Hydrochloric Acid → 1h-Pyrrolo[2,3-c]pyridine-2-methanamine,a-methyl-,dihydrochloride

HRID 1821872Notes

Reaction equation

HRID 1821872 reaction equation
[NH:1]1[C:5]2=[CH:6][N:7]=[CH:8][CH:9]=[C:4]2[CH:3]=[C:2]1[C:10](=[N:12]O)[CH3:11].[H-].[Al+3].[Li+].[H-].[H-].[H-].CCO.[ClH:23]>C1COCC1.CCOC(C)=O.CCOCC>[ClH:23].[ClH:23].[NH:1]1[C:5]2=[CH:6][N:7]=[CH:8][CH:9]=[C:4]2[CH:3]=[C:2]1[CH:10]([NH2:12])[CH3:11]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 702EthanolHCID 21226445Aluminium lithium hydrideHCID 1363865051-(1H-pyrrolo[2,3-c]pyridin-2-yl)ethanone oxime

Product 1

HCID 689820051h-Pyrrolo[2,3-c]pyridine-2-methanamine,a-methyl-,dihydrochlorideYield 72%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a heterogeneous solution of 1-(1H-pyrrolo[2,3-c]pyridin-2-yl)ethanone oxime (Example 72) (0.31 g, 1.75 mmol) in THF (27.5 mL) was added lithium aluminum hydride (0.33 g, 8.79 mmol) at room temperature under a nitrogen atmosphere. The reaction mixture was refluxed for 1 h and then quenched by careful addition of hydrated Na2SO4. Ethyl acetate was added and the reaction mixture was stirred overnight. The solid was filtered off and thoroughly rinsed with EtOAc and EtOH. The filtrate was concentrated to give a yellow oil. The crude residue was dissolved in EtOAc and EtOH (100 mL; 1:1) and 2 M HCl in Et2O was added (1.85 mL). The precipitate was filtered off, rinsed with EtOAc and Et2O, and dried to provide 1-(1H-pyrrolo[2,3-c]pyridin-2-yl)ethylamine dihydrochloride (0.29 g, 72%) as a light orange solid: mp 289-292° C.; 1H NMR (300 MHz, CD3OD) δ1.82 (3H, d, J=6.9 Hz), 4.88-4.95 (1H, m), 7.09 (1H, s), 8.17 (1H, d, J=6.4 Hz), 8.29 (1H, d, J=64 Hz), 9.13 (1H, s); ESI MS m/z 162 [C9H11N3+H]+; HPLC (Method A) 97.7% (AUC), tR=6.50 min.

Workup

  1. temperatureThe reaction mixture was refluxed for 1 h
  2. customquenched by careful addition of hydrated Na2SO4
  3. additionEthyl acetate was added
  4. filtrationThe solid was filtered off
  5. washthoroughly rinsed with EtOAc and EtOH
  6. concentrationThe filtrate was concentrated
  7. customto give a yellow oil
  8. filtrationThe precipitate was filtered off
  9. washrinsed with EtOAc and Et2O
  10. customdried

Sources & evidence

ORD record
ord-cb3276c3aa6a4c11869d5998882b47e0
Source dataset
uspto-grants-2009_10
Patent number
US07608627B2

Reaction notes

Loading…