Hydrochloric Acid → HCID 20301090, compound

HRID 1733287Notes

Reaction equation

HRID 1733287 reaction equation
[N+:1]([C:4]1[CH:20]=[CH:19][C:7]([CH:8]2[CH2:17][C:16](=[O:18])[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[O:9]2)=[CH:6][CH:5]=1)([O-:3])=[O:2].C=O.Cl.[CH3:24]NC.Cl>C(OCC)(=O)C.CC(C)=O.CC(O)C>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH:8]2[C:17](=[CH2:24])[C:16](=[O:18])[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[O:9]2)=[CH:19][CH:20]=1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 10473Dimethylamine, hydrochlorideHCID 111498742-(4-Nitrophenyl)-2,3-dihydro-4H-1-benzopyran-4-one

Product 1

HCID 20301090HCID 20301090, compoundYield 4.3%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 3776IsopropanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 18.1 g (67 mmol) of 4'-nitro flavanone, prepared as described in J. Chem. Soc. Japan, Pure Chem. Sect. 74, 827 (1953), 4.04 g (134 mmol) of paraformaldehyde, 10.97 g (134 mmol) of dimethylamine hydrochloride, 1 ml of concentrated HCl, and 200 ml of 2-propanol was refluxed for three hours. When cool, the solvent was removed under reduced pressure and the residue partitioned between CHCl3 and 5 percent aqueous HCl. The layers were separated and the organic layer was washed with 3-100 ml portions of 5 percent HCl. The combined aqueous extracts were neutralized with solid Na2CO3 and extracted with ether. The ether was dried over anhydrous Na2SO4, filtered, and concentrated. The oily residue was dissolved in ethyl acetate and treated with 1 ml of ethanol and 1.5 ml of acetyl chloride. The solvent was then evaporated to give a glassy residue. This was taken up in 500 ml of hot ethyl acetate containing 20 ml of acetone and cooled. A precipitate formed that was recrystallized from methanol to give 810 mg of 4'-nitro-3-methylene flavanone as a solid, m.p. 135°-136° C.

Workup

  1. customprepared
  2. temperatureWhen cool
  3. customthe solvent was removed under reduced pressure
  4. customthe residue partitioned between CHCl3 and 5 percent aqueous HCl
  5. customThe layers were separated
  6. washthe organic layer was washed with 3-100 ml portions of 5 percent HCl
  7. extractionextracted with ether
  8. dry with materialThe ether was dried over anhydrous Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. dissolutionThe oily residue was dissolved in ethyl acetate
  12. additiontreated with 1 ml of ethanol and 1.5 ml of acetyl chloride
  13. customThe solvent was then evaporated
  14. customto give a glassy residue
  15. temperaturecooled
  16. customA precipitate formed
  17. customthat was recrystallized from methanol

Sources & evidence

ORD record
ord-1e490d291c164af1a30857650d28b120
Source dataset
uspto-grants-1980_12
Patent number
US04241069

Reaction notes

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