Hydrogen Peroxide → Azelaic Acid

HRID 861670Notes

Reaction equation

HRID 861670 reaction equation
[C:1]([O:20]C)(=[O:19])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8]/[CH:9]=C\CCCCCCCC.C(OC)(=[O:40])CCCCCCC/C=C\C/C=C\CCCCC.[OH:43][C:44]([OH:64])([CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55]CCCCCCCC)C(O)=O.OO.[OH-:67].[Na+].S(=O)(=O)(O)O>[Co](Cl)Cl.O>[C:1]([OH:20])(=[O:19])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]([OH:40])=[O:67].[C:44]([OH:64])(=[O:43])[CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55]

Participants

10

Reactant 6

HCID 784Hydrogen Peroxide3×HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 5284421Methyl linoleateHCID 5364509Methyl OleateHCID 20391236Dihydroxyoctadecanoic acid

Product 2

HCID 2266Azelaic AcidYield 70%HCID 8158Nonanoic AcidYield 68.8%

Reagents, catalysts & solvents 2

HCID 24288Cobalt(II) chlorideCatalystHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

Into the same apparatus as in Example 1, 100 g of crude methyl oleate (82% purity) containing 9.9% methyl linoleate, 0.75 g of H2WO4 and 1.25 g of dihydroxystearic acid is added. The stirred mixture is brought to 60°-65° C. and 28.6 g of 60% w/w H2O2 is added. The H2O2 is gradually added over about 30 mins in order to maintain the temperature between 60°-70° C. Once the addition of H2O2 is completed the mixture is left at that temperature for another 4 hours. The crude reaction product so obtained is charged into a stirred 500 ml autoclave containing 150 ml of water and 1.0 g of hydrous cobalt chloride. The autoclave is then pressurised with 75 atm of air and the temperature is raised to 65° C. The reaction mixture is stirred at this temperature for 7 hours. At the end, NaOH is added to the reaction mixture until an alkaline pH is reached and saponified for 2 hours at 95° C. After acidification with sulphuric acid, the crude reaction products are treated in the same way as described in example 1. 40.8 g of azelaic acid (yield=70%) and 33.5 g of pelargonic acid (yield=68.8%) are obtained.

Workup

  1. additionis added
  2. customis brought to 60°-65° C.
  3. temperatureto maintain the temperature between 60°-70° C
  4. customThe crude reaction product
  5. customso obtained
  6. additionis charged into a stirred 500 ml autoclave
  7. waitsaponified for 2 hours at 95° C
  8. additionare treated in the same way

Sources & evidence

ORD record
ord-043a004487284c918b266cb82dcd7fdd
Source dataset
uspto-grants-1998_02
Patent number
US05714623

Reaction notes

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