Carbazole → 9-(4-Bromophenyl)carbazole

HRID 41784

反応式

HRID 41784 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.[CH:9]1[C:21]2[NH:20][C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[C:13]=2[CH:12]=[CH:11][CH:10]=1.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>[Cu]I.C1(C)C=CC=CC=1.CN1C(=O)N(C)CCC1>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([N:20]2[C:21]3[CH:9]=[CH:10][CH:11]=[CH:12][C:13]=3[C:14]3[C:19]2=[CH:18][CH:17]=[CH:16][CH:15]=3)=[CH:3][CH:4]=1

参加物

8

反応物 4

HCID 6854CarbazoleHCID 78041,4-DibromobenzeneHCID 11430Potassium CarbonateHCID 2855718-Crown-6

生成物 1

HCID 223613909-(4-Bromophenyl)carbazole収率 35%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 1140Toluene溶媒HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-溶媒

反応条件

温度
100 °C

実験手順

56 g (240 mmol) of p-dibromobenzene, 31 g (180 mmol) of 9H-carbazole, 4.6 g (24 mmol) of copper(I) iodide, 66 g (480 mmol) of potassium carbonate, and 2.1 g (8 mmol) of 18-crown-6-ether were put into a 300 mL three-neck flask. The mixture was heated at about 100° C., and then 8 mL of N,N′-dimethylpropyleneurea (DMPU) was added thereto. This mixture was stirred at 180° C. for 6 hours. After the stirring, the mixture was cooled to 100° C. To the mixture was added about 200 mL of toluene, and then the mixture was cooled to room temperature. After the cooling, this mixture was subjected to suction filtration so that the precipitate was removed. The obtained filtrate was washed with dilute hydrochloric acid, a saturated sodium hydrogen carbonate solution, and a saturated saline solution in this order. The organic layer was dried with magnesium sulfate. Then, the mixture was subjected to gravity filtration. The obtained filtrate was condensed to give an oily substance. This oily substance was purified by silica gel column chromatography (a developing solvent was a mixed solvent of hexane:ether acetate=9:1), and then recrystallized with chloroform/hexane to give 21 g of a light brown plate-like crystal, which was the object of the synthesis, at a yield of 35%. A synthesis scheme of Step 1 is shown in (f-1) given below.

後処理

  1. temperatureAfter the stirring, the mixture was cooled to 100° C
  2. temperaturethe mixture was cooled to room temperature
  3. filtrationAfter the cooling, this mixture was subjected to suction filtration so that the precipitate
  4. customwas removed
  5. washThe obtained filtrate was washed with dilute hydrochloric acid
  6. dry with materialThe organic layer was dried with magnesium sulfate
  7. filtrationThen, the mixture was subjected to gravity filtration
  8. customcondensed
  9. customto give an oily substance
  10. customThis oily substance was purified by silica gel column chromatography (a developing solvent
  11. customether acetate=9:1), and then recrystallized with chloroform/hexane
  12. customto give 21 g of a light brown plate-like crystal, which
  13. customthe object of the synthesis
  14. customA synthesis scheme of Step 1

出典と根拠

ORDレコード
ord-afe72853a6b44081ba7aa8cea5f42dcc
出典データセット
uspto-grants-2013_09
特許番号
US08530672B2

関連ノート

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