1,3-Propanediol → HCID 87298678, compound

HRID 74138Notes

Reaction equation

HRID 74138 reaction equation
[C:1]([OH:8])(=[O:7])[CH2:2][CH2:3][C:4]([CH3:6])=[O:5].[CH2:9]([OH:13])[CH2:10][CH2:11]O>[Pd]>[OH:5][CH2:4][CH2:3][CH2:2][O:5][CH:4]([CH3:6])[CH2:3][CH2:2][C:1]([O:8][CH2:11][CH2:10][CH2:9][OH:13])=[O:7]

Participants

4

Reactant 2

HCID 104421,3-PropanediolHCID 11579Levulinic Acid2×

Product 1

HCID 87298678HCID 87298678, compoundYield 5.3%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Conditions

Temperature
200 °C

Procedure

Levulinic acid (11.6 g; 0.1 mol), 1,3-propanediol (67.6 g; 0.89 mol), and 2.32 g of 10% Pd/C from Aldrich (20 wt % relative to levulinic acid) are charged to a Parr reactor, purged with nitrogen three times, heated to 200° C. with stirring, and reacted with 1000 psi of hydrogen for 20 hrs. GC analysis reveals that the reaction is complete. 1,3-Propylene glycol is distilled off at 58-59° C./0.1 mm to give 14.7 g of the crude product containing 79% of the desired monomer. The crude product (1.0 g) is chromatographed on silica gel using hexane-ethyl acetate from 3:1 to 1:1 to isolate about 0.62 g of 3-hydroxypropyl 4-(3-hydroxypropoxy)pentanoate. 1H NMR (δ, ppm, CDCl3): 1.07 d (3H, CH3), 1.66-1.80 m (6H, CH2), 2.31 m (2H, CH2CO), 3.1 (broad, 2H, OH), 3.39 m (2H, CH2O), 3.57 m (5H, 2×CH2OH, CH), 4.11 m (2H, COOCH2). 13C NMR (δ, ppm, CDCl3): 19.69 (CH3); 30.67, 31.85, 31.88; 32.68 (CH2 groups); 59.02, 61.21, 61.70, 67.06 (CH2O groups), 74.97 (CH), 174.15 (COO). Mass spectrum: m/e 234 (M+).

Workup

  1. custompurged with nitrogen three times
  2. customreacted with 1000 psi of hydrogen for 20 hrs
  3. distillation1,3-Propylene glycol is distilled off at 58-59° C./0.1 mm
  4. customto give 14.7 g of the crude product
  5. customThe crude product (1.0 g) is chromatographed on silica gel

Sources & evidence

ORD record
ord-4e2e43bb37c54a8e8088c6570141fad2
Source dataset
uspto-grants-2014_09
Patent number
US08829229B2

Reaction notes

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