Isopentyltriphenylphosphonium bromide → 2-(3,4-Difluorophenyl)-4-(6-methyl-3-heptenyl)-5-[4-(methylsulfonyl)phenyl]-3(2h)-pyridazinone

HRID 1241763Notes

Reaction equation

HRID 1241763 reaction equation
[Br-].[CH2:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:3][CH:4]([CH3:6])[CH3:5].CC(C)([O-])C.[K+].[F:32][C:33]1[CH:34]=[C:35]([N:40]2[C:45](=[O:46])[C:44]([CH2:47][CH2:48][CH:49]=O)=[C:43]([C:51]3[CH:56]=[CH:55][C:54]([S:57]([CH3:60])(=[O:59])=[O:58])=[CH:53][CH:52]=3)[CH:42]=[N:41]2)[CH:36]=[CH:37][C:38]=1[F:39]>C1(C)C=CC=CC=1>[F:32][C:33]1[CH:34]=[C:35]([N:40]2[C:45](=[O:46])[C:44]([CH2:47][CH2:48][CH:49]=[CH:2][CH2:3][CH:4]([CH3:6])[CH3:5])=[C:43]([C:51]3[CH:56]=[CH:55][C:54]([S:57]([CH3:60])(=[O:58])=[O:59])=[CH:53][CH:52]=3)[CH:42]=[N:41]2)[CH:36]=[CH:37][C:38]=1[F:39]

Participants

5

Reactant 3

HCID 2759379Isopentyltriphenylphosphonium bromideHCID 219341612-(3,4-Difluorophenyl)-4-(2-formylethyl)-5-[4-(methylsulfonyl)phenyl]-3(2h)-pyridazinoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 537185062-(3,4-Difluorophenyl)-4-(6-methyl-3-heptenyl)-5-[4-(methylsulfonyl)phenyl]-3(2h)-pyridazinoneYield 13%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of isoamyltriphenylphosphonium bromide (414 mg, 1 mmol) and potassium t-butoxide (112 mg, 1 mmol) in toluene (25 mL) was refluxed for 30 minutes and then cooled to room temperature. The crude aldehyde was added and the mixture was refluxed for 14 hours. The reaction mixture was then cooled to room temperature and concentrated in vacuo. The residue was dissolved in ethyl acetate and was washed with water, 10% citric acid, brine, dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (silica gel, 1:1 hexanes-ethyl acetate) provided the title compound as an oil (yield: 120 mg, 13%). 1H NMR (300 MHz, DMSO-d6) δ 0.74 (d, J=7 Hz, 6H), 1.44 (m, 1H), 1.70 (t, J=7 Hz, 2H), 2.22 (m, 2H), 2.54 (m, 2H); 3.30 (s, 3H), 5.29 (m, 2H), 7.51 (m, 1H), 7.63 (m, 1H), 7.74 (d, J=9 Hz, 2H), 7.82 (m, 1H), 8.02 (s, 1H), 8.10 (d, J=9 Hz, 2H). MS (APCI+) m/z 473 (M+H)+ and (APCI−) m/z 471 (M−H)−, m/z 507 (M+Cl)−. Anal. calc. for C25H26F2N2O3S: C, 63.54; H, 5.54; N, 5.92. Found: C, 63.74; H, 5.67; N, 5.58.

Workup

  1. temperaturewas refluxed for 30 minutes
  2. temperaturethe mixture was refluxed for 14 hours
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. concentrationconcentrated in vacuo
  5. dissolutionThe residue was dissolved in ethyl acetate
  6. washwas washed with water, 10% citric acid, brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customPurification by column chromatography (silica gel, 1:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-62de3124667f4f83a5b2f3a2106aecd6
Source dataset
uspto-grants-2006_10
Patent number
US07115591B2

Reaction notes

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