Carbazole → 9-(1-Naphthyl)-9H-carbazole

HRID 926674Notes

Reaction equation

HRID 926674 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][CH:3]=1.[CH:12]1[C:24]2[NH:23][C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16]=2[CH:15]=[CH:14][CH:13]=1.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>[Cu](I)I.C1OCCOCCOCCOCCOCCOC1.C1(C)C=CC=CC=1.CN1CCCN(C)C1=O>[C:2]1([N:23]2[C:24]3[CH:12]=[CH:13][CH:14]=[CH:15][C:16]=3[C:17]3[C:22]2=[CH:21][CH:20]=[CH:19][CH:18]=3)[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 6854CarbazoleHCID 70011-Bromonaphthalene3×HCID 11430Potassium CarbonateHCID 2855718-Crown-6

Product 1

HCID 6262189-(1-Naphthyl)-9H-carbazoleYield 75%

Reagents, catalysts & solvents 4

HCID 2855718-Crown-6CatalystHCID 83717Copper iodideCatalyst2×HCID 1140TolueneSolventHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Conditions

Temperature
170 °C

Procedure

21 g (0.1 mol) of 1-bromonaphthalene, 17 g (0.1 mol) of carbazole, 950 mg (5 mmol) of copper iodide (1), 33 g (240 mmol) of potassium carbonate, and 660 mg (2.5 mmol) of 18-crown-6-ether were put into a 500 mL three-neck flask, and nitrogen substitution was carried out in the flask. To this mixture was added 80 mL of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: DMPU), which was followed by stirring for 6 hours at 170° C. under nitrogen. To this reaction mixture was further added 10 g (50 mmol) of 1-bromonaphthalene, 2.0 g (10 mmol) of copper iodide (I), and 2.6 g (10 mmol) of 18-crown-6-ether, and stirring was further conducted for 7.5 hours at 170° C. Furthermore, to this reaction mixture was added 10 g (50 mmol) of 1-bromonaphthalene, and additional stirring was carried out for 6 hours at 180° C. After the reaction was completed, to this reaction mixture was added about 200 mL of toluene and about 100 of 1 mol/L hydrochloric acid, and then the mixture was filtered through celite. The obtained filtrate was filtered through Florisil and celite. The obtained filtrate was separated into an organic layer and an aqueous layer, and after this organic layer was washed with 1 mol/L hydrochloric acid and then with water, the organic layer was dried over magnesium sulfate. This suspension was filtered through Florisil and celite. The filtrate was concentrated to give an oily substrate, and methanol was added to this oily substrate, followed by irradiation with ultrasound to precipitate a solid. The solid precipitated was collected by suction filtration, giving 22 g of 9-(1-naphthyl)carbazole as white powder (75% yield). The Rf values (SiO2, eluent; hexane:ethyl acetate=10:1) of 9-(1-naphthyl)carbazole, 1-bromonaphthalene, and carbazole were 0.61, 0.74, and 0.24, respectively.

Workup

  1. stirringstirring
  2. waitwas further conducted for 7.5 hours at 170° C
  3. stirringadditional stirring
  4. waitwas carried out for 6 hours at 180° C
  5. filtrationabout 100 of 1 mol/L hydrochloric acid, and then the mixture was filtered through celite
  6. filtrationThe obtained filtrate was filtered through Florisil and celite
  7. customThe obtained filtrate was separated into an organic layer
  8. washan aqueous layer, and after this organic layer was washed with 1 mol/L hydrochloric acid
  9. dry with materialwith water, the organic layer was dried over magnesium sulfate
  10. filtrationThis suspension was filtered through Florisil and celite
  11. concentrationThe filtrate was concentrated
  12. customto give an oily substrate, and methanol
  13. additionwas added to this oily substrate
  14. customfollowed by irradiation with ultrasound
  15. customto precipitate a solid
  16. customThe solid precipitated
  17. filtrationwas collected by suction filtration

Sources & evidence

ORD record
ord-8f6badfec15c44f6bf59bab913c0b320
Source dataset
uspto-grants-2016_03
Patent number
US09287511B2

Reaction notes

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