2-(Tri-n-butylstannyl)thiophene → HCID 57438959, compound

HRID 1383848Notes

Reaction equation

HRID 1383848 reaction equation
Br[C:2]1[N:6]2[N:7]=[C:8]([O:17][CH2:18][C:19]3[N:23]=[CH:22][N:21]([CH3:24])[N:20]=3)[C:9]([N:11]3[CH2:16][CH2:15][O:14][CH2:13][CH2:12]3)=[CH:10][C:5]2=[N:4][N:3]=1.C([Sn](CCCC)(CCCC)[C:30]1[S:31][CH:32]=[CH:33][CH:34]=1)CCC>CN(C=O)C>[CH3:24][N:21]1[CH:22]=[N:23][C:19]([CH2:18][O:17][C:8]2[C:9]([N:11]3[CH2:16][CH2:15][O:14][CH2:13][CH2:12]3)=[CH:10][C:5]3[N:6]([C:2]([C:30]4[S:31][CH:32]=[CH:33][CH:34]=4)=[N:3][N:4]=3)[N:7]=2)=[N:20]1

Participants

4

Reactant 2

HCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 22744172HCID 22744172, compound

Product 1

HCID 57438959HCID 57438959, compoundYield 60.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 3-bromo-6-(1-methyl-1 H-1,2,4-triazol-3-ylmethoxy)-7-(morpholin-4-yl)-1,2,4-triazolo[4,3-b]pyridazine (100 mg, 0.25 mmol) and 2-(tributylstannyl)thiophene (240 mL 0.75 mmol) in dry DMF (3 ml) was deoxygenated by bubbling through nitrogen gas for 15 minutes. Dichlorobis(triphenylphosphine)palladium (II) (20 mg) was then added. The whole apparatus was further deoxygenated by three ‘evacuate/fill N2’ cycles. The mixture was then stirred and heated at 100° C. for 16 hours under nitrogen. The reaction mixture was partitioned between dichloromethane and water. The aqueous layer was further extracted with dichloromethane (x2). The combined extracts were dried (Na2SO4), filtered and evaporated. Residual DMF was removed under high vacuum. The residue was purified by chromatography on silica gel, eluting with 5% methanol/dichloromethane to give the title compound (60 mg, 60%). Data for the title compound: 1H NMR (360 MHz, CDCl3) δ3.26-3.29 (4 H, m), 3.85-3.89 (4 H, m), 3.94 (3 H,-s), 5.64 (2 H, s), 7.19-7.23 (2 H, m), 7.47-7.59 (1 H, m), 8.05 (1 H, s), 8.18-8.20 (1 H, m); MS (ES+) m/e 399 [MH+]. Anal. Found C, 50.84; H, 4.39; N, 27.35. C17H18N8O2S. 0.3(H2O) requires C, 50.56; H, 4.64; N, 27.75%.

Workup

  1. customwas deoxygenated
  2. customby bubbling through nitrogen gas for 15 minutes
  3. additionDichlorobis(triphenylphosphine)palladium (II) (20 mg) was then added
  4. customThe whole apparatus was further deoxygenated by three ‘
  5. customevacuate/fill N2’ cycles
  6. customThe reaction mixture was partitioned between dichloromethane and water
  7. extractionThe aqueous layer was further extracted with dichloromethane (x2)
  8. dry with materialThe combined extracts were dried (Na2SO4)
  9. filtrationfiltered
  10. customevaporated
  11. customResidual DMF was removed under high vacuum
  12. customThe residue was purified by chromatography on silica gel
  13. washeluting with 5% methanol/dichloromethane

Sources & evidence

ORD record
ord-054a860d79a4493db1432dfa96c50d17
Source dataset
uspto-grants-2001_07
Patent number
US06255305B1

Reaction notes

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