Sodium Carbonate → 3-(pyridin-4-yl)benzaldehyde

HRID 885023Notes

Reaction equation

HRID 885023 reaction equation
Cl.Br[C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1.C([O-])([O-])=O.[Na+].[Na+].[CH:15]([C:17]1[CH:18]=[C:19](B(O)O)[CH:20]=[CH:21][CH:22]=1)=[O:16]>O.C1(C)C=CC=CC=1.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>[N:6]1[CH:7]=[CH:8][C:3]([C:21]2[CH:22]=[C:17]([CH:18]=[CH:19][CH:20]=2)[CH:15]=[O:16])=[CH:4][CH:5]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 881004-Bromopyridinium chlorideHCID 27343563-Formylphenylboronic acid

Product 1

HCID 27955633-(pyridin-4-yl)benzaldehydeYield 85%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of 4-bromopyridine hydrochloride (533.4 mg, 2.7 mmol) in water (4.0 mL) and toluene (4.8 mL) was added slowly a solution of Na2CO3 (714 mg, 6.7 mmol) in water (7.0 mL) at room temperature. The solution was then mixed with 3-formylbenzeneboronic acid (431 mg, 2.9 mmol), Pd(PPh3)4 (100 mg, 0.086 mmol). The reaction mixture was stirred at 85° C. for 24 h, and then cooled to room temperature. The reaction was worked up by extraction of the mixture with CH2Cl2 (4×5 mL). The combined organic phase was dried over anhydrous Na2SO4. The solvent was removed under vacuum, and the residue was purified by a flash chromatography (silica gel, petroleum ether/EtOAc=¼) to give product 10 (420 mg) in 85% yield; 1H NMR (300 MHz, CDCl3): 10.1 (s, 1H), 8.72-8.74 (m, 2H), 8.17 (s, 1H), 7.90-7.99 (m, 2H), 7.69 (t, J=11.4 Hz, 1H), 7.57 (d, J=6.6 Hz, 2H); 13C NMR (75 MHz CDCl3): δ191.5, 150.3, 146.5, 138.8, 136.8, 132.5, 130.1, 129.6, 127.5, 121.3; HRMS (ESI) calcd for C12H9NO (M. Hi) 184.07569; found 184.07538.

Workup

  1. temperaturecooled to room temperature
  2. extractionThe reaction was worked up by extraction of the mixture with CH2Cl2 (4×5 mL)
  3. dry with materialThe combined organic phase was dried over anhydrous Na2SO4
  4. customThe solvent was removed under vacuum
  5. customthe residue was purified by a flash chromatography (silica gel, petroleum ether/EtOAc=¼)

Sources & evidence

ORD record
ord-5b66e37257fa4019b41cb9da16d10e5c
Source dataset
uspto-grants-2012_08
Patent number
US08242142B2

Reaction notes

Loading…