Acetic Acid → HCID 86662313, compound

HRID 1431043Notes

Reaction equation

HRID 1431043 reaction equation
Cl.CO[N:4]1[CH2:7][CH2:6][CH2:5]1.C(N(CC)CC)C.[Cl:15][C:16]1[CH:23]=[CH:22][C:19]([CH:20]=O)=[CH:18][N:17]=1.[C:24](O)(=[O:26])C.[Na]>C(Cl)Cl.O>[Cl:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][N:4]2[CH2:5][CH:6]([O:26][CH3:24])[CH2:7]2)=[CH:18][N:17]=1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 8471TriethylamineHCID 27640536-Chloropyridine-3-carbaldehydeHCID 5360545SodiumHCID 66742532HCID 66742532, compound

Product 1

HCID 86662313HCID 86662313, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a slurry of methoxy azetidine HCL salt (24.2 g, 198 mmol, Eq: 1.00) in 400 mL of methylene chloride was added triethylamine (24.0 g, 33.1 ml, 237 mmol, Eq: 1.2). The precipitate formed went back into solution. Next 6-chloronicotinaldehyde (28 g, 198 mmol, Eq: 1.00) and acetic acid (22.6 ml, 396 mmol, Eq: 2.0) was added. Finally sodium triacetoxyhydroborate (41.9 g, 198 mmol, Eq: 1.00) was added in portions. The first 11 g were added and waited for the chunks to disperse. The second 11 g were then added and an aliquot was checked by TLC. Added the remainder still in portions and continued stirring the slurry. After completion of addition, by TLC, some aldehyde seems to remain so stirring was continued. After another 30 minutes it looked essentially done. Added 400 mL of water and an additional 200 mL of methylene chloride and separated layers. The aqueous phase was made basic with ˜400 mL of 1.0M NaOH and then extracted with 3 times 400 mL of methylene chloride. Concentrated to afford a thick colorless oil. Pumped down to constant weight 28.3 g (67.3%).

Workup

  1. customThe precipitate formed
  2. additionThe first 11 g were added
  3. waitwaited for the chunks
  4. additionto disperse
  5. additionThe second 11 g were then added
  6. additionAdded the remainder still in portions
  7. additionAfter completion of addition
  8. stirringto remain so stirring
  9. customan additional 200 mL of methylene chloride and separated layers
  10. extractionextracted with 3 times 400 mL of methylene chloride
  11. concentrationConcentrated
  12. customto afford a thick colorless oil

Sources & evidence

ORD record
ord-59514221dd3445d4afc68d8504039225
Source dataset
uspto-grants-2015_01
Patent number
US08940741B2

Reaction notes

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