3-Bromobenzoic acid → 3-(4-methoxyphenyl)sulfanylbenzoic Acid

HRID 2245899Notes

Reaction equation

HRID 2245899 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]([OH:10])=[O:9])[CH:5]=[CH:6][CH:7]=1.CCN(C(C)C)C(C)C.[CH3:20][O:21][C:22]1[CH:27]=[CH:26][C:25]([SH:28])=[CH:24][CH:23]=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].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.O1CCOCC1>[CH3:20][O:21][C:22]1[CH:27]=[CH:26][C:25]([S:28][C:2]2[CH:3]=[C:4]([C:8]([OH:10])=[O:9])[CH:5]=[CH:6][CH:7]=2)=[CH:24][CH:23]=1

Participants

7

Reactant 3

HCID 114563-Bromobenzoic acidHCID 127654-MethoxybenzenethiolHCID 81531Diisopropylethylamine

Product 1

HCID 112424193-(4-methoxyphenyl)sulfanylbenzoic AcidYield 83%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

3-Bromobenzenecarboxylic acid (402 mg, 2 mmol), i-Pr2NEt (700 μL, 4 mmol) and dry 1,4-dioxane (8 mL) were put into a round-bottomed flask, and the round-bottomed flask with the resulting mixture therein was purged repeated three times with nitrogen gas. Next, Pd2(dba)3 (46 mg, 0.05 mmol), Xantphos (58 mg, 0.1 mmol) and 4-methoxythiophenol (246 μL, 2 mmol) were added to it, and this was purged repeatedly twice with nitrogen gas, and then heated under reflux for 6 hours. Next, the completion of the reaction was confirmed through high-performance liquid chromatography, then this was cooled to room temperature, and made to have a pH of 3 to 4 with acetic acid. The insoluble matter was removed through filtration, and the filtrate was concentrated. The resulting concentrate liquid was isolated and purified through flash column chromatography (developer: hexane/ethyl acetate=10/1) with silica gel serving as a carrier, thereby giving 432 mg (yield: 83%) of 3-(4-methoxyphenyl)sulfanylbenzenecarboxylic acid as a white solid.

Workup

  1. customthe round-bottomed flask with the resulting mixture therein was purged
  2. customthis was purged repeatedly twice with nitrogen gas
  3. temperatureheated
  4. temperatureunder reflux for 6 hours
  5. customThe insoluble matter was removed through filtration
  6. concentrationthe filtrate was concentrated
  7. concentrationThe resulting concentrate liquid
  8. customwas isolated
  9. custompurified through flash column chromatography (developer: hexane/ethyl acetate=10/1) with silica gel serving as a carrier

Sources & evidence

ORD record
ord-29a60c1e0746461e81b3647ce1afc57e
Source dataset
uspto-grants-2010_03
Patent number
US07683218B2

Reaction notes

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