Dichloromethane → HCID 10644380, compound

HRID 1839954Notes

Reaction equation

HRID 1839954 reaction equation
Cl[C:2]1[CH:7]=[C:6]([S:8]([C:11](F)(F)F)(=[O:10])=[O:9])[C:5](C2C=CC(SC)=CC=2)=[CH:4]C=1Cl.[F:24][C:25]1[CH:30]=[CH:29][C:28](B(O)O)=[CH:27][CH:26]=1.C([O-])([O-])=O.[K+].[K+].[Cl:40][C:41]1[CH:46]=[CH:45][CH:44]=[C:43]([C:47](OO)=O)[CH:42]=1.C(Cl)[Cl:52]>C1(C)C=CC=CC=1.C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:40][C:41]1[CH:42]=[C:43]([C:47]2[CH:2]=[CH:7][C:6]([S:8]([CH3:11])(=[O:10])=[O:9])=[CH:5][CH:4]=2)[C:44]([C:28]2[CH:29]=[CH:30][C:25]([F:24])=[CH:26][CH:27]=2)=[CH:45][C:46]=1[Cl:52]

Participants

9

Reactant 5

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 70297m-Chloroperbenzoic acidHCID 2856454-Fluorophenylboronic acidHCID 23451096HCID 23451096, compound

Product 1

HCID 10644380HCID 10644380, compoundYield 33%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Under nitrogen, 480 mg (0.42 mmol) of Pd(PPh3)4 was added to a stirred solution of 1.64 g (3.93 mmol) of 1,2-dichloro-4-[4-(methylthio)phenyl]-5-(trifluoromethanesulfonyl)benzene (Step 5), 1.1 g (7.9 mmol) of 4-fluorophenylboronic acid and 1.6 g (11.6 mmol) of anhydrous K2CO3 powder in 20 mL of toluene. The reaction was vigorously stirred at reflux for 7 days, and cooled to ambient temperature. The reaction mixture was diluted with ethyl acetate. The resulting solution was washed with water, and dried over MgSO4. Purification by silica gel plug with ethyl acetate/hexane (5:95) gave an oil residue which was subsequently dissolved in 15 mL of CH2Cl2. The resulting solution was treated with 1.4 g (11.8 mmol) of 3-chloroperbenzoic acid (MCPBA) (70%) at 0° C.; and the reaction was stirred overnight at ambient temperature. Excess MCPBA was quenched by the addition of Na2SO3 at 0° C., and stirred for 30 minutes at ambient temperature. The mixture was diluted with CH2Cl2, the resulting solution was washed with water and brine, and dried over Na2SO4. Purification by silica gel chromatography (MPLC) with ethyl acetate/hexane (3:7) gave 505 mg (33%) of 1,2-dichloro-4-(4-fluorophenyl)-5-[4-(methylsulfonyl)phenyl]benzene as a colorless solid: mp 143.5-144.5° C.; NMR (CDCl3) δ 3.05 (s, 3H), 6.95 (d, J=9 Hz, 2H), 6.99-7.07 (m, 2H), 7.30 (d, J=9 Hz, 2H), 7.52 (d, J=9 Hz, 2H), 7.83 (d, J=9 Hz, 2H); MS (CI) m/z 395 (M+H)+; HRMS calc'd for (M+Li)+ 401.0157, found 401.0142. Anal. Calc'd for C19H13O2SFCl2: C, 57.73; H, 3.31; F, 4.81; Cl, 17.94. Found: C, 57.89; H, 3.45; F, 4.81; Cl, 17.56.

Workup

  1. temperatureat reflux for 7 days
  2. washThe resulting solution was washed with water
  3. dry with materialdried over MgSO4
  4. customPurification by silica gel plug with ethyl acetate/hexane (5:95)
  5. customgave an oil residue which
  6. stirringand the reaction was stirred overnight at ambient temperature
  7. customExcess MCPBA was quenched by the addition of Na2SO3 at 0° C.
  8. stirringstirred for 30 minutes at ambient temperature
  9. additionThe mixture was diluted with CH2Cl2
  10. washthe resulting solution was washed with water and brine
  11. dry with materialdried over Na2SO4
  12. customPurification by silica gel chromatography (MPLC) with ethyl acetate/hexane (3:7)

Sources & evidence

ORD record
ord-3a122f9611e8402492351b59c833c4a1
Source dataset
uspto-grants-2004_01
Patent number
US06677488B2

Reaction notes

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