Carbazole → 9-(9,10-diphenyl-2-anthryl)-9H-carbazole

HRID 1517158노트

반응식

HRID 1517158 반응식
Br[C:2]1[CH:15]=[CH:14][C:13]2[C:4](=[C:5]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C:6]3[C:11]([C:12]=2[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:10][CH:9]=[CH:8][CH:7]=3)[CH:3]=1.[CH:28]1[C:40]2[NH:39][C:38]3[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=3)[C:32]=2[CH:31]=[CH:30][CH:29]=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>[C:22]1([C:5]2[C:6]3[C:11]([C:12]([C:16]4[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=4)=[C:13]4[C:4]=2[CH:3]=[C:2]([N:39]2[C:38]5[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=5[C:32]5[C:40]2=[CH:28][CH:29]=[CH:30][CH:31]=5)[CH:15]=[CH:14]4)=[CH:10][CH:9]=[CH:8][CH:7]=3)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

참가 물질

7

반응물 4

HCID 6854CarbazoleHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 222471632-Bromo-9,10-diphenylanthraceneHCID 23676156Sodium t-butoxide

생성물 1

HCID 579092029-(9,10-diphenyl-2-anthryl)-9H-carbazole수율 93%

시약·촉매·용매 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium촉매HCID 1140Toluene용매2회

반응 조건

온도
110 °C

실험 절차

First, 1.5 g (3.7 mmol) of 2-bromo-9,10-diphenylanthracene, which was used in Step 1 of Synthesis Example 5, 610 mg (3.7 mmol) of 9H-carbazole, and 1.5 g (16 mmol) of sodium tert-butoxide were put into a 100 mL three-neck flask, and the air in the flask was replaced with nitrogen. 20 mL of toluene and 0.10 mL of tri(tert-butyl)phosphine (10 wt % hexane solution) were added to this mixture. This mixture was degassed while being stirred under reduced pressure, and after the degassing, 58 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0) was added. This mixture was refluxed at 110° C. for 5 hours. After the reflux, this mixture was cooled to room temperature and about 20 mL of toluene was added to this mixture. The mixture was then filtered through alumina, Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135). The obtained filtrate was concentrated to give a light-brown oily substance. This oily substance was purified by silica gel column chromatography (a developing solvent was a mixed solvent of hexane:toluene=6:4). The obtained light-yellow solid substance was recrystallized from ethanol, so that 1.7 g of a light-yellow powdered solid was obtained in a yield of 93%. At a pressure of 8.7 Pa and with an argon gas flowing at a flow rate of 3.0 mL/min, 1.6 g of the obtained light-yellow powdered solid substance was heated at 230° C. so as to be sublimated and purified (a train sublimation method). After the sublimation purification, 1.5 g of a light-yellow solid substance was recovered in a yield of 93%. A synthesis scheme of Step 1 is shown in (F-3) given below.

후처리

  1. customwere put into a 100 mL three-neck flask
  2. customThis mixture was degassed
  3. temperatureAfter the reflux, this mixture was cooled to room temperature
  4. filtrationThe mixture was then filtered through alumina, Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135)
  5. concentrationThe obtained filtrate was concentrated
  6. customto give a light-brown oily substance
  7. customThis oily substance was purified by silica gel column chromatography (a developing solvent
  8. customThe obtained light-yellow solid substance was recrystallized from ethanol, so that 1.7 g of a light-yellow powdered solid
  9. customwas obtained in a yield of 93%
  10. temperaturewas heated at 230° C. so as
  11. custompurified (a train sublimation method)
  12. customAfter the sublimation purification, 1.5 g of a light-yellow solid substance
  13. customwas recovered in a yield of 93%
  14. customA synthesis scheme of Step 1

출처 및 근거

ORD 기록
ord-7fa5fdee9d74461aba979458c79f87ac
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08231942B2

반응 노트

불러오는 중…