Toluene → 2-[3,5-Bis(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline

HRID 1054000Notes

Reaction equation

HRID 1054000 reaction equation
Cl[C:2]1[CH:11]=[N:10][C:9]2[C:4](=[C:5]3[CH:19]=[CH:18][CH:17]=[CH:16][C:6]3=[C:7]3[CH:15]=[CH:14][CH:13]=[CH:12][C:8]3=2)[N:3]=1.[CH:20]1[C:28]2[C:27]3[CH:29]=[CH:30][CH:31]=[CH:32][C:26]=3[S:25][C:24]=2[C:23]([C:33]2[CH:34]=[C:35](B(O)O)[CH:36]=[C:37]([C:39]3[C:44]4[S:45][C:46]5[CH:51]=[CH:50][CH:49]=[CH:48][C:47]=5[C:43]=4[CH:42]=[CH:41][CH:40]=3)[CH:38]=2)=[CH:22][CH:21]=1.C(=O)([O-])[O-].[K+].[K+].C1(C)C=CC=CC=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(O)C.O>[CH:20]1[C:28]2[C:27]3[CH:29]=[CH:30][CH:31]=[CH:32][C:26]=3[S:25][C:24]=2[C:23]([C:33]2[CH:34]=[C:35]([C:2]3[CH:11]=[N:10][C:9]4[C:4](=[C:5]5[CH:19]=[CH:18][CH:17]=[CH:16][C:6]5=[C:7]5[CH:15]=[CH:14][CH:13]=[CH:12][C:8]5=4)[N:3]=3)[CH:36]=[C:37]([C:39]3[C:44]4[S:45][C:46]5[CH:51]=[CH:50][CH:49]=[CH:48][C:47]=5[C:43]=4[CH:42]=[CH:41][CH:40]=3)[CH:38]=2)=[CH:22][CH:21]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 580194962-Chlorodibenzo[f,h]quinoxalineHCID 866802703,5-Bis(dibenzothiophen-4-yl)phenylboronic acid

Product 1

HCID 866802692-[3,5-Bis(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxalineYield 46%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
320 °C

Procedure

Into a 200-mL three-neck flask were put 1.2 g (4.5 mmol) of 2-chlorodibenzo[f,h]quinoxaline, 2.2 g (4.5 mmol) of 3,5-bis(dibenzothiophen-4-yl)phenylboronic acid, and 1.2 g (9.0 mmol) of potassium carbonate. To this mixture were added 23 mL of toluene, 4.5 mL of water, and 5 mL of ethanol, and this mixture was degassed by being stirred under reduced pressure. To the mixture was added 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium(0), and this mixture was stirred under a nitrogen stream at 100° C. for 3.5 hours. After the stirring, the obtained mixture was filtrated, and the solid was washed with water and then with ethanol. To the obtained solid was added toluene, and the mixture was suction-filtered through Celite, alumina, and Florisil. The filtrate was concentrated to give a solid. This solid was recrystallized from toluene, so that 1.4 g of a white solid was obtained in a yield of 46%. By a train sublimation method, 1.3 g of the obtained solid was purified. In the purification by sublimation, 2DBT2PDBq-II was heated at 320° C. under a pressure of 2.8 Pa with a flow rate of argon gas of 5 mL/min. After the purification by sublimation, 0.94 g of a white solid was obtained at a collection rate of 72%. The synthesis scheme of Step 3 is shown in (b-3).

Workup

  1. customInto a 200-mL three-neck flask were put
  2. customthis mixture was degassed
  3. stirringthis mixture was stirred under a nitrogen stream at 100° C. for 3.5 hours
  4. filtrationAfter the stirring, the obtained mixture was filtrated
  5. washthe solid was washed with water
  6. additionTo the obtained solid was added toluene
  7. filtrationthe mixture was suction-filtered through Celite, alumina, and Florisil
  8. concentrationThe filtrate was concentrated
  9. customto give a solid
  10. customThis solid was recrystallized from toluene, so that 1.4 g of a white solid
  11. customwas obtained in a yield of 46%
  12. customBy a train sublimation method, 1.3 g of the obtained solid was purified
  13. customIn the purification by sublimation
  14. customAfter the purification by sublimation

Sources & evidence

ORD record
ord-6e8d7b59c00a48fc9782a74c613c834b
Source dataset
uspto-grants-2016_07
Patent number
US09394280B2

Reaction notes

Loading…