Nitrogen → [1,1'-Biphenyl]-3,5-dicarboxaldehyde

HRID 58970Notes

Reaction equation

HRID 58970 reaction equation
[CH:1]1[C:6]([CH:7]=[O:8])=[CH:5][C:4](Br)=[CH:3][C:2]=1[CH:10]=[O:11].[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=O)([O-])[O-].[K+].[K+].N#N>COCCOC.O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:4]1([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:5]=[C:6]([CH:7]=[O:8])[CH:1]=[C:2]([CH:10]=[O:11])[CH:3]=1

Participants

7

Reactant 4

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 66827Phenylboronic AcidHCID 143832305-Bromobenzene-1,3-dicarbaldehyde

Product 1

HCID 14199327[1,1'-Biphenyl]-3,5-dicarboxaldehydeYield 74%

Reagents, catalysts & solvents 2

HCID 11776TriphenylphosphineCatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

A solution of 5-bromoisophthaldehyde (40.0 g, 187.8 mmol) (Med. Chem. Commun., 2012, 3, 763-770), phenylboronic acid (22.9 g, 187.8 mmol) and potassium carbonate (64.8 g, 469.5 mmol) in DME/H2O (5:1, 600 mL) was purged with N2 for 5 min. Tetrakispalladium triphenylphosphine (1.1 g, 0.9 mmol) was added, and the reaction mixture was heated to 90° C. and stirred for 16 h. The reaction mixture was cooled to rt, filtered through a pad of Celite diatomaceous earth, and the solvent evaporated under reduced pressure. Purification by column chromatography (10% EtOAc/hexanes) afforded the desired product (74%, 29.1 g) as an off-white solid. 1H NMR (300 MHz, CDCl3) δ ppm 10.18 (s, 2H), 8.37 (d, J=1.2 Hz, 2H), 8.35 (t, J=1.5 Hz, 1H), 7.70-7.66 (m, 2H), 7.55-7.43 (m, 3H).

Workup

  1. temperatureThe reaction mixture was cooled to rt
  2. filtrationfiltered through a pad of Celite diatomaceous earth
  3. customthe solvent evaporated under reduced pressure
  4. customPurification by column chromatography (10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-f759d7b6e5c44021974bb2f2423d3a34
Source dataset
uspto-grants-2016_09
Patent number
US09439433B2

Reaction notes

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