Triethylamine → HCID 14390515, compound

HRID 621848Notes

Reaction equation

HRID 621848 reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1.Cl.C([O:14][C:15](=[O:19])[C@H:16]([CH3:18])[NH2:17])C.C(N(CC)CC)C>C(O)C>[ClH:1].[N+:8]([C:7]1[C:2]([NH:17][C@H:16]([C:15]([OH:19])=[O:14])[CH3:18])=[N:3][CH:4]=[CH:5][CH:6]=1)([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 796132-Chloro-3-nitropyridineHCID 2724356L-Alanine, ethyl ester, hydrochloride (1:1)

Product 1

HCID 14390515HCID 14390515, compoundYield 0.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A suspension of 2-chloro-3-nitropyridine (68.6 g, 0.434 mole), (S)-alanine ethyl ester hydrochloride (100 g, 0.651 mole) and triethylamine (103.7 g, 1.03 mole) in 95% ethanol was heated at reflux for 4.5 hours, during which time a dark yellow solution formed. The reaction mixture was stirred at room temperature overnight and then refluxed for an additional 2 hours. The solvents were evaporated under reduced pressure, and the resulting solid was triturated in ethyl acetate, filtered, and rinsed with additional ethyl acetate. The filtrate and washings were combined and washed three times with water, dried over sodium sulfate, filtered, and evaporated to an oil weighing 107 g (quantitative yield). The oil was eluted through 600 g of silica gel, using ethyl acetate as the eluent, and evaporated to an oil. A 3.5-g portion of the oil was dissolved in isopropyl alcohol and acidified with ethereal hydrogen chloride. The mixture was evaporated and redissolved in acetonitrile. Addition of isopropyl ether caused a solid to precipitate. The solid was collected by filtration and its mother liquor was evaporated and the residue was triturated in ethereal hydrogen chloride. A yellow solid formed which was collected by filtration. Upon standing, more solid formed in the mothor liquor. This solid was collected by filtration, rinsed with diethyl ether and dried under high vacuum to give 0.14 g of title compound, mp >260° C. (darkens 178°-185° C.).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 4.5 hours, during which time a dark yellow solution
  3. customformed
  4. temperaturerefluxed for an additional 2 hours
  5. customThe solvents were evaporated under reduced pressure
  6. customthe resulting solid was triturated in ethyl acetate
  7. filtrationfiltered
  8. washrinsed with additional ethyl acetate
  9. washwashed three times with water
  10. dry with materialdried over sodium sulfate
  11. filtrationfiltered
  12. customevaporated to an oil
  13. washThe oil was eluted through 600 g of silica gel
  14. customevaporated to an oil
  15. dissolutionA 3.5-g portion of the oil was dissolved in isopropyl alcohol
  16. customThe mixture was evaporated
  17. dissolutionredissolved in acetonitrile
  18. additionAddition of isopropyl ether
  19. customto precipitate
  20. filtrationThe solid was collected by filtration and its mother liquor
  21. customwas evaporated
  22. customthe residue was triturated in ethereal hydrogen chloride
  23. customA yellow solid formed which
  24. filtrationwas collected by filtration
  25. custommore solid formed in the mothor liquor
  26. filtrationThis solid was collected by filtration
  27. washrinsed with diethyl ether
  28. customdried under high vacuum

Sources & evidence

ORD record
ord-c545b8cfddb44f49a1ef0abf586c3963
Source dataset
uspto-grants-1989_04
Patent number
US04824951

Reaction notes

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