4-Fluorobenzonitrile → HCID 23507807, compound

HRID 381599Notes

Reaction equation

HRID 381599 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:5]=[CH:6][CH:7]=1.F[C:15]1[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[CH:17][CH:16]=1.[OH-].[K+]>CS(C)=O.O>[C:19]([C:18]1[CH:21]=[CH:22][C:15]([O:1][C:2]2[CH:3]=[C:4]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:5]=[CH:6][CH:7]=2)=[CH:16][CH:17]=1)#[N:20]

Participants

6

Reactant 3

HCID 145174-FluorobenzonitrileHCID 14797Potassium HydroxideHCID 572437Ethyl (3-Hydroxyphenyl)acetate

Product 1

HCID 23507807HCID 23507807, compoundYield 49.3%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Procedure

A solution of ethyl 3-hydroxyphenylacetate (28 g, 0.15 mole) and 4-fluorobenzonitrile (25 g, 0.21 mole) in dimethylsulfoxide (150 ml) was stirred with 87% potassium hydroxide (10 g, 0.15 mole) at 75-80° C. for 80 minutes under nitrogen. The resulting mixture was allowed to cool, diluted with water (1000 ml), and extracted with diethyl ether (2×50 ml). The organic solution was washed with water (100 ml), dried (MgSO4), concentrated in vacuo and the residue eluted on silica gel (500 g) with ethyl acetate: hexane (0 to 1:6). A solution of the product in diethyl ether (125 ml) was washed with 1N NaOH (15 ml) to remove some residual phenol, dried (K2CO3 and MgSO4), and concentrated in vacuo to give ethyl 3-(4-cyanophenyloxy)phenylacetate (20.8 g). 1H NMR (DMSO-d6, 300 MHz) δ: 1.18 (t, J=7 Hz, 3H, CH3), 3.71 (s, 2H, Ar CH2), 4.08 (q, J=7 Hz, 2H, ester CH2), 7.02-7.13 (m, 4H, Ar), 7.18 (d, J=8 Hz, 1H, Ar), 7.42 (t, J=8 Hz, 1H, Ar), 7.85 (d, J=9 Hz, 2H, Ar). Anal. Calculated for C17H15NO3: C, 72.58; H, 5.37; N, 4.98. Found: C, 72.67; H, S.43; N, 4.94.

Workup

  1. temperatureto cool
  2. extractionextracted with diethyl ether (2×50 ml)
  3. washThe organic solution was washed with water (100 ml)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. washthe residue eluted on silica gel (500 g) with ethyl acetate
  7. washA solution of the product in diethyl ether (125 ml) was washed with 1N NaOH (15 ml)
  8. customto remove some residual phenol
  9. dry with materialdried (K2CO3 and MgSO4)
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ba6f22c8ce054b64870c877090050c82
Source dataset
uspto-grants-2001_10
Patent number
US06306865B1

Reaction notes

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