Acetic Acid → 8-bromo-2,3,5,6-tetrahydropyrido[2,3-b][1,5]diazocin-4(1H)-one hydrobromide

HRID 1880004Notes

Reaction equation

HRID 1880004 reaction equation
[O:1]=[C:2]1[CH2:5][CH2:4][N:3]1[C:6]1[N:13]=[CH:12][CH:11]=[CH:10][C:7]=1[C:8]#[N:9].C(O)(=O)C.[Br:18]Br>[Pd].CCOCC>[BrH:18].[Br:18][C:11]1[CH:12]=[N:13][C:6]2[NH:3][CH2:4][CH2:5][C:2](=[O:1])[NH:9][CH2:8][C:7]=2[CH:10]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 24408BromineHCID 593328632-(2-Oxoazetidin-1-yl)nicotinonitrile

Product 1

HCID 684127008-bromo-2,3,5,6-tetrahydropyrido[2,3-b][1,5]diazocin-4(1H)-one hydrobromide

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

A round bottom flask was purged with argon and charged with 2-(2-oxoazetidin-1-yl)nicotinonitrile (600 mg, 3.46 mmol) and palladium (10%) on activated carbon (250 mg, 0.23 mmol) followed by acetic acid (15 mL). The flask was stirred under a hydrogen balloon overnight. A TLC analysis indicated that the starting material has been consumed. The mixture was filtered through a pad of celite and the filtrate was treated with bromine (0.27 mL, 5.19 mmol) dropwise over 20 minutes. The yellow-orange suspension was stirred for 3.5 hours at room temperature. The suspension was then treated with 150 mL Et2O and stirred rapidly then sonicated. The solvent was decanted and the solid was filtered and washed with 200 mL Et2O. The solid was collected and dried under reduced pressure. Yield: 600 mg (51.3%). 1H-NMR (400 MHz, DMSO-d6) δ 8.06 (d, 1H, J=2.4 Hz), 7.75 (d, 1H, J=2.4 Hz), 7.43 (t, 1H, J=7.6 Hz), 4.48 (d, 2H, J=7.6 Hz), 3.65 (t, 2H, J=8.0 Hz), 2.74 (t, 2H, J=8.0 Hz)

Workup

  1. customA round bottom flask was purged with argon
  2. customhas been consumed
  3. filtrationThe mixture was filtered through a pad of celite
  4. stirringThe yellow-orange suspension was stirred for 3.5 hours at room temperature
  5. stirringstirred rapidly
  6. customthen sonicated
  7. customThe solvent was decanted
  8. filtrationthe solid was filtered
  9. washwashed with 200 mL Et2O
  10. customThe solid was collected
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-8286d5589dd54561b0fecf809a227a33
Source dataset
uspto-grants-2012_11
Patent number
US08318720B2

Reaction notes

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