Cesium carbonate → HCID 68900138, compound

HRID 735374Notes

Reaction equation

HRID 735374 reaction equation
FC(F)(F)S([O:6][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:17]3[CH:22]=[CH:21][C:20]([F:23])=[CH:19][C:18]=3[C:24]#[N:25])[CH:13]=2)[CH:8]=1)(=O)=O.[C:28]1([S:34]([O-:36])=[O:35])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[Na+].C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2[C:64]3[O:63][C:62]4C(=CC=C[C:61]=4P(C4C=CC=CC=4)C4C=CC=CC=4)[C:56](C)(C)[C:55]=3[CH:54]=[CH:53][CH:52]=2)C=CC=CC=1>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[C:62]([O:6][CH2:7][CH3:16])(=[O:63])[CH3:61].[CH3:52][CH2:53][CH2:54][CH:55]([CH3:56])[CH3:64].[F:23][C:20]1[CH:21]=[CH:22][C:17]([C:12]2[CH:11]=[CH:10][C:9]3[C:14](=[CH:15][CH:16]=[C:7]([S:34]([C:28]4[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=4)(=[O:36])=[O:35])[CH:8]=3)[CH:13]=2)=[C:18]([CH:19]=1)[C:24]#[N:25]

Participants

10

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2723840Benzenesulfinic acid, sodium saltHCID 86616739HCID 86616739, compound

Product 2

HCID 21882781Isohexane ethyl acetateYield 40%HCID 68900138HCID 68900138, compoundYield 484%

Reagents, catalysts & solvents 4

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 6-(2-cyano-4-fluorophenyl)-2-naphthyl trifluoromethanesulfonate (0.65 g, 1.65 mmol), sodium benzene sulfinate (0.33 g, 1.97 mmol), cesium carbonate (0.81 g, 2.48 mmol), tris(dibenzylideneacetone)dipalladium(0) (38 mg, 0.04 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (49 mg, 0.08 mmol) and tetrabutylammonium chloride (0.55 g, 1.98 mmol) in toluene (15 mL) was heated at 120° C. under nitrogen for 4 hours. It was allowed to cool, poured into water (150 mL) and extracted with ethyl acetate (2×100 mL). These extracts were washed with water and brine then dried (MgSO4), filtered and solvent removed in vacuo. Purification by flash column chromatography eluting with 20% ethyl acetate/isohexane then 40% ethyl acetate/isohexane gave 5-fluoro-2-[6-(phenylsulfonyl)-2-naphthyl]benzonitrile (150 mg, 23%). 1H NMR (500 MHz, d6-DMSO) δ 8.82 (1H, s), 8.38 (1H, d, J=8.5 Hz), 8.26 (1H, s), 8.23 (1H, d, J=8.7 Hz), 8.05-8.03 (3H, m), 7.98 (1H, d, J=8.6 Hz), 7.88 (1H, d, J=8.5 Hz), 7.81-7.63 (5H, m); m/z (ES+) 388 [MH+].

Workup

  1. temperatureto cool
  2. extractionextracted with ethyl acetate (2×100 mL)
  3. washThese extracts were washed with water and brine
  4. dry with materialthen dried (MgSO4)
  5. filtrationfiltered
  6. customsolvent removed in vacuo
  7. customPurification by flash column chromatography
  8. washeluting with 20% ethyl acetate/isohexane

Sources & evidence

ORD record
ord-38ab949f9b6b4467ac4f28b69b2d4ba4
Source dataset
uspto-grants-2009_09
Patent number
US07592456B2

Reaction notes

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