Carbon Tetrachloride → HCID 21933937, compound

HRID 891322Notes

Reaction equation

HRID 891322 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:13](=[O:14])[C:12]([CH3:15])=[C:11]([C:16]3[CH:21]=[CH:20][C:19]([S:22]([CH3:25])(=[O:24])=[O:23])=[CH:18][CH:17]=3)[CH:10]=[N:9]2)=[CH:4][CH:3]=1.C(Cl)(Cl)(Cl)Cl.[Br:31]N1C(=O)CCC1=O>C(OCC)(=O)C.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:13](=[O:14])[C:12]([CH2:15][Br:31])=[C:11]([C:16]3[CH:21]=[CH:20][C:19]([S:22]([CH3:25])(=[O:23])=[O:24])=[CH:18][CH:17]=3)[CH:10]=[N:9]2)=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 5943Carbon TetrachlorideHCID 67184N-bromobutanimideHCID 21934174HCID 21934174, compound

Product 1

HCID 21933937HCID 21933937, compoundYield 74%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalyst3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
23 °C

Procedure

To a heterogeneous, refluxing solution of 2-(4-fluorophenyl)-4-methyl-5-[4-(methylsulfonyl)phenyl]-3(2H)-pyridazinone (590 mg, 1.65 mmol) and carbon tetrachloride (24 mL) was quickly added N-bromosuccinimide (yield: 308 mg, 1.73 mmol) followed by benzoyl peroxide (12 mg, 0.05 mmol). After 1 hour the reaction had only run to near 50% completion. Additional benzoyl peroxide (12 mg, 0.05 mmol) was added, and the reaction checked after another 1 hour. The reaction was still not complete, and so more benzoyl peroxide (4 mg, 0.017 mmol) was added. After 30 minutes, the reaction was completed. The mixture was cooled to 23° C. and diluted with ethyl acetate. The acetate solution was washed with saturated NaHCO3, water, and brine. The solution was dried over MgSO4, filtered, and concentrated in vacuo. The residue was chromatographed (flash silica gel, ethyl acetate/hexanes gradient 1:1 to 4:1) to provide the product (yield: 530 mg, 74%). 1H NMR (300 MHz, CDCl3) δ 3.16 (s, 3H), 4.34 (s, 2H), 7.20 (dd, J=8.8, 8.8 Hz, 2H), 7.67-7.74 (m, 2H), 7.82 (d, J=8.7 Hz, 2H), 7.86 (s, 1H), 8.17 (d, J=8.7 Hz, 2H). MS (APCI+) m/z 437 (M+H)+.

Workup

  1. waitthe reaction checked after another 1 hour
  2. waitAfter 30 minutes
  3. washThe acetate solution was washed with saturated NaHCO3, water, and brine
  4. dry with materialThe solution was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was chromatographed (flash silica gel, ethyl acetate/hexanes gradient 1:1 to 4:1)

Sources & evidence

ORD record
ord-44eedd284d3945cbb73f3e743e0caf3d
Source dataset
uspto-grants-2006_02
Patent number
US07001895B2

Reaction notes

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