HCID 19760432, compound → HCID 19760419, compound

HRID 1587042Notes

Reaction equation

HRID 1587042 reaction equation
[O:1]([C:16]1[CH:21]=[CH:20][C:19]([C:22]([O:24][CH3:25])=[O:23])=[C:18]([C:26]([O:28][CH3:29])=[O:27])[CH:17]=1)[C:2]1[CH:7]=[CH:6][C:5]([C:8]([O:10][CH3:11])=[O:9])=[C:4]([C:12]([O:14][CH3:15])=[O:13])[CH:3]=1>[Rh].C1COCC1>[O:1]([CH:16]1[CH2:21][CH2:20][CH:19]([C:22]([O:24][CH3:25])=[O:23])[CH:18]([C:26]([O:28][CH3:29])=[O:27])[CH2:17]1)[CH:2]1[CH2:7][CH2:6][CH:5]([C:8]([O:10][CH3:11])=[O:9])[CH:4]([C:12]([O:14][CH3:15])=[O:13])[CH2:3]1

Participants

4

Reactant 1

HCID 19760432HCID 19760432, compound

Product 1

HCID 19760419HCID 19760419, compound

Reagents, catalysts & solvents 2

HCID 23948RhodiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
120 °C

Procedure

A 1-L stainless steel autoclave was charged with 100 g of oxydi(3,4-dicarbomethoxybenzene), 3.00 g of 5% rhodium on alumina, and 750 mL of THF. With stirring, the reactor was purged several times with hydrogen and then charged to approximately 2000 psi of hydrogen. The reaction mixture was heated to 120° C., and the mixture was allowed to stir for 20 h. The reactor was cooled and vented, and the crude reaction mixture removed. The solution was filtered to remove catalyst and then concentrated using a rotary evaporator. The oily residue was partitioned between water and ethyl acetate. The organic phase was washed with brine, dried (MgSO4), and concentrated to a clear lightly colored oil using a rotary evaporator. Gas chromatographic analysis of the crude product reveals a mixture of tetramethyl oxydi(cyclohexane-3,4-dicarboxylate) (major), dimethyl cyclohexanedicarboxylate (minor), and dimethyl 4-hydroxycyclohexanedicarboxylate (minor).

Workup

  1. customthe reactor was purged several times with hydrogen
  2. additioncharged to approximately 2000 psi of hydrogen
  3. stirringto stir for 20 h
  4. temperatureThe reactor was cooled
  5. customthe crude reaction mixture
  6. customremoved
  7. filtrationThe solution was filtered
  8. customto remove catalyst
  9. concentrationconcentrated
  10. customa rotary evaporator
  11. customThe oily residue was partitioned between water and ethyl acetate
  12. washThe organic phase was washed with brine
  13. dry with materialdried (MgSO4)
  14. concentrationconcentrated to a clear lightly colored oil
  15. customa rotary evaporator
  16. additiona mixture of tetramethyl oxydi(cyclohexane-3,4-dicarboxylate) (major), dimethyl cyclohexanedicarboxylate (minor), and dimethyl 4-hydroxycyclohexanedicarboxylate (minor)

Sources & evidence

ORD record
ord-aad54534c7cd4a88827a22b77574dfa1
Source dataset
uspto-grants-1993_06
Patent number
US05216173

Reaction notes

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