Toluene → 3-chloro-6-(2-triphenyleneyl)-[1]Benzothieno[2,3-c]pyridine

HRID 2178738Notes

Reaction equation

HRID 2178738 reaction equation
[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[S:8][C:9]3[CH:14]=[CH:13][C:12](Br)=[CH:11][C:10]=3[C:4]=2[CH:3]=1.[CH:16]1[C:33]2[C:32]3[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:20]=2[CH:19]=[CH:18][C:17]=1B(O)O.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C1(C)C=CC=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.O>[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[S:8][C:9]3[CH:14]=[CH:13][C:12]([C:29]4[CH:30]=[CH:31][C:32]5[C:33]6[C:20](=[CH:19][CH:18]=[CH:17][CH:16]=6)[C:21]6[C:26](=[CH:25][CH:24]=[CH:23][CH:22]=6)[C:27]=5[CH:28]=4)=[CH:11][C:10]=3[C:4]=2[CH:3]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 62657Potassium Phosphate, TribasicHCID 59805119Triphenylen-2-ylboronic acidHCID 866435773-Chloro-6-bromo-[1]benzothieno[2,3-c]pyridine

Product 1

HCID 866435763-chloro-6-(2-triphenyleneyl)-[1]Benzothieno[2,3-c]pyridineYield 70%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylCatalystHCID 962WaterSolvent

Procedure

The mixture of 3-chloro-6-bromo-[1]benzothieno[2,3-c]pyridine (1.7 g, 5.8 mmol), triphenylen-2-ylboronic acid (1.6 g, 5.8 mmol), potassium phosphate tribasic (3.7 g, 17 mmol), 200 mL toluene and 10 mL water was prepared and bubbled with nitrogen for twenty minutes. Then the tris(dibenzylideneacetone)dipalladium (53 mg, 0.060 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (96 mg, 0.23 mmol) were added. The mixture was bubbled with nitrogen for another twenty minutes. After refluxed overnight under nitrogen, then reaction mixture was cooled to room temperature and filtered through a silica plug and washed with dichloromethane. The first several portions were discarded since they only contained impurities. The combined filtrate was concentrated to give crude product, which was recrystallized from hot dichloromethane and hexanes to give 1.8 g 3-chloro-6-(2-triphenyleneyl)-[1]Benzothieno[2,3-c]pyridine as yellow solid (4.0 mmol, 70% yield).

Workup

  1. customwas prepared
  2. custombubbled with nitrogen for twenty minutes
  3. customThe mixture was bubbled with nitrogen for another twenty minutes
  4. temperatureAfter refluxed overnight under nitrogen
  5. customreaction mixture
  6. filtrationfiltered through a silica plug
  7. washwashed with dichloromethane
  8. concentrationThe combined filtrate was concentrated
  9. customto give crude product, which
  10. customwas recrystallized from hot dichloromethane and hexanes

Sources & evidence

ORD record
ord-00b28203e81b4c78bc2f9352b24d6721
Source dataset
uspto-grants-2015_06
Patent number
US09067947B2

Reaction notes

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