Sulfuric Acid → Gamma-Decalactone

HRID 1648836Notes

Reaction equation

HRID 1648836 reaction equation
S(=O)(=O)(O)O.[CH:6](=[O:13])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[C:14](OC)(=O)[CH:15]=[CH2:16].S([O-])([O-])(=O)=[O:21].C([N+](CC)(CC)CC)C.C([N+](CC)(CC)CC)C.S([O-])([O-])(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC>O>[CH2:10]([CH:9]1[O:21][C:6](=[O:13])[CH2:7][CH2:8]1)[CH2:11][CH2:12][CH2:14][CH2:15][CH3:16]

Participants

7

Reactant 5

HCID 1118Sulfuric AcidHCID 7294Methyl Acrylate2×HCID 8130Heptanal2×HCID 75782Tetraethylammonium sulphateHCID 11433187Bis(tetrabutylammonium) sulphate

Product 1

HCID 12813Gamma-DecalactoneYield 224.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

The circulation type electrolytic apparatus as described in Example 24 and 10 wt% sulfuric acid as an anolyte were used. As a catholyte was used a mixture of 73.9 g (0.648 mol) of heptanal, 18.6 g (0.216 mol) of methyl acrylate, 418 g of water, 53 g (0.149 mol) of tetraethylammonium sulfate and 36 g (0.062 mol) of tetra-n-butylammonium sulfate. The electrolysis was carried out at a catholyte temperature of 27° to 29° C. and a current density of 10.0 A/dm2 while stirring the catholyte in the electrolytic apparatus by circulating the catholyte at a flow rate of 200 cm/sec between the cathode chamber and the catholyte tank. A mixture of 45.9 g (0.403 mol) of heptanal and 48.8 g (0.567 mol) of methyl acrylate was fed into the catholyte tank little by little over five hours during the electrolysis. When the relative current quantity reached 66%, the electrolysis was stopped. During the electrolysis, the voltage fluctuated between 5.8 V and 5.9 V. After the electrolysis, the catholyte was allowed to stand so as to be separated into an organic phase and a water phase. The organic phase was washed with 50 g of water and, then, distilled. 10 g of methyl acrylate was recovered from the organic and water phases. 66 g of heptanal was recovered from the organic phase. By distilling the organic phase, 22 g of dimethyl adipate as a by-product and 57 g of 4-n-hexyl-4-butanolide were obtained. The results are summarized as follows:

Workup

  1. customwas carried out at a catholyte temperature of 27° to 29° C.
  2. customlittle over five hours
  3. customto be separated into an organic phase
  4. washThe organic phase was washed with 50 g of water
  5. distillationdistilled
  6. custom10 g of methyl acrylate was recovered from the organic and water phases
  7. custom66 g of heptanal was recovered from the organic phase
  8. distillationBy distilling the organic phase, 22 g of dimethyl adipate as a by-product

Sources & evidence

ORD record
ord-4c4fa308eb1a4c45adaa38ca8a2fc627
Source dataset
uspto-grants-1983_11
Patent number
US04414079

Reaction notes

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