4-Iodobenzonitrile → HCID 57390371, compound

HRID 2167341Notes

Reaction equation

HRID 2167341 reaction equation
CC(C)([O-])C.[K+].[OH:7][C:8]1[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=1.I[C:15]1[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[CH:17][CH:16]=1>CS(C)=O>[N:11]1[CH:12]=[CH:13][C:8]([O:7][C:15]2[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[CH:17][CH:16]=2)=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 764674-IodobenzonitrileHCID 23665647Potassium tert-butoxideHCID 178418642HCID 178418642, compound

Product 1

HCID 57390371HCID 57390371, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Conditions

Temperature
160 °C

Procedure

Potassium tert-butoxide (1.0 M in THF, 10.5 mL) was slowly added to a solution of 4-hydroxypyridine (997 mg, 10.5 mmol) in anhydrous DMSO (10.0 mL). After the mixture was stirred for 3 hours, a solution of 4-iodobenzonitrile (1.2 g, 5.2 mmol) in DMSO (10.0 mL) was added and the reaction mixture was heated at 160° C. for 44 hours. The mixture was cooled to room temperature and partitioned between methylene chloride (100 mL) and water (100 mL). The organic layer was separated and the aqueous layer was extracted with methylene chloride (2×100 mL). The organic layers were combined and concentrated in vacuo. The crude solid was purified by silica gel column chromatography (Hex/EtOAc 1:1) then (CH2Cl2/MeOH 98:2 to 96:4) to give the product as a light yellow solid (480 mg, 47%). 1H NMR (500 MHz, CDCL3) δ(ppm): 6.52 (2H, d, J=8.0 Hz), 7.53 (2H, d, J=8.8 Hz), 7.64 (2H, d, J=8.0 Hz), 7.87 (2H, d, J=8.8 Hz). 13C NMR (125 MHz, CDCL3) δ(ppm): 112.4, 117.6, 119.8 (CH), 123.2 (CH), 134.5 (CH), 138.2 (CH), 146.2, 179.0. MS (FAB+): 197 (MH+). HRMS for O12H8N2O (MH+): calculated: 197.0715; found 197.0716.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. custompartitioned between methylene chloride (100 mL) and water (100 mL)
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with methylene chloride (2×100 mL)
  5. concentrationconcentrated in vacuo
  6. customThe crude solid was purified by silica gel column chromatography (Hex/EtOAc 1:1)

Sources & evidence

ORD record
ord-4a472944e15c45d7ab1fd2f3e4605d44
Source dataset
uspto-grants-2015_06
Patent number
US09045442B2

Reaction notes

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