CHEMO- AND REGIOSELECTIVE REACTION OF VINYL FURFURYL ETHERS
1165
2-{[1-(tert-Butoxy)ethoxy]methyl}furan (XIId).
Colorless liquid. Yield 1.35 g (68%), bp 62–64°C
(4 mm), nD20 = 1.4473. IR spectrum, ν, cm–1: 3147,
3118, 2977, 2936, 2908, 2874, 1504, 1474, 1460,
1446, 1383, 1366, 1322, 1260, 1236, 1226, 1198,
1150, 1112, 1092, 1035, 1016, 991, 966, 920, 884, 839,
807, 736, 600. 1H NMR spectrum, δ, ppm: 1.23 s (9H,
t-Bu), 1.30 d (3H, Me, J = 5.2 Hz), 4.46 s (2H, OCH2),
5.00 q (1H, OCHO, J = 5.2 Hz), 6.24 d and 6.34 d
(1H each, 3-H, 4-H, J = 1.3 Hz), 7.34 s (1H, 5-H).
13C NMR spectrum, δC, ppm: 21.16 (Me), 28.05
(CMe3), 56.51 (CH2), 73.30 (CMe3), 92.94 (CH),
107.47 (C4), 109.53 (C3), 141.72 (C5), 151.75 (C2).
Found, %: C 66.49; H 9.20. C11H18O3. Calculated, %:
C 66.64; H 9.15.
2-{[1-(2,2,3,3-Tetrafluoropropoxy)ethoxy]-
methyl}furan (XIIg). Colorless liquid. Yield 2.23 g
(87%), bp 85°C (3 mm), n2D0 = 1.4122. IR spectrum, ν,
cm–1: 3153, 3125, 2995, 2942, 2893, 1504, 1461, 1446,
1391, 1369, 1341, 1279, 1231, 1206, 1151, 1121, 1103,
1030, 1016, 968, 941, 921, 910, 886, 835, 818, 743,
711, 691, 601, 547. 1H NMR spectrum, δ, ppm: 1.37 d
(3H, Me, J = 5.3 Hz), 3.89 m (2H, CH2), 4.50 d and
4.58 d (1H each, OCH2, J = 12.7 Hz), 4.93 q (1H,
OCHO, J = 5.3 Hz), 5.94 t.t (1H, CH2F, J = 54.0,
4.9 Hz), 6.34 s and 6.35 s (1H each, 3-H, 4-H),
7.42 br.s (1H, 5-H). 13C NMR spectrum, δC, ppm:
18.59 (Me), 59.27 (OCH2), 61.01 t (CH2CF2, J =
28.7 Hz), 98.74 (CH), 109.31 t.t (HCF2, J = 248.8,
34.6 Hz), 110.00 (C4), 111.38 (C3), 115.26 t.t (CF2, J =
248.8, 26.5 Hz), 142.69 (C5), 150.68 (C2). Found, %:
C 46.52; H 4.51; F 29.60. C10H12F4O3. Calculated, %:
C 46.88; H 4.72; F 29.66.
2-{[1-(Allyloxy)ethoxy]methyl}furan (XIIe).
Colorless liquid. Yield 1.49 g (82%), bp 68°C (4 mm),
n2D0 = 1.4705; published data [21]: bp 84°C (13 mm),
n2D0 = 1.4647. IR spectrum, ν, cm–1: 3148, 3120, 3082,
2989, 2937, 2869, 1647, 1504, 1458, 1447, 1391,
1367, 1337, 1268, 1253, 1150, 1125, 1097, 1030, 992,
2-{[1-(2-Methoxyethoxy)ethoxy]methyl}furan
(XIIh). Colorless liquid. Yield 1.48 g (74%), bp 82–
84°C (2 mm), nD20 = 1.4582. IR spectrum, ν, cm–1:
3148, 3118, 2987, 2930, 2879, 2827, 1504, 1454,
1387, 1369, 1340, 1282, 1244, 1225, 1200, 1150,
1124, 1100, 1067, 1015, 991, 971, 949, 920, 885, 853,
815, 750, 601. 1H NMR spectrum, δ, ppm: 1.30 d (3H,
Me, J = 5.2 Hz), 3.33 s (3H, OMe), 3.49 t (2H, OCH2,
J = 4.8 Hz), 3.54–3.59 m and 3.64–3.70 m (1H each,
OCH2), 4.46 d and 4.51 d (1H each, CH2O, J =
12.8 Hz), 4.81 q (1H, OCHO, J = 5.2 Hz), 6.27 m (2H,
3-H, 4-H), 7.35 d (1H, 5-H, J = 0.8 Hz). 13C NMR
spectrum, δC, ppm: 18.59 (Me), 58.88 (OMe); 60.60,
66.40, 70.92 (OCH2); 98.72 (CH), 109.21 (C4), 110.26
(C3), 142.57 (C5), 151.79 (C2). Found, %: C 60.06;
H 8.11. C10H16O4. Calculated, %: C 59.98; H 8.05.
1
920, 886, 812, 739, 600. H NMR spectrum, δ, ppm:
1.38 d (3H, Me, J = 5.4 Hz), 4.04 m and 4.12 m (1H
each, OCH2), 4.51 d and 4.56 d (1H each, OCH2, J =
12.7 Hz), 4.88 q (1H, OCHO, J = 5.4 Hz), 5.19 d.d
(1H, CH2=, J = 10.2, 1.2 Hz), 5.31 d.d (1H, CH2=, J =
17.1, 1.2 Hz), 5.94 m (1H, CH=), 6.32 d and 6.35 d.d
(1H each, 3-H, 4-H, J = 3.0, 1.6 Hz), 7.42 d.d (1H,
5-H, J = 1.6, 0.8 Hz). 13C NMR spectrum, δC, ppm:
19.46 (Me), 58.71 (CH2), 65.77 (CH2), 98.37 (CH),
108.82 (C4), 110.13 (C3), 116.59 (CH2=), 134.53
(CH=), 142.59 (C5), 151.68 (C2). Found, %: C 65.25;
H 7.65. C10H14O3. Calculated, %: C 65.91; H 7.74.
2-{[1-(Prop-2-yn-1-yloxy)ethoxy]methyl}furan
(XIIf). Colorless liquid. Yield 1.67 g (93%), bp 95°C
(5 mm), nD20 = 1.4769; published data [21]: bp 74°C
(3 mm), nD20 = 1.4738. IR spectrum, ν, cm–1: 3294,
3149, 3122, 2990, 2933, 2870, 2119, 1504, 1454,
1445, 1393, 1367, 1338, 1268, 1225, 1202, 1151,
1125, 1095, 1032, 1016, 987, 972, 920, 894, 886, 847,
2-{[1-(2-Furylmethoxy)ethoxy]methyl}furan
(XIIi). Colorless liquid. Yield 2.04 g (92%), bp 112°C
(2 mm), nD20 = 1.4910; published data [20]: bp 126°C
(4 mm), nD20 = 1.4929. IR spectrum, ν, cm–1: 3145,
3116, 2992, 2935, 2871, 1503, 1446, 1394, 1372,
1338, 1280, 1270, 1220, 1150, 1133, 1090, 1010, 969,
913, 810, 735, 600. 1H NMR spectrum, δ, ppm: 1.33 d
(3H, Me, J = 5.2 Hz), 4.48 d and 4.54 d (2H each,
CH2O, J = 12.8 Hz), 4.88 q (1H, OCHO, J = 5.2 Hz),
6.29 m (4H, 3-H, 4-H), 7.36 d (2H, 5-H, J = 0.8 Hz).
13C NMR spectrum, δC, ppm: 15.23 (Me), 58.80 (CH2),
98.95 (CH), 109.08 (C4), 110.28 (C3), 141.27 (C5),
150.26 (C2). Found, %: C 64.73; H 6.30. C12H14O4.
Calculated, %: C 64.85; H 6.35.
1
815, 743, 673, 638, 600. H NMR spectrum, δ, ppm:
1.36 d (3H, Me, J = 5.4 Hz), 2.41 t (1H, CH≡, J =
2.4 Hz), 4.21 t (2H, OCH2, J = 2.4 Hz), 4.50 d and
4.55 d (1H each, OCH2, J = 12.6 Hz), 4.95 q (1H,
OCHO, J = 5.4 Hz), 6.31 m (2H, 3-H, 4-H), 7.38 br.s
(1H, 5-H). 13C NMR spectrum, δC, ppm: 19.55 (Me),
52.60 and 59.16 (OCH2), 74.03 (CH≡), 79.94 (C≡),
98.28 (CH), 109.19 (C4), 110.34 (C3), 142.88 (C5),
151.60 (C2). Found, %: C 66.50; H 6.66. C10H12O3.
Calculated, %: C 66.65; H 6.71.
2-[(1-Methoxyethoxy)methyl]tetrahydrofuran
(XIIj). Colorless liquid. Yield 0.99 g (62%), bp 98–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012