Triethylamine → HCID 68380544, compound

HRID 573659Notes

Reaction equation

HRID 573659 reaction equation
Br[C:2]1[S:22][C:5]2=[N:6][C:7]([CH3:21])=[CH:8][C:9]([NH:10][S:11]([C:14]3[CH:19]=[CH:18][CH:17]=[C:16]([Cl:20])[CH:15]=3)(=[O:13])=[O:12])=[C:4]2[C:3]=1[C:23]1[CH:28]=[CH:27][CH:26]=[C:25]([O:29][CH3:30])[CH:24]=1.[CH3:31][N:32]([CH3:36])[CH2:33][C:34]#[CH:35].C(N(CC)CC)C>C1COCC1.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:20][C:16]1[CH:15]=[C:14]([S:11]([NH:10][C:9]2[CH:8]=[C:7]([CH3:21])[N:6]=[C:5]3[S:22][C:2]([C:35]#[C:34][CH2:33][N:32]([CH3:36])[CH3:31])=[C:3]([C:23]4[CH:28]=[CH:27][CH:26]=[C:25]([O:29][CH3:30])[CH:24]=4)[C:4]=23)(=[O:13])=[O:12])[CH:19]=[CH:18][CH:17]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 81643N,N-DimethylpropargylamineHCID 53250396N-{2-Bromo-6-methyl-3-[3-(methyloxy)phenyl]thieno[2,3-b]pyridin-4-yl}-3-chlorobenzenesulfonamide

Product 1

HCID 68380544HCID 68380544, compoundYield 4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of N-{2-bromo-6-methyl-3-[3-(methyloxy)phenyl]thieno[2,3-b]pyridin-4-yl}-3-chlorobenzenesulfonamide (Example 33) (122 mg, 0.233 mmol), N,N-dimethyl-2-propyn-1-amine (0.037 mL, 0.349 mmol), copper(I) iodide (4.44 mg, 0.023 mmol), bis(triphenylphosphine)palladium(II) chloride (6.54 mg, 9.32 μmol) and triethylamine (0.097 mL, 0.699 mmol) in THF (1.0 mL) was stirred under an atmosphere of nitrogen at 70° C. for 3 h. The mixture was allowed to cool to RT and was then partitioned between saturated aqueous NaHCO3 (25 mL) and ethyl acetate (75 mL). The aqueous phase was separated and extracted with additional ethyl acetate (25 mL). The organic extracts were combined, washed with brine (25 mL), dried with anhydrous MgSO4, filtered and evaporated to dryness. The residue was purified on silica, eluting with a gradient of 0-10% MeOH in DCM, and then further purified on silica, eluting with a gradient of 0-10% 2M NH3 in MeOH in DCM to afford the title compound (4.9 mg). 1H NMR (MeOD, 400 MHz) δ ppm: 2.42 (6H, s), 2.55 (3H, s), 3.80 (5H, s), 6.89 (2H, m), 7.01 (1H, d, J=7.7 Hz), 7.26 (1H, s), 7.32-7.48 (3H, m), 7.49-7.60 (2H, m).

Workup

  1. temperatureto cool to RT
  2. customwas then partitioned between saturated aqueous NaHCO3 (25 mL) and ethyl acetate (75 mL)
  3. customThe aqueous phase was separated
  4. extractionextracted with additional ethyl acetate (25 mL)
  5. washwashed with brine (25 mL)
  6. dry with materialdried with anhydrous MgSO4
  7. filtrationfiltered
  8. customevaporated to dryness
  9. customThe residue was purified on silica
  10. washeluting with a gradient of 0-10% MeOH in DCM
  11. customfurther purified on silica
  12. washeluting with a gradient of 0-10% 2M NH3 in MeOH in DCM

Sources & evidence

ORD record
ord-0e6312387f674cc080264f2d3d0ec0f1
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

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