Ethanol → HCID 57615229, compound

HRID 1644136Notes

Reaction equation

HRID 1644136 reaction equation
Br[C:2]1[C:3]2[C:8]([C:9](Br)=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[CH:11]3)=[CH:7][CH:6]=[CH:5][CH:4]=2.[CH:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1B(O)O)=[O:18].[C:28](=[O:31])([O-])[O-].[Na+].[Na+].[CH2:34](O)[CH3:35]>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl.C1(P([Pd-4](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)C=CC=CC=1.O>[CH:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[C:2]1[C:3]2[C:8]([C:9]([C:35]3[CH:34]=[CH:14][CH:15]=[CH:2][C:3]=3[CH:28]=[O:31])=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[CH:11]3)=[CH:7][CH:6]=[CH:5][CH:4]=2)=[O:18]

Participants

9

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 682269,10-DibromoanthraceneHCID 2921892-Formylphenylboronic acid

Product 1

HCID 57615229HCID 57615229, compound

Reagents, catalysts & solvents 4

HCID 178420553HCID 178420553, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 6212ChloroformSolvent

Procedure

2.3 g (2 mmol) of tetrakistriphenylphosphinopalladium(0) are added to a well-stirred, degassed suspension of 33.6 g (100 mmol) of 9,10-dibromo-anthracene, 45.0 g (300 mmol) of 2-formylbenzeneboronic acid and 55.1 g (520 mmol) of sodium carbonate in a mixture of 500 ml of toluene, 150 ml of ethanol and 400 ml of water, and the mixture is refluxed for 60 h. After cooling, the organic phase is separated off, washed three times with 500 ml of water and once with 500 ml of saturated, aqueous sodium chloride solution and subsequently dried over magnesium sulfate. After the drying agent has been filtered off, the organic phase is evaporated to dryness under reduced pressure in a rotary evaporator. The oily residue obtained in this way is dissolved in 300 ml of chloroform and filtered through a silica-gel frit with suction. After evaporation of the chloroform phase under reduced pressure, the pasty residue is taken up in 200 ml of ethanol and stirred at room temperature for 1 h. The deposited crystals are filtered off with suction, washed with 50 ml of ethanol and subsequently dried under reduced pressure; yield. 24.5 g, 63.4% of theory, 98% according to 1H-NMR. According to 1H-NMR, this fraction comprises two atropisomers, evident from the two spectroscopically resolved signals of the formyl protons, in the ratio 1.0 (δ=9.43 ppm):1.5 (δ=9.40 ppm). The ethanol mother liquor is concentrated to an oil under reduced pressure; yield: 12.8 g, 33.1% of theory, 97% according to 1H-NMR. According to 1H-NMR, this fraction comprises two atropisomers in the ratio 1.0 (δ=9.43 ppm):2.9 (δ=9.40 ppm).

Workup

  1. customdegassed
  2. temperaturethe mixture is refluxed for 60 h
  3. temperatureAfter cooling
  4. customthe organic phase is separated off
  5. washwashed three times with 500 ml of water
  6. dry with materialonce with 500 ml of saturated, aqueous sodium chloride solution and subsequently dried over magnesium sulfate
  7. filtrationAfter the drying agent has been filtered off
  8. customthe organic phase is evaporated to dryness under reduced pressure in a rotary evaporator
  9. customThe oily residue obtained in this way
  10. filtrationfiltered through a silica-gel frit with suction
  11. customAfter evaporation of the chloroform phase under reduced pressure
  12. filtrationThe deposited crystals are filtered off with suction
  13. washwashed with 50 ml of ethanol
  14. customsubsequently dried under reduced pressure
  15. customyield
  16. concentrationThe ethanol mother liquor is concentrated to an oil under reduced pressure

Sources & evidence

ORD record
ord-5e8d4c7957524a648a0c7d26530c4da0
Source dataset
uspto-grants-2012_02
Patent number
US08124249B2

Reaction notes

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