Sodium Carbonate → 8-chloro-4,6-dimethyl-9-vinylbenzo[c][2,7]naphthyridin-5(6H)-one

HRID 1398364Notes

Reaction equation

HRID 1398364 reaction equation
[Cl:1][C:2]1[C:3](I)=[CH:4][C:5]2[C:14]3[C:9](=[C:10]([CH3:15])[N:11]=[CH:12][CH:13]=3)[C:8](=[O:16])[N:7]([CH3:17])[C:6]=2[CH:18]=1.B1(C=C)OB([CH:26]=[CH2:27])OB(C=C)O1.C1C=CN=CC=1.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.O.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>[Cl:1][C:2]1[C:3]([CH:26]=[CH2:27])=[CH:4][C:5]2[C:14]3[C:9](=[C:10]([CH3:15])[N:11]=[CH:12][CH:13]=3)[C:8](=[O:16])[N:7]([CH3:17])[C:6]=2[CH:18]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 867103578-chloro-9-iodo-4,6-dimethylbenzo[c][2,7]naphthyridin-5(6H)-one

Product 1

HCID 867103588-chloro-4,6-dimethyl-9-vinylbenzo[c][2,7]naphthyridin-5(6H)-oneYield 68%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

A solution of 8-chloro-9-iodo-4,6-dimethylbenzo[c][2,7]naphthyridin-5(6H)-one (1.2 g, 2.71 mmol), 2,4,6-trivinylcyclotriboroxane pyridine complex (0.784 g, 3.26 mmol), tetrakis(triphenylphosphine)palladium (0.157 g, 0.136 mmol) and Na2CO3 (0.575 g, 5.43 mmol) in toluene (30 mL) and water (0.5 mL) was purged with nitrogen and heated at 90° C. for 16 h. After cooling to room temperature, the mixture was concentrated under reduced pressure. The residue was taken up in ethyl acetate and filtered through diatomaceous earth (Celite®). The EtOAc layer was washed with brine and water. The combined organic layers were dried over Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel flash chromatography using EtOAc-hexane as the eluent to afford 8-chloro-4,6-dimethyl-9-vinylbenzo[c][2,7]naphthyridin-5(6H)-one (0.6 g, 1.43 mmol, 68% yield)) as brown gummy solid. LC/MS (ESI) m/e 285.0 [(M+H)+, calcd for C16H14ClN2O, 285.1]; LC/MS retention time (method B): tR=2.25 min.

Workup

  1. temperatureAfter cooling to room temperature
  2. concentrationthe mixture was concentrated under reduced pressure
  3. filtrationfiltered through diatomaceous earth (Celite®)
  4. washThe EtOAc layer was washed with brine and water
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude material was purified by silica gel flash chromatography

Sources & evidence

ORD record
ord-56a504162dc14a20b3a05fef7f2251ce
Source dataset
uspto-grants-2014_12
Patent number
US08901305B2

Reaction notes

Loading…