Ethanol → HCID 14200631, compound

HRID 1725600Notes

Reaction equation

HRID 1725600 reaction equation
Br[CH2:2][C:3]1[C:4]([CH2:9]Br)=[CH:5][CH:6]=[CH:7][CH:8]=1.[C:11]([O:19]CC)(=[O:18])[CH2:12][C:13](OCC)=O.C[O-].[Na+].C(O)C>CCOCC.CO.S(=O)(=O)(O)O>[CH3:2][CH:3]1[CH2:8][C:7]2[C:13](=[CH:9][CH:4]=[CH:5][CH:6]=2)[CH:12]1[C:11]([OH:19])=[O:18]

Participants

8

Reactant 4

HCID 702EthanolHCID 7761Diethyl MalonateHCID 66665o-Bis(bromomethyl)benzeneHCID 10942334Sodium Methoxide

Product 1

HCID 14200631HCID 14200631, compoundYield 54.2%

Reagents, catalysts & solvents 3

HCID 1118Sulfuric AcidCatalystHCID 887MethanolSolventHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
200 °C

Procedure

A solution of α,α′-dibromo-o-xylene (203.51 g, 0.77 mol) in 1.5 l of ether is added to a solution of diethyl malonate (127 g, 0.79 mol), sodium methoxide (314 ml, 1.70 mol), ethanol (100 ml) and ether (500 ml). The mixture is refluxed for 5 hours, then filtered, and finally concentrated. The residue is taken up in 500 ml of water. 173 g of potassium hydroxide are added, and the mixture is refluxed for 18 hours. The reaction medium is poured into a hydrochloric acid solution and the precipitate formed is filtered off by suction and then dried. The solid obtained is maintained at 200° C. for 20 minutes and the new solid obtained is recrystallised from 400 ml of heptane. The crystals obtained are taken up in 400 ml of methanol and, after 5 drops of concentrated sulfuric acid have been added, the mixture is refluxed for 4 hours and then concentrated. The residue is dissolved in 600 ml of ether. This ether phase is washed with saturated sodium bicarbonate solution and saturated sodium chloride solution and then dried over sodium sulfate and concentrated, giving 73.6 g (54%) of a clear oil.

Workup

  1. temperatureThe mixture is refluxed for 5 hours
  2. filtrationfiltered
  3. concentrationfinally concentrated
  4. addition173 g of potassium hydroxide are added
  5. temperaturethe mixture is refluxed for 18 hours
  6. additionThe reaction medium is poured into a hydrochloric acid solution
  7. customthe precipitate formed
  8. filtrationis filtered off by suction
  9. customdried
  10. customThe solid obtained
  11. customthe new solid obtained
  12. customis recrystallised from 400 ml of heptane
  13. customThe crystals obtained
  14. temperaturethe mixture is refluxed for 4 hours
  15. concentrationconcentrated
  16. dissolutionThe residue is dissolved in 600 ml of ether
  17. washThis ether phase is washed with saturated sodium bicarbonate solution and saturated sodium chloride solution
  18. dry with materialdried over sodium sulfate
  19. concentrationconcentrated

Sources & evidence

ORD record
ord-7676cad80a7f4b298cc437ff3f615030
Source dataset
uspto-grants-2009_02
Patent number
US07491733B2

Reaction notes

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