Aniline → HCID 86679340, compound

HRID 1422467Notes

Reaction equation

HRID 1422467 reaction equation
[CH3:1][C:2]1[C:3](=O)[C:4]2[C:25]([C:26](=O)[C:27]=1[CH3:28])=[CH:24][C:23]1[C:6](=[CH:7][C:8]3[C:21]([CH:22]=1)=[CH:20][C:19]1[C:10](=[CH:11][C:12]4[C:13](=O)[C:14]([CH3:32])=[C:15]([CH3:31])[C:16](=O)[C:17]=4[CH:18]=1)[CH:9]=3)[CH:5]=2.[NH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.[N:42]12[CH2:49][CH2:48]N(CC1)CC2>ClC1C=CC=CC=1.Cl[Ti](Cl)(Cl)Cl>[C:36]1([N:35]=[C:16]2[C:17]3[C:12](=[CH:11][C:10]4[C:19]([CH:18]=3)=[CH:20][C:21]3[C:8](=[CH:7][C:6]5[C:23]([CH:22]=3)=[CH:24][C:25]3[C:26](=[N:35][C:36]6[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=6)[C:27]([CH3:28])=[C:2]([CH3:1])[C:3](=[N:35][C:36]6[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=6)[C:4]=3[CH:5]=5)[CH:9]=4)[C:13](=[N:42][C:49]3[CH:48]=[CH:26][CH:27]=[CH:2][CH:1]=3)[C:14]([CH3:32])=[C:15]2[CH3:31])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1

Participants

6

Reactant 3

HCID 6115AnilineHCID 9237DabcoHCID 86679341HCID 86679341, compound

Product 1

HCID 86679340HCID 86679340, compoundYield 56.5%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 7964ChlorobenzeneSolvent2×

Conditions

Temperature
125 °C

Procedure

A solution of TiCl4 (0.15 ml, 1.4 mmol) dissolved in chlorobenzene (5 ml) was slowly added at 75° C. to a mixture of the crude hexacenetetrone (10) (0.118 g), aniline (0.15 ml, 1.6 mmol) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (0.900 g, 8.0 mmol) dissolved in chlorobenzene (20 ml). The reaction mixture was then stirred for 1.5 hours at 125° C. This reaction mixture was then concentrated by passing through a silica gel column (CHCl3). The residue was again dissolved in CHCl3 and re-precipitated in a large amount of acetonitrile. The precipitate was then filtered with Celite, washed with acetonitrile and MeOH, and dried in a vacuum to obtain N,N′,N″,N′″-tetraphenyl-2,3,10,11-tetramethyl-1,4,9,12-hexacenetetrone tetraimine (11) (0.0560 g, 0.075 mmol) at a yield of 25% with respect to 1,4:9,12-dicarboxy-5, 16:8,13-diepoxy-4a,5,8,8a,12a,13,16,16a-octahydro-1,2,3,4,9,10,11,12-octaphenylhexacene (9).

Workup

  1. concentrationThis reaction mixture was then concentrated
  2. dissolutionThe residue was again dissolved in CHCl3
  3. customre-precipitated in a large amount of acetonitrile
  4. filtrationThe precipitate was then filtered with Celite
  5. washwashed with acetonitrile and MeOH
  6. customdried in a vacuum

Sources & evidence

ORD record
ord-bd7843de246b4976bfc31c1db8ba378f
Source dataset
uspto-grants-2015_01
Patent number
US08927157B2

Reaction notes

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