Carbazole → 9-[4-(benzoxazol-2-yl)phenyl]-9H-carbazole

HRID 420018Notes

Reaction equation

HRID 420018 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[O:9][C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[N:12]=2)=[CH:4][CH:3]=1.[CH:17]1[C:29]2[NH:28][C:27]3[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=3)[C:21]=2[CH:20]=[CH:19][CH:18]=1.CC(C)([O-])C.[Na+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1(C)C=CC=CC=1.CCCCCC>[O:9]1[C:10]2[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=2[N:12]=[C:8]1[C:5]1[CH:6]=[CH:7][C:2]([N:28]2[C:29]3[CH:17]=[CH:18][CH:19]=[CH:20][C:21]=3[C:22]3[C:27]2=[CH:26][CH:25]=[CH:24][CH:23]=3)=[CH:3][CH:4]=1

Participants

8

Reactant 4

HCID 6854CarbazoleHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 28294142-(4-Iodophenyl)benzoxazoleHCID 23676156Sodium t-butoxide

Product 1

HCID 592279319-[4-(benzoxazol-2-yl)phenyl]-9H-carbazoleYield 89%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
110 °C

Procedure

In a 100 mL three-neck flask were put 1.5 g (4.7 mmol) of 2-(4-iodophenyl)benzoxazole, 0.78 g (4.7 mmol) of 9H-carbazole, and 0.99 g (10 mmol) of sodium tert-butoxide. The atmosphere in the flask was replaced with nitrogen. To this mixture was added 15 mL of toluene. The resulting mixture was degassed under reduced pressure, and then the atmosphere in the flask was replaced with nitrogen. To this mixture were added 0.10 mL of a 10% hexane solution of tri(tert-butyl)phosphine and 0.030 g (0.48 mmol) of bis(dibenzylideneacetone)palladium(0). This mixture was stirred under a nitrogen stream at 110° C. for 11 hours. After that, toluene was added to this mixture, and this suspension was washed with 1M dilute hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and saturated brine in that order. After that, magnesium sulfate was added to the organic layer to dry it. Next, this mixture was suction filtered. The resulting filtrate was suction filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The resulting filtrate was concentrated, followed by purification by silica gel column chromatography. As developing solvents for the column chromatography, a mixed solvent of a 1:1 ratio of toluene to hexane, and then toluene were used. The fraction obtained was concentrated to give a solid. This solid was recrystallized with a mixed solvent of chloroform and methanol to give 1.5 g of a white powdered solid in a yield of 89%.

Workup

  1. customIn a 100 mL three-neck flask were put
  2. customThe resulting mixture was degassed under reduced pressure
  3. washthis suspension was washed with 1M dilute hydrochloric acid
  4. additionAfter that, magnesium sulfate was added to the organic layer
  5. customto dry it
  6. filtrationfiltered
  7. filtrationfiltered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855)
  8. concentrationThe resulting filtrate was concentrated
  9. customfollowed by purification by silica gel column chromatography
  10. customThe fraction obtained
  11. concentrationwas concentrated
  12. customto give a solid
  13. customThis solid was recrystallized with a mixed solvent of chloroform and methanol

Sources & evidence

ORD record
ord-9f89a26cc7384d74a1e5a40984278cb9
Source dataset
uspto-grants-2012_01
Patent number
US08093399B2

Reaction notes

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