Hydrochloric Acid → HCID 22118303, compound

HRID 1274867Notes

Reaction equation

HRID 1274867 reaction equation
[CH2:1]([Zn]CC)C.[CH3:6][C:7]1[O:12][CH2:11][N:10]([C:13]([CH3:21])([CH:15]([OH:20])[CH2:16][C:17]([CH3:19])=[CH2:18])[CH3:14])[C:9](=[O:22])[C:8]=1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.ICI.Cl.[Cr](Cl)([O-])(=O)=O.[NH+]1C=CC=CC=1>CCCCCC.ClCCl.CCOCC>[CH3:6][C:7]1[O:12][CH2:11][N:10]([C:13]([CH3:14])([C:15](=[O:20])[CH2:16][C:17]2([CH3:1])[CH2:19][CH2:18]2)[CH3:21])[C:9](=[O:22])[C:8]=1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6346DiiodomethaneHCID 22118269HCID 22118269, compoundHCID 178418287HCID 178418287, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 22118303HCID 22118303, compound

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×HCID 8058HexaneSolvent

Procedure

A solution of 1M diethyl zinc in n-hexane(1.4 ml) was added to a solution of 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2,5-dimethyl-hex-5-en-3-ol (0.40 g) in dichloromethane at 20° C. Diiodomethane (0.13 ml) was then added and the mixture stirred and heated at reflux for 2 hours. Hydrochloric acid (1N) was added and the organic layer washed with brine, dried (magnesium sulphate), and evaporated to give crude 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methyl-4-(1-methylcyclopropyl)-butan-3-ol. Powdered molecular sieve 4A (3 g) and pyridinium chlorochromate (0.6 g) were added to a stirred dichloromethane solution of the above compound at 20° C. After 3 hours, ether was added and the mixture filtered, evaporated and purified by silica gel column chromatography, eluting with n-hexane/ethyl acetate (3:1) to give 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methyl-4-(1-methylcyclopropyl)butan-3-one (Compound 1066, 0.25 g), NMR: 1.33(4H), 1.08(s,3H), 1.42(s,6H), 1.92(s,3H), 2.47(s,2H), 5.26(s,2H), 7.20-7.40(5H).

Workup

  1. temperatureheated
  2. temperatureat reflux for 2 hours
  3. washthe organic layer washed with brine
  4. dry with materialdried (magnesium sulphate)
  5. customevaporated
  6. customto give crude 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methyl-4-(1-methylcyclopropyl)-butan-3-ol
  7. filtrationthe mixture filtered
  8. customevaporated
  9. custompurified by silica gel column chromatography
  10. washeluting with n-hexane/ethyl acetate (3:1)

Sources & evidence

ORD record
ord-a782e20921f748689d2a8636b8e2bf3f
Source dataset
uspto-grants-2000_12
Patent number
US06159902

Reaction notes

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