Formaldehyde → 4,4-Di(hydroxymethyl)bicyclo(2.2.1)heptene

To a mixture of 364 g of 5-norbornene-2-carbaldehyde (which had been synthesized by Diels-Alder reaction of acrolein with cyclopentadiene) and 1500 ml of methanol under ice cooling, 560 g of a 37% formaldehyde aqueous solution was added and then 546 g of a 25% sodium hydroxide aqueous solution was added dropwise over 30 minutes. After the completion of dropwise addition, the ice bath was removed, and the reaction mixture was stirred for 18 hours at room temperature. The reaction mixture was concentrated by distilling off methanol under a reduced pressure. The resulting solid was dissolved in tetrahydrofuran and washed with a sodium hydroxide aqueous solution. The organic layer was concentrated in vacuum, obtaining crude 5-norbornene-2,2-dimethanol. This crude product was combined with 500 ml of tetrahydrofuran and 10 g of 5% palladium on activated carbon as a hydrogenation catalyst. Hydrogenation was carried out under a hydrogen pressure of 1.4 MPa in an autoclave which was maintained at 30-40° C. by occasional placement in a water bath. The reaction mixture was filtered of the catalyst, combined with ethyl acetate, and washed with a saturated potassium carbonate aqueous solution. The organic layer was dried over sodium sulfate and concentrated in vacuum, obtaining 435 g (yield 94%) of the target compound.

1. additionAfter the completion of dropwise addition
2. customthe ice bath was removed
3. concentrationThe reaction mixture was concentrated
4. distillationby distilling off methanol under a reduced pressure
5. dissolutionThe resulting solid was dissolved in tetrahydrofuran
6. washwashed with a sodium hydroxide aqueous solution
7. concentrationThe organic layer was concentrated in vacuum

ORD-Eintrag

ord-164d08bfd1274ed4aec296776026dbfe

Quelldatensatz

uspto-grants-2011_11

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08053165B2