3-Bromo-4-chloropyridine → 8-Methoxy-10,10-dimethyl-5,10-dihydro-11-oxa-3-aza-benzo[b]fluorene

HRID 2275290Notes

Reaction equation

HRID 2275290 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][CH2:8][C:9](=[O:15])[C:10]2([CH3:14])[CH3:13])=[CH:5][CH:4]=1.Br[C:17]1[CH:18]=[N:19][CH:20]=[CH:21][C:22]=1Cl.CC(C)([O-])C.[Na+].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>C(OCC)(=O)C.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(C)C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[CH2:7][C:8]3[C:21]4[CH:20]=[N:19][CH:18]=[CH:17][C:22]=4[O:15][C:9]=3[C:10]([CH3:13])([CH3:14])[C:11]=2[CH:12]=1

Participants

8

Reactant 4

HCID 8176963-Bromo-4-chloropyridineHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 130110077-Methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one2×HCID 23676156Sodium t-butoxide

Product 1

HCID 668353178-Methoxy-10,10-dimethyl-5,10-dihydro-11-oxa-3-aza-benzo[b]fluoreneYield 4%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To 7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (Compound A2, 2.5 g), 3-bromo-4-chloro-pyridine (2 g), sodium t-butoxide (3 g), Pd2dba3 (476 mg), and S-Phos (512 mg), toluene (20 ml) was added, and the mixture was stirred and heated at 100° C. overnight under nitrogen atmosphere. After cooling, the reaction mixture was diluted with ethyl acetate and filtered through Celite. The organic layer was washed with saturated aqueous solution of sodium bicarbonate and saturated brine. Thereafter, the organic layer was dried over sodium sulfate. The residues obtained after concentration under reduced pressure were purified by silica gel column (ethyl acetate/hexane) to obtain the title compound (112 mg, 4%).

Workup

  1. temperatureAfter cooling
  2. filtrationfiltered through Celite
  3. washThe organic layer was washed with saturated aqueous solution of sodium bicarbonate and saturated brine
  4. dry with materialThereafter, the organic layer was dried over sodium sulfate
  5. customThe residues obtained
  6. concentrationafter concentration under reduced pressure
  7. customwere purified by silica gel column (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-7215ad0b19e24fb69ad5ffc5e7268ff9
Source dataset
uspto-grants-2015_09
Patent number
US09126931B2

Reaction notes

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