Sodium Hydroxide → HCID 21217005, compound

HRID 1586525Notes

Reaction equation

HRID 1586525 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:13]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)=[C:12]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:11]=C[C:9]=2[C:26]([O:28][CH2:29][CH3:30])=[O:27])=[CH:4][CH:3]=1.FC1C=CC(C(=O)C(=[O:45])C2C=CC(F)=CC=2)=CC=1.CCOC(CC(CC(OCC)=O)=O)=O.[OH-].[Na+]>CO>[C:26]([C:9]1[C:11](=[O:45])[C:12]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[C:13]([C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)[C:8]=1[C:5]1[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=1)([O:28][CH2:29][CH3:30])=[O:27]

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 66045Diethyl acetonedicarboxylateHCID 1230724,4'-DifluorobenzilHCID 21217002HCID 21217002, compound

Product 1

HCID 21217005HCID 21217005, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Diethyl 2,3-di(4-fluorophenyl)-1,4-benzenedicarboxylate In a 500 mL round bottom flask was loaded difluorobenzil (12.3 g, 50.0 mmol), diethyl acetonedicarboxylate (12.1 g, 60.0 mmol) and methanol (100 mL) with stirring. This was cooled in an ice/water bath and methanolic NaOH (2 g in 50 mL of methanol) added to the mixture. This was stirred overnight. The resultant yellow precipitate was filtered and washed with methanol (2×20 mL) and air-dried. The yellow precipitate was then added to acetic anhydride (300 mL). The mixture was cooled in an ice/water bath and then sulfuric acid was added dropwise until an orange solution resulted. Several more drops of sulfuric was then added and the solution stirred for 30 min. The excess acetic anhydride was destroyed by addition of water. Excess water (1 L) was added to precipitate out the orange product. The orange precipitate was filtered and washed repeatedly water and air-dried to give 2,5-dicarboethoxy-3,4-di-(4-fluorophenyl)-cyclopentadienone (16.7 g, 81% yield). In a 100 mL round-bottom flask was loaded 2,5-dicarboethoxy-3,4-di-(4-fluorophenyl)-cyclopentadienone (2.6 g, 6.3 mmol), norbornadiene (2.9 g, 31.5 mmol) and toluene (45 mL) with stirring. The mixture was refluxed for 5 hour and then the solvent was removed. Methanol was then added to precipitate out the white product. The white precipitate was filtered and washed with methanol (2×5 mL) and air-dried (1.22 g, 47% yield).

Workup

  1. temperatureThis was cooled in an ice/water bath
  2. filtrationThe resultant yellow precipitate was filtered
  3. washwashed with methanol (2×20 mL)
  4. customair-dried
  5. additionThe yellow precipitate was then added to acetic anhydride (300 mL)
  6. temperatureThe mixture was cooled in an ice/water bath
  7. additionsulfuric acid was added dropwise until an orange solution
  8. customresulted
  9. additionSeveral more drops of sulfuric was then added
  10. stirringthe solution stirred for 30 min
  11. customThe excess acetic anhydride was destroyed by addition of water
  12. additionExcess water (1 L) was added
  13. customto precipitate out the orange product
  14. filtrationThe orange precipitate was filtered
  15. washwashed repeatedly water
  16. customair-dried

Sources & evidence

ORD record
ord-4756b26076624c678b865a502a4824a1
Source dataset
uspto-grants-1999_08
Patent number
US05945502

Reaction notes

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