Sodium Bicarbonate → Benzyl 2-(benzyloxy)-5-(pyridin-4-yl)benzoate

HRID 454465Notes

Reaction equation

HRID 454465 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=2)O1.C(=O)(O)[O-].[Na+].[CH2:21]([O:28][C:29]1[CH:44]=[CH:43][C:42](Br)=[CH:41][C:30]=1[C:31]([O:33][CH2:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:32])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)(=O)C.O.COCCOC>[CH2:21]([O:28][C:29]1[CH:44]=[CH:43][C:42]([C:9]2[CH:10]=[CH:11][N:12]=[CH:13][CH:14]=2)=[CH:41][C:30]=1[C:31]([O:33][CH2:34][C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)=[O:32])[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

Participants

8

Reactant 3

HCID 516892Sodium Bicarbonate2×HCID 27346484-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine2×HCID 17750009Benzyl 2-(benzyloxy)-5-bromobenzoate

Product 1

HCID 66990917Benzyl 2-(benzyloxy)-5-(pyridin-4-yl)benzoateYield 72.8%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalyst2×HCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Water (1.2 mL), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (0.25 g), sodium bicarbonate (0.21 g), and bis(triphenylphosphine)palladium(II) dichloride (14 mg) were added to an ethylene glycol dimethyl ether (4 mL) solution of benzyl 2-(benzyloxy)-5-bromobenzoate (0.40 g), followed by heating to reflux under a nitrogen atmosphere for 2 hours. The reaction mixture was cooled to room temperature, and then 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (0.12 g), sodium bicarbonate (0.10 g), and bis(triphenylphosphine)palladium(II) dichloride (14 mg) were added thereto, followed by heating to reflux under a nitrogen atmosphere for 2 hours. After cooling the reaction mixture to room temperature, water and ethyl acetate were added thereto, and the insoluble substance was removed by filtration. The organic layer was separated, washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography [Fuji Silysia Chemical Ltd., PSQ100B (spherical), eluent: 90-45% hexane/ethyl acetate] to obtain 0.29 g of benzyl 2-(benzyloxy)-5-(pyridin-4-yl)benzoate as a white solid.

Workup

  1. temperatureby heating
  2. temperatureto reflux under a nitrogen atmosphere for 2 hours
  3. temperatureby heating
  4. temperatureto reflux under a nitrogen atmosphere for 2 hours
  5. temperatureAfter cooling the reaction mixture to room temperature
  6. customthe insoluble substance was removed by filtration
  7. customThe organic layer was separated
  8. washwashed with a saturated aqueous solution of sodium chloride
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customthe solvent was evaporated under reduced pressure
  11. customThe obtained residue was purified by silica gel column chromatography [Fuji Silysia Chemical Ltd., PSQ100B (spherical), eluent: 90-45% hexane/ethyl acetate]

Sources & evidence

ORD record
ord-de91a38cd9594c439c0551da31e42b8a
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

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