Ammonia → HCID 5270974, compound

HRID 433967Notes

Reaction equation

HRID 433967 reaction equation
[OH:1][C:2]1[C:11]([C:12](=O)[CH2:13][CH3:14])=[C:10]2[C:5]([C:6]([CH2:17][CH2:18][CH3:19])=[CH:7][C:8](=[O:16])[O:9]2)=[C:4]2[O:20][C:21]([CH3:25])([CH3:24])[CH:22]=[CH:23][C:3]=12.CO.[BH4-].[Na+].Cl.[NH3:31]>>[NH2:31][CH:12]([C:11]1[C:2]([OH:1])=[C:3]2[CH:23]=[CH:22][C:21]([CH3:25])([CH3:24])[O:20][C:4]2=[C:5]2[C:10]=1[O:9][C:8](=[O:16])[CH:7]=[C:6]2[CH2:17][CH2:18][CH3:19])[CH2:13][CH3:14]

Participants

6

Reactant 5

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 887MethanolHCID 4311764Sodium borohydrideHCID 54948815-Hydroxy-2,2-dimethyl-6-propionyl-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one

Product 1

HCID 5270974HCID 5270974, compoundYield 61%

Procedure

5-Hydroxy-2,2-dimethyl-6-propionyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one (30) (1.0 g, 2.9 mmol, 1.0 eq) was dissolved in 7 N ammonia in methanol (100 mL, 0.7 mol, 241 eq). The mixture was stirred overnight at ambient temperature. Solvent and excess of ammonia were removed under vacuum and the residue re-dissolved in methanol (100 mL). The solution was cooled to 0° C. and sodium borohydride (550 mg, 14.6 mmol, 5.0 eq) added portionwise. The mixture was allowed to warm up room temperature and stirred for 3 h. The mixture was then poured into ice-water and pH adjusted to 8.5 with concentrated hydrochloric acid. The product was extracted into ethyl acetate (3×50 mL). The extracts were combined and washed with brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was chromatographed on silica gel column eluted with 5-10% methanol in dichloromethane to yield 612 mg of 24a (61% yield). 1H NMR (CDCl3): 0.97 (t, J=7.5 Hz, 3H), 1.03 (t, J=7.5 Hz, 3H), 1.47 (s, 3H), 1.49 (s, 3H), 1.67 (m, 2H), 1.78 (m, 2H), 2.89 (m, 2H), 4.85 (t, J=7.0 Hz, 1H), 5.52 (d, J=10.0 Hz, 1H), 5.88 (s, 1H), 6.67 (d, J=10.0 Hz, 1H); 13C NMR (DMSO-d6): 10.17, 13.99, 23.54, 26.24, 27.23, 27.31, 37.99, 49.84, 76.35, 96.60, 102.88, 103.95, 107.80, 118.29, 123.55, 150.87, 153.82, 158.66, 160.26, 167.83; IR: 1683 cm−1; MS (ACPI+): 344 (M+1), 327 (M-NH3+1); Anal. Calcd. for C20H25NO4: C 69.95, H 7.34, N 4.08; Found C 69.97, H 7.30, N 4.08.

Workup

  1. customSolvent and excess of ammonia were removed under vacuum
  2. dissolutionthe residue re-dissolved in methanol (100 mL)
  3. temperatureThe solution was cooled to 0° C.
  4. temperatureto warm up room temperature
  5. stirringstirred for 3 h
  6. extractionThe product was extracted into ethyl acetate (3×50 mL)
  7. washwashed with brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated under vacuum
  10. customThe residue was chromatographed on silica gel column
  11. washeluted with 5-10% methanol in dichloromethane

Sources & evidence

ORD record
ord-2ee7f62c332f44e38aa4d15b366a0897
Source dataset
uspto-grants-2003_12
Patent number
US06670383B2

Reaction notes

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