D-(-)-Fructose → Naphthalene

HRID 926935Notes

Reaction equation

HRID 926935 reaction equation
O=[CH:2][C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([CH2:11]O)O)O)O)O.[CH3:13][C:14]1C=C(Cl)C=[CH:16][C:15]=1OCC(O)=O.CNC.C(O)[C@H]1O[C@H](O[C@]2(CO)O[C@H](CO)[C@@H](O)[C@@H]2O)[C@H](O)[C@@H](O)[C@@H]1O.OCC([C@H]([C@@H]([C@@H](CO)O)O)O)=O.O=C[C@H]([C@H]([C@@H]([C@@H](CO)O)O)O)O>S(=O)(=O)(O)O>[CH:5]1[C:7]2[C:9](=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:11]=[CH:2][CH:3]=1

Participants

7

Reactant 5

HCID 5984D-(-)-FructoseHCID 5988SucroseHCID 62420MCPA dimethylamine saltHCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal3×HCID 161658Demannose

Product 1

HCID 931Naphthalene

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
160 °C

Procedure

A 50 ml autoclave (Microclave reactor from Autoclave Engineers) was charged with 250 mg glucose, 150 mg of one of the catalysts: HY 2.6, HY 6, HY 30, Hbeta 12.5, Hbeta 19, Hbeta 150, and HZSM-5 (purchased from Zeolyst International, USA) and 10 mL solvent (methanol, ethanol, propanol or butanol) and then pressurized with argon (20 bar). The autoclave was heated to 160° C. and the stirring was started at 300 rpm once the temperature reached 150° C. After 20 hours of stirring, the autoclave was quenched with cold water and 50 mg naphthalene (internal standard) added to the reaction mixture and the content thereafter analyzed. Aliquots of the reaction mixtures were subjected to GC-FID analysis (Agilent 6890N instrument, HP-5 capillary column 30.0 m×320 μm×0.25 μm). The reaction mixtures were also analyzed by HPLC with RI detection (Agilent 1200 series, 30 cm Aminex© HPX-87H column, 0.005 M aqueous sulfuric acid solution as eluent at a flow rate of 0.6 ml/min). An Agilent 6850 GC system coupled with an Agilent 5975C mass detector was used for qualitative analysis. Sugar conversions to levulinic acid esters were determined by HPLC. The amounts of unreacted monosaccharides were calculated from their individual HPLC standards. Sucrose inverts to fructose and glucose on the acidic HPLC-column used, and the conversions were calculated from the monosaccharides fructose, glucose and mannose on a carbon-basis. The yield of levulinate esters were calculated from GC results on series of individual levulinate ester standards with naphthalene as internal standard. The results are shown in Tables 3 and 7.

Workup

  1. customreached 150° C
  2. customthe autoclave was quenched with cold water and 50 mg naphthalene (internal standard)
  3. additionadded to the reaction mixture
  4. customAliquots of the reaction mixtures
  5. customThe reaction mixtures

Sources & evidence

ORD record
ord-ad42c625dbc74343b1e08fbf61c0d0f6
Source dataset
uspto-grants-2016_03
Patent number
US09290429B2

Reaction notes

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