Formic Acid → Tricyclo [2.2.1.02,6]heptan-5-ol bisformate

HRID 267555Notes

Reaction equation

HRID 267555 reaction equation
[CH2:1]=[O:2].[C:3]12[CH2:9][C:6]([CH2:7][CH2:8]1)=[CH:5]C=2.[CH:10]([OH:12])=[O:11]>OS(O)(=O)=O>[CH:10]([OH:12])=[O:11].[CH:10]([OH:12])=[O:11].[CH:6]12[CH2:7][CH:8]3[CH:1]([OH:2])[CH:5]1[CH:9]2[CH2:3]3

Participants

5

Reactant 3

HCID 284Formic AcidHCID 712FormaldehydeHCID 18006658Norborna-diene

Product 1

HCID 86733116Tricyclo [2.2.1.02,6]heptan-5-ol bisformateYield 84%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

To a stirred solution of 39.9 g paraformaldehyde in formic acid (800 ml) and conc. H2SO4 (15 ml) under nitrogen and at 20°C was added dropwise 132 g norbornadiene while keeping the temperature between 20°-25°C. After 1.5 hr the reaction was quenched by adding to 800 ml of ice-water. Extraction with ether (3 × 750 ml), washing the organic layer with water (1 × 250 ml), brine (3 × 250 ml) and drying (Na2SO4) afforded the crude 3-hydroymethyl tricyclo [2.2.1.02,6 ]heptan-5-ol bisformate (1') as an oil. Distillation, after a forerum of bp. 40°C/15mm, gave 235 g pure tricyclenebisformate, bp. 104°C/0.3 mm (84% yield).

Workup

  1. custombetween 20°-25°C
  2. customAfter 1.5 hr the reaction was quenched
  3. additionby adding to 800 ml of ice-water
  4. extractionExtraction with ether (3 × 750 ml)
  5. washwashing the organic layer with water (1 × 250 ml), brine (3 × 250 ml)
  6. dry with materialdrying (Na2SO4)

Sources & evidence

ORD record
ord-c185b88dd3534f00869d5c4baccbb341
Source dataset
uspto-grants-1976_03
Patent number
US03943151

Reaction notes

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