Triethylamine → HCID 11784952, compound

HRID 1986363Notes

Reaction equation

HRID 1986363 reaction equation
C(OC([N:8]1[CH2:17][CH2:16][C:15]2[C:10](=[CH:11][C:12]([N:18]3[C:26]4[CH:25]=[C:24]([O:27][C:28]5[CH:33]=[CH:32][CH:31]=[C:30]([NH:34][C:35](=[O:37])[CH3:36])[CH:29]=5)[N:23]=[CH:22][C:21]=4[N:20]=[C:19]3[CH2:38][C:39]#[N:40])=[CH:13][CH:14]=2)[CH2:9]1)=O)(C)(C)C.[N:41]([O-:43])=O.[Na+].CC[N:47](CC)CC>CO.Cl.O1CCOCC1>[NH2:47][C:39]1[C:38]([C:19]2[N:18]([C:12]3[CH:11]=[C:10]4[C:15]([CH2:16][CH2:17][NH:8][CH2:9]4)=[CH:14][CH:13]=3)[C:26]3[CH:25]=[C:24]([O:27][C:28]4[CH:29]=[C:30]([NH:34][C:35](=[O:37])[CH3:36])[CH:31]=[CH:32][CH:33]=4)[N:23]=[CH:22][C:21]=3[N:20]=2)=[N:41][O:43][N:40]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 23668193Sodium NitriteHCID 68872204HCID 68872204, compound

Product 1

HCID 11784952HCID 11784952, compoundYield 18%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 887MethanolSolventHCID 312751,4-DioxaneSolvent

Procedure

The product from Step 4 (0.250 g, 0.46 mmol) was dissolved in MeOH (5 mL) and 2N HCl (3 mL). To the solution was added NaNO2 (0.065 g, 0.92 mmol), and the mixture was allowed to stir at rt for 30 min. The reaction mixture was concentrated, then dissolved in THF (3 mL). Triethylamine (0.25 mL), and NH2OH (50% aqueous solution, 0.07 mL) were added and the mixture was heated in a sealed tube to 90° C. for 1 hour. The reaction mixture was then cooled, poured into EtOAc and washed with H2O. The organic layer was dried over MgSO4, filtered, then concentrated in-vacuo to give a dark oil. The oil was dissolved in dioxane (3 mL) and Et3N (0.5 mL) and the reaction mixture was heated in a sealed tube to 150° C. for 1 hour. The mixture was then cooled, and concentrated in-vacuo. The crude oil was dissolved in dichloromethane (2 mL) and to the solution was added 4N HCl in dioxane and the resulting solution was allowed to stir at rt for 30 min. The mixture was then concentrated in-vacuo, and the oil was dissolved in a minimal amount of MeOH then poured into Et2O to afford the title compound as a tan solid (40 mg, 18%). MS (ES+) m/e 484 [M+H]+.

Workup

  1. concentrationThe reaction mixture was concentrated
  2. dissolutiondissolved in THF (3 mL)
  3. additionTriethylamine (0.25 mL), and NH2OH (50% aqueous solution, 0.07 mL) were added
  4. temperaturethe mixture was heated in a sealed tube to 90° C. for 1 hour
  5. temperatureThe reaction mixture was then cooled
  6. additionpoured into EtOAc
  7. washwashed with H2O
  8. dry with materialThe organic layer was dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in-vacuo
  11. customto give a dark oil
  12. temperatureThe mixture was then cooled
  13. concentrationconcentrated in-vacuo
  14. dissolutionThe crude oil was dissolved in dichloromethane (2 mL) and to the solution
  15. additionwas added 4N HCl in dioxane
  16. stirringto stir at rt for 30 min
  17. concentrationThe mixture was then concentrated in-vacuo
  18. dissolutionthe oil was dissolved in a minimal amount of MeOH
  19. additionthen poured into Et2O

Sources & evidence

ORD record
ord-1303bd8547e04f5d90ef6a840c2a805d
Source dataset
uspto-grants-2009_06
Patent number
US07547779B2

Reaction notes

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