4-Fluoroiodobenzene → 2,4-Bis(4-fluorophenyl)-5-[4-(methylsulfonyl)phenyl]-3(2H)-pyridazinone

HRID 891285Notes

Reaction equation

HRID 891285 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9](=[O:24])[NH:10][N:11]=[CH:12][C:13]=2[C:14]2[CH:19]=[CH:18][C:17]([S:20]([CH3:23])(=[O:22])=[O:21])=[CH:16][CH:15]=2)=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[F:31][C:32]1[CH:37]=[CH:36][C:35](I)=[CH:34][CH:33]=1>N1C=CC=CC=1>[F:31][C:32]1[CH:37]=[CH:36][C:35]([N:10]2[C:9](=[O:24])[C:8]([C:5]3[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=3)=[C:13]([C:14]3[CH:19]=[CH:18][C:17]([S:20]([CH3:23])(=[O:22])=[O:21])=[CH:16][CH:15]=3)[CH:12]=[N:11]2)=[CH:34][CH:33]=1

Participants

5

Reactant 3

HCID 96054-FluoroiodobenzeneHCID 11430Potassium CarbonateHCID 102911854-(4-Fluorophenyl)-5-[4-(methylsulfonyl)phenyl]-3(2H)-pyridazinone

Product 1

HCID 102748312,4-Bis(4-fluorophenyl)-5-[4-(methylsulfonyl)phenyl]-3(2H)-pyridazinoneYield 79.9%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A mixture of 4-(4-fluorophenyl)-5-[4-(methylsulfonyl)phenyl]-3(2H)-pyridazinone (172 mg, 0.5 mmol), prepared according to the method of Example 10, Cu powder (32 mg), anhydrous K2CO3 (207 mg, 1.5 mmol) and 4-fluoroiodobenzene (0.12 mL, 1 mmol) was prepared in 20 mL of pyridine. The solution was stirred at reflux for 14 hours. The mixture was then cooled to room temperature and partitioned between water and ethyl acetate. The ethyl acetate layer was washed with 10% citric acid, water, brine and concentrated in vacuo. Separation by column chromatography (silica gel, CH2Cl2-diethyl ether 15:1) provided 190 mg of crude product. Crystallization from CH2Cl2-diethyl ether-hexanes furnished the title compound (yield: 175 mg, 79.9%). mp 168-169° C. 1H NMR (300 MHz, CDCl3) δ 3.07 (s, 3H), 6.98 (t, J=9 Hz, 2H), 7.20 (m, 4H), 7.40 (d, J=9 Hz, 2H), 7.69 (m, 2H), 7.92 (d, J=9 Hz, 2H), 7.98 (s, 1H). MS (DCI/NH3) m/z 439 (M+H)+, 456 (M+NH4)+. Anal. calc. for C23H16F2N2O3S.0.25H2O: C, 62.36; H, 3.75; N, 6.32. Found: C, 62.23; H, 3.55; N, 6.26.

Workup

  1. customprepared
  2. temperatureat reflux for 14 hours
  3. custompartitioned between water and ethyl acetate
  4. washThe ethyl acetate layer was washed with 10% citric acid, water, brine
  5. concentrationconcentrated in vacuo
  6. customSeparation by column chromatography (silica gel, CH2Cl2-diethyl ether 15:1)
  7. customprovided 190 mg of crude product
  8. customCrystallization from CH2Cl2-diethyl ether-hexanes

Sources & evidence

ORD record
ord-f1e840dddf2f44af81917a0721e8f1ab
Source dataset
uspto-grants-2006_02
Patent number
US07001895B2

Reaction notes

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