Toluene → 3,4-Dichlorophenoxy-5-phenyl-benzaldehyde

HRID 2188263Notes

Reaction equation

HRID 2188263 reaction equation
[C:1]1(C)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:9]1[CH:10]=[CH:11][C:12]([O:17][C:18]2[CH:23]=[CH:22][C:21]([Cl:24])=[C:20]([Cl:25])[CH:19]=2)=[C:13]([CH:16]=1)[CH:14]=[O:15].C1(B(O)O)C=CC=CC=1.C([O-])([O-])=O.[Na+].[Na+]>O.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.C(O)C>[Cl:25][C:20]1[CH:19]=[C:18]([CH:23]=[CH:22][C:21]=1[Cl:24])[O:17][C:12]1[CH:11]=[CH:10][C:9]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[CH:16][C:13]=1[CH:14]=[O:15]

Participants

8

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 120170305-Bromo-2-(3,4-dichlorophenoxy)benzaldehyde

Product 1

HCID 120170323,4-Dichlorophenoxy-5-phenyl-benzaldehyde

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Under N2 in a 50 mL round bottomed flask fitted with a magnetic stirrer were placed the following reactants in order: 15 mL of toluene, 500 mg (1.4 mmol) of 5-bromo-2-(3,4-dichlorophenoxy)-benzaldehyde (from Preparation 1), 341 mg (2.8 mmol) of phenylboronic acid (Aldrich Chem. Co.), 1.5 mL of ethanol and 774 mg (5.6 mmol) of Na2CO3 in 3 mL of water. To this was added 45 mg (0.04 mmol) of tetrakis(triphenylphosphine)palladium (0) (Aldrich Chem. Co.), and the mixture was degassed with N2. The reaction was next heated to reflux for 4 hr, at which time a thin layer chromatography (tlc), using 1:1 CH2Cl2: hexane on silica gel coated plates, showed the absence of the starting aldehyde. After cooling, the mixture was diluted with 100 mL of EtOAc, washed twice with water, twice with 2 N NaOH, twice with water and finally with saturated aqueous NaCl. After drying over MgSO4, the solvent was removed in vacuo to give an oily residue, 690 mg. This was chromatographed on silica gel, eluting with CH2Cl2:hexane (1:1) to give the title product as an oil, 462 mg.

Workup

  1. customUnder N2 in a 50 mL round bottomed flask fitted with a magnetic stirrer
  2. customthe mixture was degassed with N2
  3. temperatureThe reaction was next heated
  4. temperatureto reflux for 4 hr, at which time a thin layer chromatography (tlc)
  5. temperatureAfter cooling
  6. additionthe mixture was diluted with 100 mL of EtOAc
  7. washwashed twice with water, twice with 2 N NaOH, twice with water and finally with saturated aqueous NaCl
  8. dry with materialAfter drying over MgSO4
  9. customthe solvent was removed in vacuo
  10. customto give an oily residue, 690 mg
  11. customThis was chromatographed on silica gel
  12. washeluting with CH2Cl2:hexane (1:1)

Sources & evidence

ORD record
ord-559db994f1264e098fd9681373bd5d17
Source dataset
uspto-grants-2002_06
Patent number
US06410736B1

Reaction notes

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