca612
Source dataset
uspto-grants-2007_05
Patent number
US07211595B2

Reaction notes

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