MOCHALOV et al.
1518
6.76 d (2H, Harom, 4J = 1.4 Hz), 6.81 d (2H, Harom, 3J =
8.2 Hz); threo isomer: 0.74 d and 1.01 d [6H each,
CH(CH3)2, J = 7.6 Hz], 1.98 m [2H, CH(CH3)2],
3.87 d (2H, CHO, J = 7.3 Hz), 4.21 s (8H, 2-H, 3-H),
6.51 d.d (2H, Harom, 3J = 8.2, 4J = 1.4 Hz), 6.57 d (2H,
Harom, J = 1.4 Hz), 6.63 d (2H, Harom, J = 8.2 Hz).
Found, % (for isomer mixture): C 72.01, 72.18; H 7.31,
7.42. C24H30O5. Calculated, %: C 72.34; H 7.59.
3-H), 6.75–6.84 m (6H, Harom); threo isomer: 0.15 m
(2H), 0.38 m (2H), 0.45 m (2H), 0.65 m (2H), and
1.19 m (2H) (C3H5); 3.83 d (2H, OCH, J = 6.5 Hz),
4.26 s (8H, 2-H, 3-H), 6.77–6.86 m (6H, Harom).
Found, % (for isomer mixture): C 72.78, 72.87; H 6.42,
6.51. C24H26O5. Calculated, %: C 73.08; H 6.64.
4
3
Reaction of alcohol 2a with hydrochloric acid in
dioxane. Alcohol 2a, 0.01 mol (1.76 g), was dissolved
in 15 mL of dioxane, 0.3 mL (0.001 mol) of 10%
aqueous HCl was added, and the mixture was refluxed
for 5 h with stirring. The mixture was cooled, poured
into 100 mL of water, and extracted with diethyl ether
(2 × 30 mL). The ether extract was washed with
a 2 N solution of NaHCO3 and dried over MgSO4, the
solvent was removed, and the residue was subjected to
preparative thin-layer chromatography on Al2O3 using
diethyl ether–hexane (1:4) as eluent. We isolated
0.81 g (51%) of 6-vinyl-1,2,3,4-tetrahydronaphthalene
[1H NMR spectrum, δ, ppm: 1.92 m (4H, 2-H, 3-H),
6,6′-[Oxydi(2-phenylethane-1,1-diyl)]bis(2,3-di-
hydro-1,4-benzodioxine) (3e). mp 141–142°C (isomer
1
mixture). H NMR spectrum, δ, ppm: erythro isomer:
2.77 d.d (2H, J = 13.8, 5.2 Hz) and 2.95 d.d (2H, J =
13.8, 8.8 Hz) (CH2Ph), 4.16 d.t (2H, CHCH2, J =
5.6 Hz), 4.25 s (8H, 2-H, 3-H), 6.31 d.d (2H, Harom
,
4
4
3J = 8.2, J = 2.0 Hz), 6.45 d (2H, Harom, J = 2.0 Hz),
3
6.65 d (2H, Harom, J = 8.2 Hz), 7.08 m (4H, Harom),
7.23 m (6H, Harom); threo isomer: 2.79 d.d (2H, J =
13.8, 5.2 Hz) and 2.99 d.d (2H, J = 13.8, 8.8 Hz)
(CH2Ph), 4.23 s (8H, 2-H, 3-H), 4.29 d.t (2H, CHCH2,
J = 5.6 Hz), 6.52 d.d (2H, Harom, 3J = 8.2, 4J = 2.0 Hz),
6.62 d (2H, Harom, 3J = 8.2 Hz), 6.64 d (2H, Harom, 4J =
2.0 Hz), 6.97 m (4H, Harom), 7.05 m (6H, Harom).
Found, % (for isomer mixture): C 77.26, 77.42; H 5.86,
5.97. C32H30O5. Calculated, %: C 77.71; H 6.11.
2.86 m (4H, 1-H, 4-H), 5.24 d (1H, CH2=, Jcis
=
10.1 Hz), 5.77 d (1H, CH2=, Jtrans = 17.2 Hz), 6.71 d.d
(1H, CH=, J = 17.2, 10.1 Hz), 7.06–7.11 m (3H,
Harom)], 0.15 g (9%) of symmetrical ether 3a and
0.51 g of unreacted 2a.
This study was performed under financial support
by the Council for Grants at the President of the
Russian Federation (project no. NSh-10268.2016.3).
6,6′-[Oxydi(phenylmethylene)]bis(2,3-dihydro-
1,4-benzodioxine) (3f). mp 122–123°C (isomer mix-
ture). H NMR spectrum, δ, ppm: 4.25 s (8H, 2-H,
1
3-H), 5.32 s (2H, OCH), 6.83 s (4H, Harom), 6.93 s (2H,
Harom), 7.32 m (2H, Harom), 7.34 m (4H, Harom), 7.39 m
(4H, Harom). Found, % (for isomer mixture): C 77.39,
77.06; H 5.58, 5.51. C30H26O5. Calculated, %: C 77.24;
H 5.62.
REFERENCES
1. Sawama, Y., Shishido, Y., Kawajiri, T., Goto, R.,
Monguchi, Y., and Sajiki, H., Chem. Eur. J., 2014,
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2. Gautret, P., El-Ghammarti, S., and Legrand, A., Synth.
Commun., 1996, vol. 26, p. 707.
6,6′-[Oxydi(4-chlorophenylmethylene)]bis-
(2,3-dihydro-1,4-benzodioxine) (3g). mp 145–146°C
(isomer mixture). H NMR spectrum, δ, ppm: erythro
1
3. Shokrollahi, A., Zali, A., and Pouretedal, H.R., Synth.
Commun., 2008, vol. 38, p. 371.
isomer: 4.25 s (8H, 2-H, 3-H), 5.24 s (2H, CHO),
6.77 d.d (2H, Harom, 3J = 8.2, 4J = 1.9 Hz), 6.83 d (2H,
4. Zolfigol, M.A., Mohammadpoor-Baltork, I., Mirja-
3
4
lili, B.F., and Bamoniri, A., Synlett, 2003, no. 12, p. 1877.
Harom, J = 8.2 Hz), 6.85 d (2H, Harom, J = 1.9 Hz),
7.28 s (8H, Harom); threo isomer: 4.26 s (8H, 2-H, 3-H),
5. Kim, S., Chung, K.-N., and Yang, S., J. Org. Chem.,
3
4
1987, vol. 52, p. 3917.
5.25 s (2H, OCH), 6.75 d.d (2H, Harom, J = 8.2, J =
3
6. Prestant, G., Vitale, M., and Poli, G., Synlett, 2002,
1.9 Hz), 6.82 d (2H, Harom, J = 8.2 Hz), 6.86 d (2H,
4
vol. 11, p. 1823.
Harom, J = 1.9 Hz), 7.29 s (8H, Harom). Found, %
7. Bunrit, A., Dahlstrand, Ch., Olsson, S.K., Srifa, P.,
Huang, G., Orthaber, A., Sjoberg, P.J.R., Biswas, S.,
Himo, F., and Samec, J.S.M., J. Am. Chem. Soc., 2015,
vol. 137, no. 14, p. 4646.
(for isomer mixture): C 66.97, 67.06; H 4.38, 4.43.
C30H24Cl2O5. Calculated, %: C 67.30; H 4.52.
6,6′-[Oxydi(cyclopropylmethylene)]bis(2,3-dihy-
1
dro-1,4-benzodioxine) (3h). Oily material. H NMR
8. Zhang, Y.-J., Dayoub, W., Chen, G.-R., and Lemaire, M.,
spectrum, δ, ppm: erythro isomer: 0.13 m (2H), 0.26 m
(2H), 0.42 m (2H), 0.61 m (2H), and 1.14 m (2H)
(C3H5); 3.24 d (2H, OCH, J = 6.5 Hz), 4.25 s (8H, 2-H,
Tetrahedron, 2012, vol. 68, no. 36, p. 7400.
9. Ibrahim, N., Hashmi, S.K., and Rominger, F., Adv. Synth.
Catal., 2011, vol. 353, nos. 2–3, p. 461.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 10 2017