SYNTHESIS AND TRANSFORMATION OF 5- AND 2-METHYLBICYCLO-.. .
951
%: C 89.02; H 10.98. C8H12. Calculated, %: C 88.88;
H 11.12.
4. Kas’yan, A.O., Maletina, I.K., Yagupol’skii, L.M.,
Markov, V.I., and Kas’yan, L.I., Russ. J. Org.
Chem., 1995, vol. 31, p. 320.
5. Kas’yan, A.O., Krasnovskaya, O.Yu., Zlenko, E.T.,
Okovityi, S.I., and Kas’yan, L.I., Russ. J. Org.
Chem., 1996, vol. 32, p. 1113.
6. Tandura, S.N., Shumskii, A.N., Litvin, E.F., Koz-
lova, L.M., Shuvalova, E.V., Sharf, V.Z., and Koles-
nikov, S.P., Izv. Ross. Akad. Nauk, Ser. Khim., 2001,
p. 971.
2-Methylbicyclo[2.2.1]hept-2-ene (III) [16]. Com-
pound V was subjected to isomerization at 200 300 C
in a flow system over a natural zeolite, clinoptilolite,
containing 70 80% of the crystalline form and having
a general formula of (K, Na)4Ca(Al6Si30O72) 20H2O
(14 10% of quartz, 2 2.5% of calcite, 2 2.5 of biotite,
and 2 3% of other species). Yield 24.6%, bp 117
120 C, d240 = 0.8608, n2D0 = 1.4630. 13C NMR spec-
7. Krieger, H. Arzneim.-Forsch., 1968, vol. 18, pp. 129,
trum, C, ppm: 45.67 (C1), 134.05 (C2), 125.54 (C3),
324, 487.
42.99 (C4), 27.12 (C5), 24.12 (C6), 45.65 (C7), 16.32
(CH3). Found, %: C 88.25; H 11.75. C8H12. Calcu-
lated, %: C 88.88; H 11.12.
8. Kas’yan, A.O., Tarabara, I.N., Zlenko, E.T., Okovi-
tyi, S.I., and Kas’yan, L.I., Russ. J. Org. Chem.,
1999, vol. 35, p. 1018.
A mixture of methyl-substituted bicyclo[2.2.1]hept-
2-enes was obtained in a similar way by isomerization
of compound I [17].
9. Bredt, J., Justus Liebigs Ann. Chem., 1924, p. 437.
10. Winstein, S., Sonnenberg, J., and de Vries, L., J. Am.
Chem. Soc., 1959, vol. 81, p. 6523.
5-Methylbicyclo[2.2.1]hept-2-ene (V) [13].
A mixture of 264 g (4.0 mol) of freshly prepared
cyclopentadiene and 369.6 g (8.8 mol) of propene
(molar ratio 1:2.2) was heated for 35 min at 200 C
in a high-pressure reactor. The adduct was obtained
in 93% yield as a mixture of endo and exo isomers,
bp 115 117 C, d240 = 0.8589, n2D0 = 1.4610. 13C NMR
spectrum, C, ppm: 39.57 (C1), 133.48 (C2), 129.31
11. Alder, K. and Muders, R., Chem. Ber., 1958, vol. 91,
p. 1088.
12. Gasanov, A.G., Abstracts of Papers, I Bakinskaya
mezhdunarodnaya konferentsiya po neftekhimii
(Ist Baku Int. Conf. on Petroleum Chemistry), Baku,
1994, p. 30.
13. Suleimanova, E.T., Gasanov, A.G., Kasumov, L.I.,
Nagiev, A.V., Pashaeva, F.A., Mirgasanova, M.I.,
and Aliev, R.R., USSR Inventor’s Certificate
no. 1391025, 1987; Byull. Izobret., 1988, no. 15.
14. Gasanov, A.G. and Musaev, M.R., Abstracts of
Papers, I Bakinskaya mezhdunarodnaya konferen-
tsiya po neftekhimii (Ist Baku Int. Conf. on Petro-
leum Chemistry), Baku, 1994, p. 41.
(C3), 41.98 (C4), 31.91 (C5), 34.31 (C6), 47.48 (C7),
18.61 (CH3). Found, %: C 88.68; H 11.32. C8H12.
Calculated, %: C 88.88; H 11.12.
2-Hydroxymethylbicyclo[2.2.1]heptane (VI).
Compound X, 186 g (1.5 mol), was subjected to
hydrogenation over Ni and Cr2O3 at 200 C in a high-
pressure reactor (reaction time 3 h, initial hydrogen
pressure 100 atm). Yield 80%, bp 73 75 C (2 mm),
15. Gasanov, A.G. and Nagiev, A.V., Zh. Org. Khim.,
1994, vol. 30, p. 70.
16. Gasanov, A.G., Musaev, M.R., and Alieva, L.I.,
USSR Inventor’s Certificate no. 1692977, 1989;
Byull. Izobret., 1994, no. 23.
17. Gasanov, A.G., Musaev, M.R., and Alieva, L.I.,
Russian Patent no. 2024473, 1991; Byull. Izobret.,
1994, no. 23.
18. Gasanov, A.G., Alieva, L.I., and Musaev, M.R.,
Neftekhimiya, 2000, vol. 40, p. 304.
19. Gasanov, A.G., Nagiev, A.V., and Alieva, L.I.,
d240 = 1.003, n2D0 = 1.4888.
5-Hydroxymethylbicyclo[2.2.1]hept-2-ene (X).
A mixture of 300 g (4.5 mol) of freshly prepared
cyclopentadiene and 530 g (9.0 mol) of allyl alcohol
was heated for 1.5 h at 180 C in a high-pressure
reactor. Distillation gave 419 g of adduct X, d420
=
1
1.029, n2D0 = 1.5008. H NMR spectrum, , ppm: 2.77
(1-H), 5.95 (2-H), 6.07 (3-H), 2.92 (4-H), 2.22 (5-H),
0.45 (endo-6-H), 1.77 (exo-6-H), 1.45 (syn-7-H), 1.24
(anti-7-H), 3.1 3.3 (5-CH2), 4.18 (OH).
Zh. Org. Khim., 1994, vol. 30, p. 785.
20. Gasanov, A.G., Doctoral (Chem.) Dissertation,
Baku, 1991.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003