Dicyclopentadiene → 5-Norbornene-2-methanol hydroxylethyl ether

Temperatur

190 °C

In a 300 mL autoclave equipped with a thermal couple and a mechanical stirrer, a mixture of 2-allyloxyethanol (109.5 g, 1.07 mol) and dicyclopentadiene (35.4 g, 0.27 mol) was stirred and heated to 190° C. The reaction was cooled after 3 h. Three such reactions were run and the reaction mixtures were combined. The mixture was distilled using a short-path distillation column under vacuum at 70° C. at 500 mTorr. The distillate (170 g) was dissolved in a mixture of 250 mL of CH3OH and 150 mL of H2O. Hexane (3×125 mL) was added to the mixture in order to extract out cyclopentadiene impurities. To the remaining methanol/water solution NaCl was added to force the product to oil out from solution. Ethyl acetate (200 mL) was added to extract the oil from water. After the solvents were removed by rotovaporation the product was dried under vacuum. Yield 157 g (58%). 1H NMR (500 MHz, CDCl3): Endo isomer: 6.13 (m, 1H); 5.93 (m, 1H); 3.72 (t, 2H); 3.52 (m, 2H); 3.22 (t, 1H); 3.10 (t, 1H); 2.90 (s, 1H); 2.80 (s, 1H); 2.37 (m, 1H); 2.09 (br s, 1H); 1.82 (m, 1H); 1.43 (d, 1H), 1.26 (d, 1H), 0.50 (d oft, 1H). Exo isomer: 6.10 (m, 1H); 6.07 (m, 1H); 3.75 (t, 2H); 3.36 (m, 2H); 3.50 (t, 1H); 3.40 (t, 1H); 2.80 (s, 1H); 2.74 (s, 1H); 2.09 (br s, 1H); 1.71 (m, 1H); 1.33 (d, 1H), 1.30 (d, 1H); 1.24 (m, partially obscured by endo isomer, 1H); 1.11 (d of t, 1H). Endo/exo ratio by 1H NMR was determined to be 82/18.

1. customIn a 300 mL autoclave equipped with a thermal couple and a mechanical stirrer
2. temperatureThe reaction was cooled after 3 h
3. customthe reaction mixtures
4. distillationThe mixture was distilled
5. distillationa short-path distillation column under vacuum at 70° C. at 500 mTorr
6. dissolutionThe distillate (170 g) was dissolved in a mixture of 250 mL of CH3OH and 150 mL of H2O
7. additionHexane (3×125 mL) was added to the mixture in order
8. extractionto extract out cyclopentadiene impurities
9. additionTo the remaining methanol/water solution NaCl was added
10. additionEthyl acetate (200 mL) was added
11. extractionto extract the oil from water
12. customAfter the solvents were removed by rotovaporation the product
13. customwas dried under vacuum

ORD-Eintrag

ord-311bf89d9df64650aaaff467f922f067

Quelldatensatz

uspto-grants-2011_02

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US07888415B2