Triethylamine → HCID 69588616, compound

HRID 1796854Notes

Reaction equation

HRID 1796854 reaction equation
[CH:1]1([CH2:7][C@@H:8]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH:9]=[O:10])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.S(=O)(O)[O-].[Na+].[C-]#N.[K+].CC([O:31][C:32](ON=C(C1C=CC=CC=1)C#N)=[O:33])(C)C.C(N(CC)CC)C.OS([O-])(=O)=O.[K+]>O.C(OCC)(=O)C>[C:14]([O:13][C:12]([NH:11][C@H:8]([CH2:7][CH:1]1[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]1)[CH:9]([OH:10])[C:32]([OH:33])=[O:31])=[O:18])([CH3:15])([CH3:17])[CH3:16]

Participants

9

Reactant 6

HCID 8471TriethylamineHCID 9032Potassium CyanideHCID 938652-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrileHCID 516920Potassium bisulfateHCID 13825239HCID 13825239, compoundHCID 23665763Sodium Bisulfite

Product 1

HCID 69588616HCID 69588616, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of Example 3B (19.7 g, 77.1 mmol) and sodium bisulfite (8.0 g, 77.1 mmol) in water (500 mL) at 5° C. was stirred for 24 hours, warmed to room temperature, treated with a solution of potassium cyanide (5.1 g, 78.8 mmol) in ethyl acetate (350 mL), and stirred for 5 hours. The aqueous phase was separated and extracted with ethyl acetate. The combined extracts were washed sequentially with water and brine, dried (MgSO4), filtered, and concentrated. The concentrate was dissolved in dioxane (150 mL), treated with 12M HCl (150 mL), heated to reflux, stirred for 21 hours, and cooled to room temperature. The mixture was concentrated, dissolved in a mixture of water (30 mL) and acetone (200 mL), adjusted to pH 5.5 with 1M NaOH, treated with acetone (3.5 L), and cooled to 0° C. for 4 hours. The resulting precipitate was collected by filtration. The filter cake was dried, dissolved in 1:1 water/dioxane, treated with BOC-ON (1.2 eq.), and triethylamine (2 eq.), heated to 45° C., stirred for 15 hours, treated with 10% aqueous KHSO4, and extracted with ethyl acetate. The extract was washed sequentially with water and brine, dried (MgSO4), filtered, and concentrated to provide the desired product.

Workup

  1. customThe aqueous phase was separated
  2. extractionextracted with ethyl acetate
  3. washThe combined extracts were washed sequentially with water and brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe concentrate was dissolved in dioxane (150 mL)
  8. additiontreated with 12M HCl (150 mL)
  9. temperatureheated
  10. temperatureto reflux
  11. stirringstirred for 21 hours
  12. temperaturecooled to room temperature
  13. concentrationThe mixture was concentrated
  14. dissolutiondissolved in a mixture of water (30 mL) and acetone (200 mL)
  15. additiontreated with acetone (3.5 L)
  16. temperaturecooled to 0° C. for 4 hours
  17. filtrationThe resulting precipitate was collected by filtration
  18. customThe filter cake was dried
  19. dissolutiondissolved in 1:1 water/dioxane
  20. temperatureheated to 45° C.
  21. stirringstirred for 15 hours
  22. extractionextracted with ethyl acetate
  23. washThe extract was washed sequentially with water and brine
  24. dry with materialdried (MgSO4)
  25. filtrationfiltered
  26. concentrationconcentrated

Sources & evidence

ORD record
ord-5df97fe3392d403299030025a73b59fa
Source dataset
uspto-grants-2006_04
Patent number
US07030262B2

Reaction notes

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