KRYSIN et al.
370
248 (4.01), 285 (3.48). IR spectrum (CCl4), ν, cm–1:
[(CH3)3C]; 34.2, 34.88, 34.91 [(CH3)3C]; 52.3 (C12),
59.5 (C4), 73.6 (C5), 105.5 (C2), 124.0 and 124.1 (C2′,
C6′, C7, C11), 130.3 and 130.5 (C6, C1′), 135.7 and
135.8 (C3′, C5′, C8, C10), 152.4 (C4′, C9).
1
3644 (OH), 1841 and 1658 (C=C, C=O). H NMR
spectrum (CDCl3–CCl4), δ, ppm: 1.00 s (9H, 7-t-Bu),
1.21 s (9H, 9-t-Bu), 1.34 s (18H, 3′-t-Bu, 5′-t-Bu),
1.70 br.s (1H, CH2OH), 3.31 d.d (1H, CH2OH, J =
11.8, 3.0 Hz), 3.52 d.d (1H, CH2OH, J = 11.8, 7.8 Hz),
3.80 t (1H, 4-H, J = 9 Hz), 4.16 d.d (1H, 1-H, J = 7.8,
3.0 Hz), 4.44 t and 4.53 t (1H each, 3-H, J = 9 Hz),
5.06 s (1H, 4′-OH), 6.51 and 6.52 (2H, 6-H, 10-H, AB
system, J = 2.9 Hz), 6.76 s (2H, Harom). 13C NMR spec-
trum (CDCl3–CCl4), δC, ppm: 29.1 (C13), 29.5 (C15),
30.1 (C17), 34.2 (C16), 34.88 (C12), 34.91 (C14), 53.6
(C5), 56.2 (C4), 62.4 (CH2OH), 70.4 (C3), 87.6 (C1),
123.9 (C2′, C6′), 125.2 (C1′), 135.4 (C3′, C5′), 136.8 (C6),
140.2 (C10), 148.0 (C7), 150.3 (C9), 152.9 (C4′), 185.9
(C8). Found: m/z 496.3563 [M]+. C32H48O4. Calculated:
[M]+ 496.3552.
1
Stereoisomer Vb. H NMR spectrum (CDCl3), δ,
ppm: 1.36 s and 1.39 s (36H, t-Bu), 2.48 d (1H, 12-H,
J = 3.0 Hz), 3.40–3.60 m (1H, 12-H), 3.80–4.00 (1H,
5-H), 4.12–4.19 d.d (1H, 5-H, J = 7.8, 3.0 Hz), 4.55 t
(1H, 4-H, J = 7.8 Hz), 4.60 s (1H, OH), 4.80 s (1H,
OH), 7.01 s and 7.10 s (2H each, Harom). 13C NMR
spectrum (CDCl3–CCl4), δC, ppm: 30.1 and 30.2
[(CH3)3C], 34.2 [3′-C(CH3)3, 5′-C(CH3)3], 34.88 and
34.91 [8-C(CH3)3, 10-C(CH3)3], 45.7 (C12), 56.7 (C4),
74.7 (C5), 99.8 (C2), 125.5 and 125.8 (C2′, C5′, C7, C11),
129.4 and 130.3 (C6, C1′), 135.5 and 135.7 (C3′, C5′, C8,
C10), 152.5 (C4′, C9).
(1RS,4SR)-7,9-Di-tert-butyl-4-(3,5-di-tert-butyl-
REFERENCES
4-hydroxyphenyl)-1-hydroxymethyl-2-oxaspiro-
1
1. Fenol’nye soedineniya: fundamental’nye i prikladnye
aspekty (Phenolic Compounds. Fundamental and
Applied Aspects). Zagoskin, N.V. and Burlakova, E.B.,
Moscow: Nauchnyi Mir, 2010, p. 400.
[4.5]deca-6,9-dien-8-one (IVb). H NMR spectrum
(CDCl3–CCl4), δ, ppm: 0.95 s (9H, 7-t-Bu), 1.24 s (9H,
9-t-Bu), 1.37 s (18H, 3′-t-Bu, 5′-t-Bu), 1.9 br.s (1H,
CH2OH), 3.48 d.d (1H, CH2OH, J = 11.8, 3.0 Hz),
3.64 d.d (1H, CH2OH, J = 11.8, 7.8 Hz), 3.55 t (1H,
4-H, J = 9 Hz), 4.00 d.d (1H, 1-H, J = 7.8, 3.0 Hz),
4.35 t and 4.53 t (1H each, 3-H, J = 9 Hz), 5.11 s (1H,
4′-OH), 6.12 and 6.75 (2H, 6-H, 10-H, AB system, J =
2.9 Hz), 6.88 s (2H, Harom). 13C NMR spectrum
(CDCl3–CCl4), δC, ppm: 29.07, 29.52, 30.11, 34.20,
34.57, 34.90, 52.45, 55.90, 62.97, 71.62, 86.20,
124.12, 127.25, 135.84, 140.21, 140.47, 147.16,
147.60, 185.89.
2. Titova, T.F. and Krysin, A.P., Zh. Org. Khim., 1987,
vol. 23, p. 597.
3. Sarkanen, K.V. and Wallis, A.F.A., J. Chem. Soc.,
Perkin Trans. 1, 1973, no. 17, p. 1878.
4. Titova, T.F., Krysin, A.P., Rusov, V.P., Ovsyannik, N.V.,
Ken’ko, L.A., Sitnikova, I.V., and Balykina, N.V., Plast.
Massy, 1990, p. 23.
5. Nikulicheva, O.N., Krysin, A.P., and Fadeeva, V.P.,
Zh. Prikl. Khim., 2008, vol. 81, p. 1517.
6. Titova, T.F. and Krysin, A.P., Izv. Sib. Otd. Akad. Nauk
Subsequent column chromatography on silica gel
using petroleum ether–chloroform as eluent (gradient
elution) gave 0.3 g of a mixture of stereoisomeric
2,6-di-tert-butyl-4-[2-(3,5-di-tert-butyl-4-hydroxyben-
zyl)-1,3-dioxan-4-yl]phenols Va and Vb at a ratio of
2:1, mp 185–187°C. UV spectrum: λmax 278 nm. Mass
spectrum: m/z (Irel, %): 496 (2) [M]+, 290 (1), 248 (2)
[M]2+, 232 (100), 219 (12), 217 (38), 57 (30). Found:
m/z 496.35 [M]+. C32H48O4. Calculated: [M]+ 496.3552.
SSSR, Ser. Khim., 1987, vol. 19, no. 6, p. 140.
7. Korul’kin, D.Yu., Abilov, Zh.A., Muzychkina, R.A., and
Tolstikov, G.A., Prirodnye flavonoidy (Natural
Flavonoids), Novosibirsk: Geo, 2007, p. 232.
8. Krysin, A.P. and Fedorenko, A.N., Izv. Akad. Nauk
SSSR, Ser. Khim., 1989, p. 1671.
9. Volod’kin, A.A., Doctoral (Chem.) Dissertation,
Moscow, 1978.
10. Ershov, V.V., Volod’kin, A.A., Kudinova, L.I., and
Vol’eva, V.B., USSR Inventor’s Certificate no. 727614,
1980; Byull. Izobret., 1980, no. 14.
11. Volod’kin, A.A., Zaitsev, A.S., Rubailo, V.A., Belya-
kov, V.A., and Zaikov, G.E., Izv. Akad. Nauk SSSR, Ser.
Khim., 1989, p. 1829.
1
Stereoisomer Va. H NMR spectrum (CDCl3), δ,
ppm: 1.37 s and 1.40 s (36H, t-Bu), 2.87 d (1H, 12-H,
J = 3.0 Hz), 3.40–3.60 m (1H, 12-H), 3.80–4.00 (1H,
5-H), 4.12–4.19 d.d (1H, 5-H, J = 7.8, 3.0 Hz), 4.30 t
(1H, 4-H, J = 7.8 Hz), 4.75 s (1H, OH), 4.80 s (1H,
OH), 7.01 s and 7.07 s (2H each, Harom). 13C NMR
spectrum (CDCl3–CCl4), δC, ppm: 30.1 and 30.2
12. Krysin, A.P., Kusov, S.Z., and Malykhin, E.V., Russian
Patent no. 2385858, 2008; Byull. Izobret., 2010, no. 10.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014