Cesium carbonate → 3-Bromo-5-{6-oxo-8-thia-4,5-diazatricyclo[7.4.0.02,7]trideca-1(9),2(7),3-trien-5-yl}pyridine-4-carbaldehyde

HRID 1411523Notes

Reaction equation

HRID 1411523 reaction equation
Br[C:2]1[CH:9]=[N:8][CH:7]=[C:6]([Br:10])[C:3]=1[CH:4]=[O:5].[C:11]12[CH2:23][CH2:22][CH2:21][CH2:20][C:19]=1[S:18][C:17]1[C:16](=[O:24])[NH:15][N:14]=[CH:13][C:12]2=1.C(=O)([O-])[O-].[Cs+].[Cs+].COC1C2C(=C3C(=CC=2)C(OC)=CC=N3)N=CC=1>O1CCOCC1>[Br:10][C:6]1[CH:7]=[N:8][CH:9]=[C:2]([N:15]2[C:16](=[O:24])[C:17]3[S:18][C:19]4[CH2:20][CH2:21][CH2:22][CH2:23][C:11]=4[C:12]=3[CH:13]=[N:14]2)[C:3]=1[CH:4]=[O:5]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 27629983,5-Dibromo-4-pyridinecarboxaldehydeHCID 104622984,7-Dimethoxy-1,10-phenanthrolineHCID 670165536,7,8,9-Tetrahydrobenzo[4,5]thieno[2,3-d]pyridazin-4(3H)-one

Product 1

HCID 866842003-Bromo-5-{6-oxo-8-thia-4,5-diazatricyclo[7.4.0.02,7]trideca-1(9),2(7),3-trien-5-yl}pyridine-4-carbaldehydeYield 30%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a 100-mL single-neck round-bottomed flask equipped with a magnetic stirrer and reflux condenser was charged with 1,4-dioxane (15 mL), 3,5-dibromoisonicotinaldehyde (200 mg, 0.76 mmol), 8-thia-4,5-diazatricyclo[7.4.0.02,7]trideca-1(9),2(7),3-trien-6-one 191d (160 mg, 0.76 mmol), and cesium carbonate (176 mg, 1.5 mmol). Cuprous iodide CuI (100 mg, 0.76 mmol) and 4,7-dimethoxy-1,10-phenanthroline (127 mg, 0.52 mmol) were added, and the reaction mixture was heated at 100° C. for 5 h. After this time the reaction was cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure and the residue was purified on flash column eluting with EtOAC/PE (1:2) to afford 116a (80 mg, 30%). MS: [M+H] 390.

Workup

  1. customTo a 100-mL single-neck round-bottomed flask equipped with a magnetic stirrer
  2. temperaturereflux condenser
  3. temperatureAfter this time the reaction was cooled to room temperature
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. customthe residue was purified on flash column
  7. washeluting with EtOAC/PE (1:2)

Sources & evidence

ORD record
ord-d99b76e60f3e4b6c91472c68889a09c6
Source dataset
uspto-grants-2014_12
Patent number
US08921353B2

Reaction notes

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