Pyridine → HCID 58528929, compound

HRID 1430997Notes

Reaction equation

HRID 1430997 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([OH:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[Br:13][C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.N1C=CC=CC=1>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH3:8][O:7][C:5](=[O:6])[C:4]1[CH:3]=[C:2]([OH:1])[CH:11]=[C:10]([O:12][C:17]2[CH:18]=[CH:19][C:14]([Br:13])=[CH:15][CH:16]=2)[CH:9]=1

Participants

6

Reactant 3

HCID 1049PyridineHCID 75076Methyl 3,5-DihydroxybenzoateHCID 79599(4-Bromophenyl)boronic acid2×

Product 1

HCID 58528929HCID 58528929, compoundYield 22.1%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of methyl 3,5-dihydroxybenzoate (8.0 g, 47.6 mmol) in DCM (800 mL) was added 4-bromophenylboronic acid (9.56 g, 47.6 mmol), copper(II) acetate (8.6 g, 47.6 mmol), 4 A molecular sieves (4 g), and pyridine (19.4 mL, 238.0 mmol). After stirring at rt for 72 h, more 4-bromophenylboronic acid (7 g, 35 mmol) was added and stirring continued for another 16 h. The solvent was evaporated and the reaction mixture was re-dissolved in diethyl ether. Washed with 1N HCl, brine, dried (MgSO4) and evaporated. The residue was subjected to silica gel chromatography using an ethyl acetate-hexane gradient to afford 3.4 g (22%) of 3-(4-Bromophenoxy)-5-hydroxybenzoic acid methyl ester. 1H NMR (300 MHz, DMSO-d6) δ 3.78 (s, 3H), 6.64-6.66 (m, 1H), 6.89 (dd, 1H, J=2, 1 Hz), 7.02 (dd, 2H, J=7, 2 Hz), 7.12 (dd, 1H, J=2, 1 Hz), 7.57 (dd, 2H, J=7, 2 Hz).

Workup

  1. stirringstirring
  2. waitcontinued for another 16 h
  3. customThe solvent was evaporated
  4. dissolutionthe reaction mixture was re-dissolved in diethyl ether
  5. washWashed with 1N HCl, brine
  6. dry with materialdried (MgSO4)
  7. customevaporated

Sources & evidence

ORD record
ord-a20debebfe0e46a1b6d417e4a5225da6
Source dataset
uspto-grants-2015_01
Patent number
US08940927B2

Reaction notes

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