Acetic Acid → HCID 14835387, compound

HRID 1199015Notes

Reaction equation

HRID 1199015 reaction equation
C(O[C:4](=O)[CH:5]([Na])[C:6]([O:8]CC)=[O:7])C.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([C:20](=[O:31])[C:21]2[CH:26]=C(Cl)[CH:24]=[CH:23][C:22]=2[N+:28]([O-:30])=[O:29])=[CH:16][CH:15]=1.O.C(O)(=O)C>C(OCC)(=O)CC(OCC)=O>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([C:20]([C:21]2[CH:26]=[C:4]([CH2:5][C:6]([OH:8])=[O:7])[CH:24]=[CH:23][C:22]=2[N+:28]([O-:30])=[O:29])=[O:31])=[CH:18][CH:19]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 14835386HCID 14835386, compoundHCID 178472565HCID 178472565, compound

Product 1

HCID 14835387HCID 14835387, compound

Reagents, catalysts & solvents 1

HCID 7761Diethyl MalonateSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 0.0175 mole of diethylsodiomalonate in 250 ml of diethyl malonate under nitrogen atmosphere at 80° C. was added 20.7 g (0.07 mole) of 4',5-dichloro-2-nitrobenzophenone. The mixture was heated at 90° C. for 2 hr, then poured into water and neutralized with glacial acetic acid. The mixture was extracted with diethyl ether and then washed and dried over sodium sulfate; extracts were concentrated and excess diethyl malonate removed by distillation. The residue was chromatographed eluting with 50-75% isopropyl ether in hexane and the appropriate fraction collected. This material was hydrolyzed by heating at reflux in a mixture of 150 ml of dioxane and 80 ml of 6N hydrochloric acid for 6 hr. The reaction mixture was diluted with water and extracted with diethyl ether. The ether extracts were washed with dilute sodium hydroxide and the basic washings were combined, acidified and extracted with diethyl ether-isopropyl ether to give after recrystallization from 80% aqueous methanol, 6.2 g of title compound as tan crystals, m.p. 182.0°-183.0° C.

Workup

  1. extractionThe mixture was extracted with diethyl ether
  2. washwashed
  3. dry with materialdried over sodium sulfate
  4. concentrationextracts were concentrated
  5. customexcess diethyl malonate removed by distillation
  6. customThe residue was chromatographed
  7. washeluting with 50-75% isopropyl ether in hexane
  8. customthe appropriate fraction collected
  9. temperatureby heating
  10. temperatureat reflux in a mixture of 150 ml of dioxane and 80 ml of 6N hydrochloric acid for 6 hr
  11. additionThe reaction mixture was diluted with water
  12. extractionextracted with diethyl ether
  13. washThe ether extracts were washed with dilute sodium hydroxide
  14. extractionextracted with diethyl ether-isopropyl ether
  15. customto give
  16. customafter recrystallization from 80% aqueous methanol, 6.2 g of title compound as tan crystals, m.p. 182.0°-183.0° C.

Sources & evidence

ORD record
ord-500d17ac180e403497e5338a87f17865
Source dataset
uspto-grants-1990_02
Patent number
US04898874

Reaction notes

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