Water → 2,3-Dihydro-1H-3a,5-diaza-cyclopenta[a]indene

HRID 1370187Notes

Reaction equation

HRID 1370187 reaction equation
IC1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[NH:8][C:9](=O)C(C)(C)C.Cl[CH2:16][CH2:17][CH2:18][C:19]#[CH:20].O.C(OCC)(=O)C>C(N(CC)CC)C.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[CH2:17]1[C:18]2=[CH:19][C:20]3[CH:7]=[CH:6][N:5]=[CH:4][C:3]=3[N:8]2[CH2:9][CH2:16]1

Participants

8

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 843081-Pentyne, 5-chloro-HCID 10447729N-(4-Iodopyridin-3-yl)-2,2-dimethylpropanamide

Product 1

HCID 185104832,3-Dihydro-1H-3a,5-diaza-cyclopenta[a]indeneYield 56.7%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 0.2885 g bis(triphenylphosphine) palladium dichloride and 0.1565 g copper (I) iodide in 200 mL triethylamine was heated to reflux for 20 min. To the resulting solution was added at room temperature 25.00 g N-(4-iodo-3-pyridinyl)-2,2-dimethyl-propanamide and 25.3 g 5-chloro-1-pentyne and the mixture was heated to reflux for 30 min. The reaction mixture was distributed between water and ethyl acetate, the phases were separated and the organic phase was washed with water and brine, dried over magnesium sulfate and evaporated. The residue was taken up in 200 mL tert-butanol and 18.45 g powdered potassium hydroxyde was added. The mixture was heated to reflux for 30 min. The reaction mixture was distributed between water and ethyl acetate, the phases were separated and the organic phase was washed with water and brine, dried over magnesium sulfate and evaporated. The residue was purified by chromatography on silica gel with ethyl acetate:methanol=7:3 to yield 7.37 g 2,3-Dihydro-1H-3a,5-diaza-cyclopenta[a]indene as slightly yellow solid melting at 90-91° C.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 20 min
  3. temperaturethe mixture was heated
  4. temperatureto reflux for 30 min
  5. customthe phases were separated
  6. washthe organic phase was washed with water and brine
  7. dry with materialdried over magnesium sulfate
  8. customevaporated
  9. additionwas added
  10. temperatureThe mixture was heated
  11. temperatureto reflux for 30 min
  12. customthe phases were separated
  13. washthe organic phase was washed with water and brine
  14. dry with materialdried over magnesium sulfate
  15. customevaporated
  16. customThe residue was purified by chromatography on silica gel with ethyl acetate

Sources & evidence

ORD record
ord-9f82b8b2e21a4642aea89f85de5236b3
Source dataset
uspto-grants-2003_06
Patent number
US06583134B2

Reaction notes

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