1,2-Diaminocyclohexane, trans- → 9-(2'-nitrobiphenyl-4-yl)-2-(pyridin-2-yl)-9H-carbazole

HRID 1509634Notes

Reaction equation

HRID 1509634 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[NH:10][C:9]=2[CH:8]=1.I[C:21]1[CH:26]=[CH:25][C:24]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=2[N+:33]([O-:35])=[O:34])=[CH:23][CH:22]=1.[C@@H]1(N)CCCC[C@H]1N.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>ClCCl.CO.[Cu]I>[N+:33]([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][C:27]=1[C:24]1[CH:23]=[CH:22][C:21]([N:10]2[C:9]3[CH:8]=[C:7]([C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][N:1]=4)[CH:19]=[CH:18][C:17]=3[C:16]3[C:11]2=[CH:12][CH:13]=[CH:14][CH:15]=3)=[CH:26][CH:25]=1)([O-:35])=[O:34]

Participants

7

Reactant 4

HCID 438061,2-Diaminocyclohexane, trans-HCID 62657Potassium Phosphate, TribasicHCID 6297494'-Iodo-2-nitrobiphenylHCID 222472152-(2-pyridyl)-9H-carbazole

Product 1

HCID 1181139679-(2'-nitrobiphenyl-4-yl)-2-(pyridin-2-yl)-9H-carbazoleYield 94.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 21226129Dichloromethane methanolSolvent

Conditions

Temperature
112.5 °C

Procedure

2-(Pyridin-2-yl)-9H-carbazole (611 mg, 2.5 mmol, 1.0 eq), 4′-iodo-2-nitrobiphenyl (975 mg, 3.0 mmol, 1.2 eq), CuI (48 mg, 0.25 mmol, 0.1 eq), trans-cyclohexane-1,2-diamine (250 uL, 2.5 mmol, 1.0 eq) and K3PO4 (1114 mg, 5.25 mmol, 2.1 eq) were added to a dry pressure vessel equipped with a magnetic stir bar. The vessel was evacuated and back-filled with nitrogen. The evacuation and back-fill procedure was repeated twice. Then solvent dioxane (10 mL) was added under nitrogen. After bubbling with nitrogen for 30 minutes, the mixture was stirred at 110-115° C. in an oil bath for 4 days. Then the mixture was cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate (10:1-3:1) then dichloromethane/methanol (20:1) as an eluent to obtain the desired product as a solid (1.04 g in 94% yield). 1H NMR (DMSO-d6, 400 MHz): δ 7.36 (t, J=6.0 Hz, 2H), 7.45 (d, J=8.0 Hz, 1H), 7.51 (d, J=8.4 Hz, 1H), 7.70-7.92 (m, 8H), 8.05 (t, J=8.4 Hz, 2H), 8.10 (d, J=8.4 Hz, 1H), 8.22 (s, 1H), 8.33 (d, J=7.2 Hz, 1H), 8.39 (d, J=8.0 Hz, 1H), 8.67 (d, J=4.8 Hz, 1H).

Workup

  1. customequipped with a magnetic stir bar
  2. customThe vessel was evacuated
  3. additionback-filled with nitrogen
  4. additionThen solvent dioxane (10 mL) was added under nitrogen
  5. customAfter bubbling with nitrogen for 30 minutes
  6. temperatureThen the mixture was cooled to ambient temperature
  7. customThe solvent was removed under reduced pressure
  8. customthe residue was purified through column chromatography on silica gel

Sources & evidence

ORD record
ord-f7a48549f2024f938bc1b880bdb3b337
Source dataset
uspto-grants-2015_12
Patent number
US09224963B2

Reaction notes

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