Toluene → HCID 53945432, compound

HRID 1365583Notes

Reaction equation

HRID 1365583 reaction equation
[CH2:1]([N:3]1[C:15]2[CH:14]=[CH:13][C:12](Br)=[CH:11][C:10]=2[C:9]2[C:4]1=[CH:5][CH:6]=[C:7](Br)[CH:8]=2)[CH3:2].[CH3:18][C:19]1[CH:20]=[C:21]([NH:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:22]=[CH:23][CH:24]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:40]1([CH3:46])[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1>C1(C)C(C)=CC=CC=1.[Cu](I)I>[CH3:18][C:19]1[CH:20]=[C:21]([N:25]([C:7]2[CH:6]=[CH:5][C:4]3[N:3]([CH2:1][CH3:2])[C:15]4[C:10]([C:9]=3[CH:8]=2)=[CH:11][C:12]([N:3]([C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)[C:42]2[CH:43]=[CH:44][CH:45]=[C:40]([CH3:46])[CH:41]=2)=[CH:13][CH:14]=4)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:22]=[CH:23][CH:24]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 14569N-(3-Methylphenyl)anilineHCID 62657Potassium Phosphate, TribasicHCID 6318553,6-Dibromo-9-ethylcarbazole

Product 1

HCID 53945432HCID 53945432, compound

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 7237O-XyleneSolvent2×

Conditions

Temperature
160 °C

Procedure

In an argon atmosphere, 16.59 g (30 mmol) of N-ethyl-3,6-dibromocarbazole and 12.09 g (66 mmol) of N-(3-methylphenyl)-N-phenylamine are dissolved in 1.00 ml of dehydrated xylene. Then, 5.7 g (30 mmol) of copper iodide and 22.8 g (200 mmol) of trans-cyclohexanediamine are added to the xylene solution, and are stirred at 160° C. for 30 minutes. After the stirring, 27.6 g (130 mmol) of potassium phosphate is added, and the mixture is further stirred for 9 days. After the stirring and cooling to a room temperature, 300 ml of toluene is added, and a precipitate is filtered out. The obtained filtrate is condensed, diethyl ether is added to the filtrate, and a precipitate is filtered out. Then, when methanol is added to the obtained filtrate, a tarry object is precipitated on a wall surface of a beaker. The filtrate with the tarry object is left at rest overnight, and the liquid phase is removed by decantation to obtain the tarry object. This obtained tarry object is purified by silica gel column purification using hexane:chloroform (1:2) to obtain 3,6-bis[N-(3-methylphenyl)-N-phenylamino]-9-ethylcarbazole (the above structural formula (56); hereinafter, referred to as EtCzmP2) that is light brownish green powder. The obtained EtCzmP2 is purified by sublimation at a higher temperature of 300° C. and a lower temperature of 200° C. The yield after the sublimation purification is approximately 10%.

Workup

  1. stirringthe mixture is further stirred for 9 days
  2. temperatureAfter the stirring and cooling to a room temperature
  3. filtrationa precipitate is filtered out
  4. customcondensed, diethyl ether
  5. additionis added to the filtrate
  6. filtrationa precipitate is filtered out
  7. additionThen, when methanol is added to the obtained filtrate
  8. customa tarry object is precipitated on a wall surface of a beaker
  9. waitThe filtrate with the tarry object is left at rest overnight
  10. customthe liquid phase is removed by decantation
  11. customto obtain the tarry object
  12. customThis obtained tarry object is purified by silica gel column purification

Sources & evidence

ORD record
ord-52836c74b40b4acfabe70d45c04eebcd
Source dataset
uspto-grants-2011_02
Patent number
US07892657B2

Reaction notes

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