Aniline → HCID 86679339, compound

HRID 1422466Notes

Reaction equation

HRID 1422466 reaction equation
[CH3:1][C:2]1[C:3](=O)[C:4]2[C:21]([C:22](=O)[C:23]=1[CH3:24])=[CH:20][C:19]1[C:6](=[CH:7][C:8]3[C:17]([CH:18]=1)=[CH:16][C:15]1[C:14](=O)[C:13]([CH3:27])=[C:12]([CH3:28])[C:11](=O)[C:10]=1[CH:9]=3)[CH:5]=2.[NH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[N:38]12[CH2:45][CH2:44]N(CC1)CC2>ClC1C=CC=CC=1.Cl[Ti](Cl)(Cl)Cl>[C:32]1([N:31]=[C:11]2[C:10]3[C:15](=[CH:16][C:17]4[C:8]([CH:9]=3)=[CH:7][C:6]3[C:19](=[CH:20][C:21]5[C:22](=[N:31][C:32]6[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=6)[C:23]([CH3:24])=[C:2]([CH3:1])[C:3](=[N:31][C:32]6[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=6)[C:4]=5[CH:5]=3)[CH:18]=4)[C:14](=[N:38][C:45]3[CH:44]=[CH:22][CH:23]=[CH:2][CH:1]=3)[C:13]([CH3:27])=[C:12]2[CH3:28])[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

Participants

6

Reactant 3

HCID 6115AnilineHCID 9237DabcoHCID 713424412,3,9,10-Tetramethylpentacene-1,4,8,11-tetrone

Product 1

HCID 86679339HCID 86679339, compoundYield 280.9%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 7964ChlorobenzeneSolvent2×

Conditions

Temperature
130 °C

Procedure

A solution of TiCl4 (0.25 ml, 2.3 mmol) dissolved in chlorobenzene (5 ml) was slowly added at 80° C. to a mixture of the crude pentacenetetrone (4) (0.126 g), aniline (0.100 g, 0.11 mmol) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (1.3 g, 11.1 mmol) dissolved in chlorobenzene (25 ml). The reaction mixture was stirred for 3.5 hours at 130° C. The precipitate was then filtered with Celite and the resulting filtrate was concentrated. The residue was again dissolved in CHCl3 and was re-precipitated in a large amount of acetonitrile. The product was purified by silica gel column chromatography (CHCl3:hexane=3:1) to obtain N,N′,N″,N′″-tetraphenyl-2,3,9,10-tetramethyl-1,4,8,11-pentacenetetrone tetraimine (5) (0.0716 g, 0.103 mmol) at a yield of 25% with respect to 1,4:8,11-dicarboxy-5,14:7,12-diepoxy-4a,5,7,7a,11a,12,14,14a-octahydro-1,2,3,4,8,9,10,11-octaphenylpentacene (3).

Workup

  1. filtrationThe precipitate was then filtered with Celite
  2. concentrationthe resulting filtrate was concentrated
  3. dissolutionThe residue was again dissolved in CHCl3
  4. customwas re-precipitated in a large amount of acetonitrile
  5. customThe product was purified by silica gel column chromatography (CHCl3:hexane=3:1)

Sources & evidence

ORD record
ord-f0fc96b178444fa48d9598f23e623223
Source dataset
uspto-grants-2015_01
Patent number
US08927157B2

Reaction notes

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