Potassium Carbonate → 5,11-Bis(4-methylphenyl)indolo[3,2-b]carbazole

HRID 1913986Notes

Reaction equation

HRID 1913986 reaction equation
[CH:1]1[CH:6]=[CH:5][CH:4]=[C:3]2[NH:7][C:8]3[C:9](=[CH:10][C:11]4[NH:12][C:13]5[C:18]([C:19]=4[CH:20]=3)=[CH:17][CH:16]=[CH:15][CH:14]=5)[C:2]=12.C1O[CH2:37][CH2:36]OCCOCCOCCOCCOC1.C([O-])([O-])=O.[K+].[K+].I[C:46]1[CH:51]=[CH:50][C:49]([CH3:52])=[CH:48][CH:47]=1>C1(C)C=CC=CC=1.CS(C)=O.[OH-].[Na+].[Cu].ClC1C=CC=CC=1Cl>[CH3:52][C:49]1[CH:50]=[CH:51][C:46]([N:12]2[C:11]3[C:19](=[CH:20][C:8]4[N:7]([C:1]5[CH:6]=[CH:5][C:36]([CH3:37])=[CH:3][CH:2]=5)[C:3]5[C:2]([C:9]=4[CH:10]=3)=[CH:1][CH:6]=[CH:5][CH:4]=5)[C:18]3[C:13]2=[CH:14][CH:15]=[CH:16][CH:17]=3)=[CH:47][CH:48]=1

Participants

10

Reactant 4

HCID 11430Potassium CarbonateHCID 122074-IodotolueneHCID 2855718-Crown-6HCID 958385,11-Dihydroindolo[3,2-b]carbazole

Product 1

HCID 667227315,11-Bis(4-methylphenyl)indolo[3,2-b]carbazoleYield 189%

Reagents, catalysts & solvents 5

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolventHCID 1140TolueneSolventHCID 72391,2-DichlorobenzeneSolventHCID 14798Sodium HydroxideSolvent

Procedure

A mixture of 5,11-dihydridoindolo[3,2-b]carbazole (2.56 g, 10 mmol), 18-crown-6 (0.52 g, 2.0 mmol), K2CO3 (11.06 g, 80 mmol), 4-iodotoluene (6.54 g, 30 mmol), copper (2.54 g, 40 mmol), and 1,2-dichlorobenzene (40 mL) was charged into an argon-filled 200 mL flask fitted with a condenser. The mixture was heated under reflux in an argon atmosphere for 24 h. Subsequently, the reaction mixture was cooled down to room temperature, diluted with toluene, and filtered. The solid was stirred in 50 mL of N,N-dimethylformamide and 50 mL of 2N HCl was added dropwise and the mixture was stirred for 30 min. The yellow suspension was decanted and filtered to give a yellow solid. The solid was then stirred in a mixture of DMSO (200 mL) and 20% NaOH (50 mL) for 30 min and then filtered. The solid was washed with deionized water, methanol, and dried to yield 1.65 g of 5,11-bis(4-methylphenyl)indolo[3,2-b]carbazole, which was then subject to train sublimation to obtain electrically pure compound for OTFT fabrication. DSC showed two endothenns at 305° C. and 322° C. on first heating. 1H NMR (CDCl3): δ8.11 (d, J=7.8 Hz, 2H), 8.04 (s, 2H), 7.57 (d, J=8.3 Hz, 4H), 7.48 (d, J=8.3 Hz, 4H), 7.39 (d, J=3.7 Hz, 4H), 7.21 (m, 2H), 2.54 (s, 6H); IR (NaCl): 3034, 2916, 1606, 1515, 1451, 1323, 1235, 1191, 819, 741 cm−1.

Workup

  1. additionwas charged into an argon-
  2. additionfilled 200 mL flask
  3. customfitted with a condenser
  4. temperatureThe mixture was heated
  5. temperatureunder reflux in an argon atmosphere for 24 h
  6. filtrationfiltered
  7. addition50 mL of 2N HCl was added dropwise
  8. stirringthe mixture was stirred for 30 min
  9. customThe yellow suspension was decanted
  10. filtrationfiltered
  11. customto give a yellow solid
  12. filtrationfiltered
  13. washThe solid was washed with deionized water, methanol
  14. customdried

Sources & evidence

ORD record
ord-dbb1e09631f64e4883d0462f3bf3a02c
Source dataset
uspto-grants-2013_12
Patent number
US08609867B2

Reaction notes

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