Benzene, 1-bromo-3-iodo- → HCID 68412747, compound

HRID 2194697Notes

Reaction equation

HRID 2194697 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N:8]1[C:12]([S:13][CH2:14][CH2:15][C:16](OCC(CC)CCCC)=O)=[CH:11][C:10]([C:27]([O:29][CH2:30][CH3:31])=[O:28])=[N:9]1.[O-]CC.[Na+].[Br:36][C:37]1[CH:42]=CC=C(I)[CH:38]=1.C(N(C(C)C)C(C)C)C>C(O)C.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]>[Br:36][C:37]1[CH:38]=[C:14]([S:13][C:12]2[N:8]([C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=3[Cl:1])[N:9]=[C:10]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH:11]=2)[CH:15]=[CH:16][CH:42]=1

Participants

8

Reactant 4

HCID 11561Benzene, 1-bromo-3-iodo-HCID 81531DiisopropylethylamineHCID 2723922Sodium ethoxideHCID 68409671HCID 68409671, compound

Product 1

HCID 68412747HCID 68412747, compoundYield 61%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

A mixture of ethyl 1-(2-chlorophenyl)-5-({3-[(2-ethylhexyl)oxy]-3-oxopropyl}thio)-1H-pyrazole-3-carboxylate (1.21 g), sodium ethoxide (362 mg), 1-bromo-3-iodobenzene (775 mg), tris(dibenzylideneacetone)dipalladium (0) (97 mg), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthine (123 mg) and N-ethyldiisopropylamine (0.88 mL) was stirred at 80° C. for 12 hr in ethanol (10 mL) and toluene (15 mL). The reaction mixture was cooled to room temperature, and concentrated under reduced pressure. Water was added to the residue, and the mixture was extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=4:1) to give the title compound as a yellow oil (yield 689 mg, yield 61%).

Workup

  1. concentrationconcentrated under reduced pressure
  2. additionWater was added to the residue
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe extract was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=4:1)

Sources & evidence

ORD record
ord-f8e8a338650d4011b3080a23fd079592
Source dataset
uspto-grants-2012_12
Patent number
US08334301B2

Reaction notes

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