Ethyl 3,4-Diaminobenzoate → 4-Methoxycarbonylphenylboronic acid

HRID 1408848Notes

Reaction equation

HRID 1408848 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[CH:9][C:8](N)=[C:7](N)[CH:6]=1)C.[B:14]1(B2OC(C)(C)C(C)(C)O2)[O:18]C(C)(C)C(C)(C)[O:15]1.C([O-])(=O)C.[K+]>O1CCOCC1.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>[CH3:1][O:3][C:4]([C:5]1[CH:10]=[CH:9][C:8]([B:14]([OH:18])[OH:15])=[CH:7][CH:6]=1)=[O:13]

Participants

7

Reactant 3

HCID 458855Ethyl 3,4-DiaminobenzoateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diborane

Product 1

HCID 27343694-Methoxycarbonylphenylboronic acidYield 228.9%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

Referring to Scheme 11-1, to a solution of the bromide 1 (2.0 g, 4.2 mmol, prepared according to published conditions) in dioxane (60 mL) was added bis(pinacolato)diboron (4.32 g, 17 mmol), Pd(PPh3)4 (0.49 g, 0.42 mmol) and potassium acetate (2.06 g, 21 mmol) under nitrogen atmosphere. The reaction mixture was stirred at 80° C. for 5 h, and then diluted with ethyl acetate (150 mL). The organic phase was washed with H2O (20 mL), dried over sodium sulfate and concentrated in vacuo. The residue was further purified by silica gel column chromatography (hexanes/ethyl acetate=1/4 to 0/1 (v/v)) to give 2 (1.73 g, 79% yield). LC-MS (ESI): m/z 523.3 (M+H)+.

Workup

  1. washThe organic phase was washed with H2O (20 mL)
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated in vacuo
  4. customThe residue was further purified by silica gel column chromatography (hexanes/ethyl acetate=1/4 to 0/1 (v/v))

Sources & evidence

ORD record
ord-b1256e96338b43389542ce5345398994
Source dataset
uspto-grants-2014_12
Patent number
US08921369B2

Reaction notes

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