1-Butanol → (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal

HRID 1525518Notes

Reaction equation

HRID 1525518 reaction equation
C(O)CCC.C(O)CCCCCCC.S(=O)(=O)(O)O.[OH:20][C@H:21]1[O:29][C@H:28]([CH2:30][OH:31])[C@@H:26]([OH:27])[C@H:24]([OH:25])[C@H:22]1[OH:23]>O>[O:20]=[CH:21][C@@H:22]([C@H:24]([C@@H:26]([C@@H:28]([CH2:30][OH:31])[OH:29])[OH:27])[OH:25])[OH:23]

Participants

6

Reactant 4

HCID 2631-ButanolHCID 9571-OctanolHCID 1118Sulfuric AcidHCID 79025Alpha-D-Glucose

Product 1

HCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
97.5 °C

Procedure

A maleic acid ester of an APG is prepared as follows. To a 1 L erlenmeyer flask, containing a magnetic stir bar, 185.1 g anhydrous n-butanol (Aldrich, 99.8%), 36.1 g n-octanol (Aldrich, 99+%), and 2.0 g deionized water are added. To the stirred mixture, 0.184 g (100 mL) of concentrated sulfuric acid (J. T. Baker, 96.6%) is added using a 1 mL glass syringe. This mixture is added to a 500 mL three necked round bottom flask containing 50.0 g of anhydrous α-D-glucose (Aldrich, 96%) and a concave magnetic stir bar. The flask is fitted with a thermocouple probe, a dry air intake, and a 25 mL Barrett receiver on which two glass condensers are mounted, which are connected to a gas bubbler. The condensate collection side of the Barrett receiver is filled with n-heptane, and the gas flow-through side is wrapped in cotton wool for the purpose of insulation. Dry air, passed over a 10 inch column filled with dry molecular sieves and Drierite, is passed through the liquid phase in the round bottom flask. The flask is heated for 4 hours at about 95 to 100° C. using a temperature controlled oil bath. Approximately 12 mL of condensate water is collected in the Barrett receiver as a result of glucose oligomerization reaction and the aldol condensation reaction to give alkylation at the C1 position. The white suspension of sugar particles disappears as the reaction from glucose to APG proceeds until a clear solution is obtained. This demonstrates that the APG is soluble in the alcohol. The resulting APG solution is colorless, indicating that byproduct formation of colored bodies, such as furfurals, is minimized.

Workup

  1. additionTo a 1 L erlenmeyer flask, containing a magnetic stir bar
  2. additionare added
  3. customThe flask is fitted with a thermocouple probe
  4. customThe condensate collection side of the Barrett receiver
  5. additionis filled with n-heptane
  6. customDry air
  7. additionfilled
  8. dry with materialwith dry molecular sieves and Drierite
  9. customApproximately 12 mL of condensate water is collected in the Barrett receiver as

Sources & evidence

ORD record
ord-a3b496de2b9749cab34b6d06ab3f7152
Source dataset
uspto-grants-2015_07
Patent number
US09080290B2

Reaction notes

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