Toluene → Phenanthrene

HRID 1091320

반응식

HRID 1091320 반응식
CC1C2C(=CC=CC=2)C(B(O)O)=CC=1.Br[C:16]1[CH:29]=[CH:28][C:27]2[C:26]3[C:21](=[CH:22][C:23](Br)=[CH:24][CH:25]=3)[C:20](C)=[C:19](C)[C:18]=2[CH:17]=1.C1(C)C=CC=CC=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH:22]1[C:21]2[CH:20]=[CH:19][C:18]3[C:27](=[CH:28][CH:29]=[CH:16][CH:17]=3)[C:26]=2[CH:25]=[CH:24][CH:23]=1

참가 물질

8

반응물 4

HCID 1140TolueneHCID 80271Tri-o-tolylphosphineHCID 27735114-Methyl-1-naphthaleneboronic acidHCID 23116746HCID 23116746, 화합물

생성물 1

HCID 995Phenanthrene

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 312751,4-Dioxane용매

실험 절차

A degassed, efficiently stirred suspension of 37.2 g (200 mmol) of 4-methylnaphtalene-1-boronic acid, 18.0 g (50 mmol) of 2,7-dibromo-9,10-dimethylphenanthrene and 52.2 g (210 mmol) of potassium phosphate 1-hydrate in a mixture of 75 ml of dioxane, 150 ml of toluene and 200 ml of water was admixed with 457 mg (1.5 mmol) of tri-o-tolylphosphine and then with 56 mg (0.25 mmol) of palladium(II) acetate. After heating under reflux for 16 h and cooling the reaction mixture, the precipitated solid was filtered off with suction and washed three times with 100 ml each time of water and three times with 100 ml each time of ethanol. After drying under reduced pressure (1 mbar, 80° C., 16 h), the product was extracted in a Soxhlett extractor with chloroform through a glass fibre extraction sleeve (pore size 0.5 μm) in order to remove palladium traces. The product which remained after concentration of the chloroform was recrystallized three times from chlorobenzene (approx. 25 ml/g) and three times from DMF (approx. 60 ml/g), and subsequently sublimed twice under high vacuum (p=5×10−5 mbar, T=320-330° C.). The yield at a purity of 99.9% by HPLC was 15.6 g (32 mmol), corresponding to 64.2% of theory.

후처리

  1. temperatureAfter heating
  2. temperatureunder reflux for 16 h
  3. temperaturecooling the reaction mixture
  4. filtrationthe precipitated solid was filtered off with suction
  5. washwashed three times with 100 ml each time of water and three times with 100 ml each time of ethanol
  6. customAfter drying under reduced pressure (1 mbar, 80° C., 16 h)
  7. extractionthe product was extracted in a Soxhlett extractor with chloroform through a glass fibre extraction sleeve (pore size 0.5 μm) in order
  8. customto remove palladium traces
  9. customwas recrystallized three times from chlorobenzene (approx. 25 ml/g) and three times from DMF (approx. 60 ml/g)
  10. customsubsequently sublimed twice under high vacuum (p=5×10−5 mbar, T=320-330° C.)
  11. customThe yield at a purity of 99.9% by HPLC

출처 및 근거

ORD 기록
ord-318781a8a5a347ab8ab6dd183c8a9669
출처 데이터셋
uspto-grants-2012_03
특허 번호
US08129037B2

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