1,3-Dioxolane-4-methanol → 1,3-Dioxan-5-yl 5-norbornene-2-carboxylate

HRID 351493

Reaction equation

HRID 351493 reaction equation
C1OCOC1CO.C12CC(C=C1)CC2C(OC)=O.C[O-].[Na+].[CH:22]12[CH2:28][CH:25]([CH:26]=[CH:27]1)[CH2:24][CH:23]2[C:29]([O:31][CH2:32][CH:33]1[CH2:37][O:36][CH2:35][O:34]1)=[O:30]>C1(C)C=CC=CC=1>[CH:22]12[CH2:28][CH:25]([CH2:26][CH2:27]1)[CH:24]=[C:23]2[C:29]([O:31][CH:32]1[CH2:33][O:34][CH2:35][O:36][CH2:37]1)=[O:30]

Participants

6

Reactant 4

HCID 216181,3-Dioxolane-4-methanolHCID 250075Methyl bicyclo[2.2.1]hept-5-ene-2-carboxylateHCID 10942334Sodium MethoxideHCID 22713062(1,3-Dioxolan-4-yl)methyl 5-norbornene-2-carboxylate

Product 1

HCID 699102001,3-Dioxan-5-yl 5-norbornene-2-carboxylateYield 93%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 104 g of glycerol formal, 152 g of methyl 5-norbornene-2-carboxylate, 2.0 g of sodium methoxide and 300 ml of toluene was heated under reflux for 5 hours while gradually distilling off methanol formed during the reaction. After cooling, the reaction solution was washed with saturated sodium bicarbonate water, dried over anhydrous sodium sulfate, and concentrated in vacuum. It was further purified by vacuum distillation, obtaining 209 g of a mixture of (1,3-dioxolan-4-yl)methyl 5-norbornene-2-carboxylate and 1,3-dioxan-5-yl 5-norbornene-2-carboxylate (boiling point 111-115° C./530 Pa, yield 93%).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 5 hours
  3. distillationwhile gradually distilling off methanol
  4. customformed during the reaction
  5. temperatureAfter cooling
  6. washthe reaction solution was washed with saturated sodium bicarbonate water
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated in vacuum
  9. distillationIt was further purified by vacuum distillation

Sources & evidence

ORD record
ord-fff2a3c571664cd69e5568bf0402cb1f
Source dataset
uspto-grants-2004_06
Patent number
US06743566B2

Linked notes

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