Acetoacetic Acid → HCID 69868084, compound

HRID 1077234Notes

Reaction equation

HRID 1077234 reaction equation
[CH2:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@@H:12]4[C:17](=[CH:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][CH:4]2[OH:21])[CH:16]=[C:15]([OH:20])[CH2:14][CH2:13]4)[CH3:2].[CH3:22][C:23](CC(O)=O)=[O:24].BrN1C(=O)CCC1=O>CC(C)=O.N1C=CC=CC=1.C([O-])(=O)C.[Na+].O.C(O)(=O)C>[CH2:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@@H:12]4[C:17]([CH:18]=[CH:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C@@H:4]2[O:21][C:23](=[O:24])[CH3:22])=[CH:16][C:15](=[O:20])[CH2:14][CH2:13]4)[CH3:2]

Participants

9

Reactant 3

HCID 96Acetoacetic AcidHCID 67184N-bromobutanimideHCID 68143129HCID 68143129, compound

Product 1

HCID 69868084HCID 69868084, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 180AcetoneSolvent2×HCID 962WaterSolventHCID 1049PyridineSolventHCID 517045Sodium AcetateSolvent

Procedure

Add dl-13-ethyl-3,17-dihydroxygona-3,5-diene, diacetate (1.0 g) dissolved in acetone (20 cc) to a solution of acetone (86 cc), pyridine (.59 ml), sodium acetate (2.72 cc), water (27.2 cc) and acetic acid (2.72 cc). Chill to 0° and add N-bromosuccinimide (0.5 g). Stir for three hours at a temperature between +5 and -5°. Pour into ice-cold brine (800 cc) and extract with ether. Wash and dry the ether layer and concentrate, deeping the temperature below +15°. Add calcium carbonate (3.0 g) and dimethylformamide (70 cc) and distil off residual ether. Reflux one hour, cool and filter; wash the cake with ether. Pour the filtrate into brine and extract with ether. Recrystallize from ethyl acetate-hexane to obtain dl-13-ethyl-17β-acetoxygona-4,6-dien-3-one (0.475 g), m.p. 163°-177°, λ max. KBr 5.77, 6.0 μ; λ max. EtOH 283 mμ (ε24,370).

Workup

  1. temperatureChill to 0°
  2. extractionextract with ether
  3. washWash
  4. dry with materialdry the ether layer
  5. concentrationconcentrate
  6. customthe temperature below +15°
  7. customAdd calcium carbonate (3.0 g) and dimethylformamide (70 cc) and distil off residual ether
  8. temperatureReflux one hour
  9. temperaturecool
  10. filtrationfilter
  11. washwash the cake with ether
  12. additionPour the filtrate into brine
  13. extractionextract with ether
  14. customRecrystallize from ethyl acetate-hexane

Sources & evidence

ORD record
ord-800ec5ed9d6a40939e9daf84a17f4ed3
Source dataset
uspto-grants-1976_05
Patent number
US03959322

Reaction notes

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