Methanol → 6-Methylheptanoic acid

HRID 1464151Notes

Reaction equation

HRID 1464151 reaction equation
S(=O)(=O)(O)O.O.[C:7]([OH:16])(=[O:15])[CH2:8][CH2:9][CH2:10][CH2:11][CH:12]([CH3:14])[CH3:13].[CH3:17]O>>[C:7]([O:16][CH3:17])(=[O:15])[CH2:8][CH2:9][CH2:10][CH2:11][CH:12]([CH3:14])[CH3:13].[C:7]([OH:16])(=[O:15])[CH2:8][CH2:9][CH2:10][CH2:11][CH:12]([CH3:14])[CH3:13]

Participants

6

Reactant 4

HCID 887Methanol3×HCID 962Water2×HCID 1118Sulfuric Acid4×HCID 907166-Methylheptanoic acid

Product 2

HCID 907166-Methylheptanoic acidHCID 520188Isooctanoic acid, methyl ester

Procedure

The sulfuric acid is employed in an amount sufficient to both catalyze the reaction and to serve as a dehydrating agent or desiccant for the by-product water. Accordingly, the sulfuric acid should be employed in an amount greater than about 0.05 moles per mole of carboxylic acid to be esterified and preferably above 0.1 moles and of sulfuric acid per mole of carboxylic acid, which is sufficient to both catalyze the dehydrate the water. Most desirably, from about 0.1 to about 0.5 moles of sulfuric acid and most preferably about 0.2 moles will be employed per mol of carboxylic acid. The reaction is carried out at elevated temperatures, conveniently reflux conditions. With methanol as the alcohol and a carboxylic acid having from about 6 to about 22 carbon atoms a temperature will be on the order of about 70° to about 100° C. However, temperatures on the order at about 40° to about 120° C. and more preferably 60° to about 80° C. will be employed. The specific temperature employed will be determined however by the specific alcohol employed and specific carboxylic acid to be esterified. In the laboratory reflux periods of about 1 to 2 hours were sufficient to provide yields of methyl isooctanoate in the methanol esterification of isooctanoic acid employing about 1.5 to about 2 moles of methanol per mole of isooctanoic acid which provided the ester of greater than 99% purity. In contrast, in reactions not using an excess of sulfuric acid (only a catalytic amount) time periods of reflux of about 10 hours or more were required to provide about an 80% yield of ester of lower purity even with a seven molar excess of methanol. Again, the reaction period will depend on the specific alcohol employed and specific acid to be esterified. Generally reaction periods will not need to exceed about 4 hours and the reaction will be complete (about 90% yield) usually within 1 to about 3 hours employing the preferred levels of carboxylic acid, alcohol and sulfuric acid. After completion of the esterification the sulfuric acid layer is removed and any unesterified acid is removed as the sodium salt by an alkaline aqueous wash. The ester may be dried by azeotropic distillation with an aliphatic hydrocarbon solvent such as heptane. The unreacted carboxylic acid in the aqueous alkaline wash can be recovered by acidification with an acid, preferably spent sulfuric acid, from the esterification step.

Workup

  1. customthe reaction
  2. customwill be on the order of about 70° to about 100° C
  3. customat about 40° to about 120° C.
  4. custommore preferably 60° to about 80° C.
  5. temperatureIn the laboratory reflux periods of about 1 to 2 hours
  6. customto provide

Sources & evidence

ORD record
ord-174703205e5b4000952d14dbb9ad02d0
Source dataset
uspto-grants-1994_04
Patent number
US05302748

Reaction notes

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