OPARINA et al.
208
3
3
3
Н2, J 6.6 Hz), 3.11 (1Н, Н6, J 6.6 Hz), 4.10 d.d (1Н,
СН2CHO, С3,4), 4.64 t (1Н, OСН, J 6.8 Hz), 4.73 m
2
3
2
3
=СНcis, J 2.4, J 6.7 Hz), 4.13 d (1Н, OСН2, J
(1Н, Н5), 5.08 br.s (1Н, Н2), 6.18 d (1Н, Н6, J
2
3
11.7 Hz), 4.30 d.d (1Н, =СНtrans, J 2.4, J 14.3 Hz),
4.43 d (1Н, OСН2, 2J 11.7 Hz), 5.42 s (1Н, Н7), 6.48 d,
6.62 d (1H each, Н8,9, 3J 5.5 Hz), 6.56 d.d (1Н, OСН=,
3.0 Hz), 6.28 br.s (2Н, Н3f,u4ran), 7.33 s (1Н, Н5furan). 13С
NMR spectrum (CDCl3), δ, ppm: 13.8 (Me), 15.9
(CH2Me), 18.8, 18.6 (C4), 26.8, 26.6 (C3), 37.7
(CH2CH), 67.6 (OCH), 93.2 (C2), 101.9 (C5), 105.4
(C3furan), 109.8 (С4furan), 140.1 (С6), 142.0 (С5furan), 156.8
(С2furan). Found, %: С 70.18; Н 8.23. C13H18O3.
Calculated, %: С 70.24; Н 8.16.
3J 14.3, J 6.7 Hz), 7.27–7.48 m (5Н, Ph); exo-adduct:
3
3.59 d (1Н, Н2, J 7.7 Hz), 3.78 d.d (1Н, Н6, J 5.5, 3J
3
3
2
3
7.7 Hz), 4.14 d.d (1Н, =СНcis, J 2.3, J 6.7 Hz), 4.29
2
d, 4.40 d (1H each, OСН2, J 11.7 Hz), 4.36 d.d (1Н,
=СНtrans, J 2.3, J 14.3 Hz), 5.43 d (1Н, СН7, J
2
3
3
4-[(Furan-2-yl)methoxy]-2-phenyl-1,2,3,4-tetra-
hydroquinoline (8). To a solution of 0.18 g (1 mmol)
of N-benzylideneaniline in 2.5 mL of 2,2,3,3-tetra-
fluoropropan-1-ol (method а) or in 2.5 mL of acetic
acid (method b) was added 0.12 g (1 mmol) of vinyl
ether 1а. The reaction mixture was stirred at room
temperature for 4 (а) or 24 h (b). On attaining a
complete conversion of vinyl ether 1а the separated
precipitate of quinoline 9 was filtered off, the filtrate
was concentrated in a vacuum (15‒20 mm Hg). The
main reaction product 8 was purified by flash
chromatography (basic Al2O3, eluent hexane‒chloro-
form, 2 : 1). Yield 0.20 g (65%, а), 0.18 g (58%, b),
yellow-brown oil. IR spectrum, ν, cm–1: 3384 (NH),
3146, 3116, 3084, 3058, 3028, 3003, 1608, 1590, 1503
5.5 Hz), 6.56 d.d (1Н, OСН=, 3J 14.3, 3J 6.7 Hz), 6.48
d, 6.62 d (1H each, СН8,9, J 5.7 Hz), 7.27–7.48 m
3
(5Н, Ph). 13С NMR spectrum (CDCl3), δ, ppm, endo-
adduct: 47.9 (С6), 49.5 (С2), 64.9 (OСН2), 81.2 (С7),
87.2 (СН2=), 89.6 (С1), 125.6 (Сo, Ph), 127.5 (Cp, Ph),
128.4 (Cm, Ph), 130.9 (Ci, Ph), 136.7, 137.2 (С8,9),
159.9 (OСН=), 169.0, 174.4 (С=O); exo-adduct: 45.5
(С6), 47.2 (С2), 65.4 (OСН2), 79.5 (С7), 87.4 (СН2=),
90.3 (С1), 125.8 (Сo, Ph), 126.0 (Cp, Ph), 128.7 (Cm,
Ph), 134.2 (Ci, Ph), 134.5, 135.3 (С8,9), 150.9 (OСН=),
173.2, 173.3 (С=O). Found, %: С 68.25; Н 4.93; N
4.50. C17H15NO4. Calculated, %: С 68.68; Н 5.09; N
4.71.
Compounds 6a and 6b. A mixture of 10.5 mmol
of vinyl ether 1a and 1b, 0.56 g (10 mmol) of freshly
distilled acrolein, and ~1 wt % of hydroquinone was
heated for 6 h in in a sealed ampule at 125°С. The
obtained reaction mixture was subjected to fractional
distillation in a vacuum.
1
(Ph, furan). H NMR spectrum (CDCl3), δ, ppm: 2.08
d.d (1Н, Н3, 2J 12.2, 3J 10.5 Hz), 2.33 d.d.d (1Н, Н3, 3J
2.7, J 5.6, J 12.2 Hz), 4.39 d.d (1Н, Н2, J 2.7, J
3
2
3
3
2
11.7 Hz), 4.48 d, 4.57 d (1H each, OСН2, J 12.7 Hz),
4.88 d.d (1Н, Н4, J 10.5, J 5.6 Hz), 6.30 s (2Н,
2
3
Н3f,u4ran), 6.44 d (1Н, Н8, J 8.0 Hz), 6.71 t (1Н, Н6, J
3
3
2-[(Furan-2-yl)methoxy]-3,4-dihydro-2Н-pyran
(6a). Yield 0.91 g (50%), bp 71°С (4 mm Hg), nD20
1.4960. IR spectrum, ν, cm–1: 3120, 3065 (СН=), 1652
(С=С), 1184, 1151, 1107, 1069, 1050 (С–O–С–O–С).
1H NMR spectrum (CDCl3), δ, ppm: 1.87–1.95 m (3Н,
Н3,4), 2.16 m (1Н, Н3), 4.61 d, 4.72 d (1H each, OСН2,
7.2 Hz), 7.02 t (1Н, Н7, J 8.0 Hz), 7.32 m (5Н, Ph),
3
7.35 s (1Н, Н5furan), 7.40 d (1Н, Н5, J 12.7 Hz). 13С
3
NMR spectrum (CDCl3), δ, ppm: 36.8 (C3), 55.9 (C2),
62.1 (OCH2), 73.2 (C4), 108.7 (C3furan), 110.1 (C8),
114.3 (C4furan), 117.8 (C6), 121.8 (Cp, Ph), 126.4 (Co,
Ph), 127.5 (C5), 128.5 (Cm, Ph), 128.8 (C7), 143.3 (Ci,
Ph), 147.0 (C8'), 152.0 (С5furan). Found, %: С 78.34; Н
6.42; N 5.02. C20H19NO2. Calculated, %: С 78.66; Н
6.27; N 4.59.
2J 13.0 Hz), 4.81 m (1Н, Н5), 5.08 d (1Н, Н2, J
2
3.4 Hz), 6.27 d.d (1Н, Н6, J 4.4, J 1.5 Hz), 6.36 br.s
3
4
(2Н, Н3f,u4ran), 7.43 d (1Н, Н5furan, J 0.9 Hz). 13С NMR
3
spectrum (CDCl3), δ, ppm: 15.9 (C4), 26.4 (C3), 61.2
(OCH2), 96.1 (C2), 102.7 (C5), 110.3 (C3furan), 111.2
(С4furan), 140.3 (С6), 143.8 (С5furan), 151.3 (С2furan).
Found, %: С 66.78; Н 6.82. C10H12O3. Calculated, %:
С 66.65; Н 6.71.
ACKNOWLEDGMENTS
This study was carried out with the financial
support for the Leading Scientific Schools by the
Council for grants at the President of the Russian
Federation (grant no. NSh-7145.2016.3) using
the equipment of material and technical base of
the Baikal Analytical Center for joint usage of
the Siberian Branch of the Russian Academy of
Sciences.
2-[4-(Furan-2-yl)butoxy)]-3,4-dihydro-2Н-pyran
(6b). Yield 0.53 g (24%), bp 81–83°С (4 mm Hg), nD20
1.4728. IR spectrum, ν, cm–1: 3118, 3066 (СН=), 1653
(С=С), 1188, 1151, 1106, 1068, 1059 (С–O–С–O–С).
1H NMR spectrum (CDCl3), δ, ppm: 0.90 t (3Н, Me, 3J
7.3 Hz), 1.30–1.43 m (2Н, СН2Me), 1.76–2.14 m (6Н,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017