Malic Acid → Dihexadecyl 2-hydroxybutanedioate

HRID 2050768Notes

Reaction equation

HRID 2050768 reaction equation
[CH2:1]([OH:17])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16].[C:18]([OH:26])(=[O:25])[CH:19]([CH2:21][C:22]([OH:24])=O)[OH:20].CO.[CH3:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34]>CS(O)(=O)=O.C(O)=O.C(O)CCC.C(OCC)(=O)C>[C:18]([O:26][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10])(=[O:25])[CH:19]([CH2:21][C:22]([O:17][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])=[O:24])[OH:20]

Participants

9

Reactant 4

HCID 525Malic AcidHCID 887Methanol2×HCID 2682Cetyl Alcohol2×HCID 8058Hexane2×

Product 1

HCID 19833574Dihexadecyl 2-hydroxybutanedioate

Reagents, catalysts & solvents 4

HCID 6395Methanesulfonic AcidCatalystHCID 2631-ButanolSolventHCID 284Formic AcidSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
22 °C

Procedure

1-Hexadecanol (87.4 g, 0.36 mole), dl-malic acid (20.1 g, 0.15 mole), methanol (600 ml), methane sulfonic acid (15 drops) and several "Chemfluor" boiling chips were placed in a 1000-ml round-bottomed flask. The mixture was refluxed for 16 hours. Most of the methanol was stripped from the mixture at a pressure of about 250 mm Hg. Stripping was then continued at 5 mm Hg and 80° C. for 6 hours. Final weight was 104.41 g. TLC indicated the composition was about 5:3:2 dihexadecyl ester: methyl hexadecyl ester: hexadecanol. Hexane (500 ml) was added and warmed to dissolve all solids. On slow cooling to about 22° C., a first crystalline crop of 38.91 g was obtained after filtration. By further cooling to about 17° C., a second crystalline crop of 27.21 g was obtained. Residuals of 37.81 g were reserved for recycle. Both crystal crops contained considerable impurity; the second crop, about 50%. Recrystallization from hexane gave material which migrated as a single spot during TLC (80:18:2:2 hexane: ethyl acetate:1-butanol: formic acid irrigant, silica gel plates). This recrystallized product melted at 61.4°-62.7° C.

Workup

  1. customwere placed in a 1000-ml round-bottomed flask
  2. temperatureThe mixture was refluxed for 16 hours
  3. temperaturewarmed
  4. dissolutionto dissolve all solids
  5. customa first crystalline crop of 38.91 g was obtained
  6. filtrationafter filtration
  7. temperatureBy further cooling to about 17° C.
  8. customa second crystalline crop of 27.21 g was obtained
  9. customRecrystallization from hexane
  10. customgave material which

Sources & evidence

ORD record
ord-dde726dd5fa94622b9684d32b44dccfd
Source dataset
uspto-grants-1991_05
Patent number
US05015418

Reaction notes

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