TRANSFORMATIONS OF (–)-MYRTENAL EPOXIDE
59
compound V, 0.030 g of a mixture of aldehydes V and
VII (2.2:1, according to the 1H NMR data), 0.077 g of
a mixture of IV and VII (2:1, H NMR), 0.019 g of
4-(1-Hydroxy-1-methylethyl)benzaldehyde (IX).
The chemical shifts of protons and carbon nuclei in the
1H and 13C NMR spectra of compound IX were similar
to those reported in [9].
1
VI, and 0.020 g of a mixture of aldehydes VIII and IX
(2:1, 1H NMR).
This study was performed under financial support
by the Presidium of the Russian Academy of Sciences
(integrated program no. 25, state contract no. 10104-
71/P-25/155-256/290404-008) and by the Federal
Science and Innovation Agency (state contract
no. 02.434.11.2026).
5,5-Dimethyl-4-(2-oxoethyl)cyclopent-1-ene-1-
20
carbaldehyde (V). [α] = +20.7° (c = 8.2). 1H NMR
580
spectrum, δ, ppm: 0.93 s (C9H3), 1.21 s (C8H3),
2.05 d.d.d (3-H, J3,3' = 18.5, J3,4 = 9, J3,2 = 2.5 Hz),
2.33 d.d.d (6-H, J6,6' = 10, J6,4 = 10, J6,7 = 2.0 Hz),
2.36 m (4-H), 2.55 m (6'-H), 2.74 d.d.d (3'-H, J = 18.5,
J3',4 = 7.5, J3',2 = 3 Hz), 6.64 d.d (2-H, J2,3' = 3, J2,3
2.5 Hz), 9.61 s (10-H), 9.75 d.d (7-H, J7,6 = 2, J7,6'
=
=
REFERENCES
1.5 Hz). 13C NMR spectrum, δC, ppm: 153.90 s (C1),
150.49 d (C2), 36.78 t (C3), 44.46 d (C4), 45.39 s (C5),
43.85 t (C6), 200.34 d (C7), 25.45 q (C8), 20.34 q (C9),
188.78 d (C10). Found: [M]+ 166.09956. C10H14O2.
Calculated: M 166.09937.
1. Solladie-Cavallo, A., Balaz, M., Salisova, M., and
Welter, R., J. Org. Chem., 2003, vol. 68, p. 6619.
2. Erman, W.F., Chemistry of the Monoterpenes, New
York: Marcel Dekker, 1985, part B, p. 965.
3. Il’ina, I.V., Korchagina, D.V., Salakhutdinov, N.F., and
Barkhash, V.A., Russ. J. Org. Chem., 2000, vol. 36,
p. 1446.
4. Klein, E.A., US Patent no. 2821547, 1958; Chem.
Abstr., 1958, vol. 52, p. 16412c.
5. Volcho, K.P., Rogoza, L.N., Salakhutdinov, N.F., Tolsti-
kov, A.G., and Tolstikov, G.A., Preparativnaya khimiya
terpenoidov. Chast’ 1. Bitsiklicheskie monoterpenoidy
(Preparative Chemistry of Terpenoids. Part 1. Bicyclic
Monoterpenoids), Novosibirsk: Sib. Otd. Ross. Akad.
Nauk, 2006.
6. Il’ina, I.V., Volcho, K.P., Korchagina, D.V., Salakhut-
dinov, N.F., and Barkhash, V.A., Russ. J. Org. Chem.,
2004, vol. 40, p. 1432.
7,7-Dimethyl-6-oxabicyclo[3.2.1]oct-3-ene-4-car-
20
1
baldehyde (VI). [α] = +29.8 (c = 9.4). H NMR
580
spectrum, δ, ppm: 1.18 s and 1.22 s (C9H3, C10H3),
1.69 d (syn-8-H, J = 11 Hz), 2.23 m (1-H, J1,8-anti = 5,
J1,2 = 4, J1,2' = 2.5 Hz), 2.33 d.d.d (anti-8-H, J = 11,
2
2
J8-anti,1 = 5, J8-anti,5 = 5 Hz), 2.53 d.d.d (2-H, J2,2' = 20,
J2,1 = 4, J2,3 = 3 Hz), 2.62 d.d.d.d (2'-H, J = 20, J2',3
=
4, J2',1 = 2.5, J = 1 Hz), 4.81 br.d (5-H, J5,8-anti = 5 Hz)
6.54 m (3-H, J3,2' = 4, J3,2 = 3, J3,5 = 1 Hz), 9.34 s
(11-H). 13C NMR spectrum, δC, ppm: 42.15 d (C1),
31.82 t (C2), 148.13 d (C3), 146.52 s (C4), 67.31 d (C5),
82.99 s (C7), 33.89 t (C8), 25.57 q and 30.38 q (C9,
C10), 189.99 d (C11). Found: [M]+ 166.09949. C10H14O2.
Calculated: M 166.09937.
7. Klein, E. and Ohloff, G., Tetrahedron, 1963, vol. 19,
p. 1091.
1
13
8. Garg, S.C. and Siddiqui, N., Pharmazie, 1992, vol. 47,
p. 467; Miyazawa, M., Okuno, Y., Nakamura, S., and
Kosaka, H., J. Agric. Food Chem., 2000, vol. 48,
p. 5440.
The H and C NMR spectra of hydroxy aldehyde
VIII and benzaldehyde IX were recorded from their
~2:1 mixture.
6-Hydroxy-4-isopropenylcyclohex-1-ene-1-carbal-
9. Motherwell, W.B., Bingham, M.J., Pothier, J., and
1
dehyde (VIII). H NMR spectrum, δ, ppm: 1.51 d.d.d
Six, Y., Tetrahedron, 2004, vol. 60, p. 3231.
(5-Hax, J5-ax,5-eq = 13.5, J5-ax,4-ax = 12, J5-ax,6'-eq
=
10. Polovinka, M.P., Korchagina, D.V., Gatilov, Yu.V.,
Vyglazov, O.G., and Barkhash, V.A., Russ. J. Org.
Chem., 1999, vol. 35, p. 1292.
4.5 Hz), 1.75 br.s (C9H3), 2.00 d.d.d.d (5-Heq, J = 13.5,
J5-eq,4-ax = 2.5, J5-eq,6'-eq = 2.5, J5-eq,3'-eq = 1.5 Hz),
2.15 d.d.d.d (3'-Hax, J3'-ax,3'-eq = 20.5, J3'-ax,4-ax = 11.5,
J3'-ax,2 = 2.5, J3'-ax,6'-eq = 1.2 Hz), 2.46–2.57 m (3'-Heq,
4-Hax), 4.60 d.d.d (6'-Heq, J6'-eq,5-ax = 4.5, J6'-eq,5-eq = 2.5,
J6'-eq,3'-ax = 1.2 Hz), 4.71 br.s (8-H), 4.76 d.q (8'-H,
J8',8 = 1.5, J8',9 = 1.2 Hz), 6.89 d.d (2-H, J2,3'-eq = 5.5,
11. Creary, X. and Wang, Y.-X., J. Org. Chem., 1992,
vol. 57, p. 4761.
12. Tatarova, L.E., Yarovaya, O.I., Volcho, K.P., Korcha-
gina, D.V., Salakhutdinov, N.F., Ione, K.G., and Bar-
khash, V.A., Russ. J. Org. Chem., 1995, vol. 31, p. 908.
13. Bohlmann, F., Zeisberg, R., and Klein, E., Org. Magn.
Reson., 1975, vol. 7, p. 426.
13
J2,3'-ax = 2.5 Hz), 9.42 s (10-H). C NMR spectrum, δC,
ppm: 142.37 s (C1), 151.94 d (C2), 31.94 t (C3),
35.32 d (C4), 34.47 t (C5), 61.03 d (C6), 147.46 s (C7),
110.05 t (C8), 20.90 q (C9), 193.66 d (C10).
14. Felix, D., Wintner, C., and Eschenmoser, A., Org.
Synth., 1963, collect. vol. 6, p. 679.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007