Chloride → HCID 18408283, compound

HRID 2372533Notes

Reaction equation

HRID 2372533 reaction equation
[CH:1]1[CH2:5][CH:4]=[CH:3][CH:2]=1.Cl.[C:7]([O:15][CH2:16][CH3:17])(=[O:14])[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[Na].[Cl-].C([O-])(=O)CC([O-])=O>C(O)C>[C:2]1([CH:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:7]([O:15][CH2:16][CH3:17])=[O:14])[CH2:1][CH2:5][CH2:4][CH:3]=1

Participants

8

Reactant 6

HCID 312ChlorideHCID 313Hydrochloric Acid2×HCID 7612Cyclopentadiene2×HCID 7761Diethyl MalonateHCID 9084Malonate Ion3×HCID 5360545Sodium

Product 1

HCID 18408283HCID 18408283, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To 174 g (2.63 mol) of freshly depolymerized cyclopentadiene, cooled and maintained at -78 C, was added 87.5 g (2.50 mol) gaseous HCl. Meanwhile, 152 mL (1.0 mol) diethyl malonate was added to a solution of 21.4 g (0.93 mol) sodium in 400 mL absolute ethanol. After HCl addition to the cyclopentadiene was complete, the crude yellow chloride, maintained at -78 C, was added in mL portions to the malonate solution. With addition of each 1 ml portion of the malonate solution, considerable heat was produced, the yellow color rapidly dissipated, and copious white precipitate formed. After addition of all of the malonate, the suspension was stirred for 17 hrs, after which most of the ethanol was removed by rotary evaporation, and the reaction was quenched with 200 mL water and extracted 5 ×, each with 100 mL of diethyl ether. The combined extracts were dried over MgSO4, filtered, and concentrated to a clear yellow oil. Distillation of a portion of this material under 0.5 mm Hg pressure yielded 19.091 g clear, light green oil, bp 91-94 C.

Workup

  1. temperaturemaintained at -78 C
  2. temperatureconsiderable heat
  3. customwas produced
  4. customcopious white precipitate formed
  5. customafter which most of the ethanol was removed by rotary evaporation
  6. customthe reaction was quenched with 200 mL water
  7. extractionextracted 5 ×
  8. dry with materialThe combined extracts were dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated to a clear yellow oil
  11. distillationDistillation of a portion of this material under 0.5 mm Hg pressure
  12. customyielded 19.091 g clear

Sources & evidence

ORD record
ord-3184323dfeb64814b1eed155f31105f7
Source dataset
uspto-grants-1992_03
Patent number
US05099020

Reaction notes

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