Chemo-and regioselective reaction of vinyl furfuryl ethers with alcohols

Article abstract of DOI:10.1134/S1070428012090023

Furfuryl and tetrahydrofurfuryl vinyl ethers reacted with various alcohols under mild conditions (20-25°C, 1-3 h, 1 wt % of CF3COOH) with high chemo- and regioselectivity to give the corresponding Markovnikov adducts at the vinyl group in up to 93% yield.

Full text of DOI:10.1134/S1070428012090023

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 9, pp. 1162–1167. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.A. Oparina, O.V. Vysotskaya, A.V. Stepanov, N.K. Gusarova, B.A. Trofimov, 2012, published in Zhurnal Organicheskoi Khimii,
2012, Vol. 48, No. 9, pp. 1166–1171.
Chemo- and Regioselective Reaction of Vinyl Furfuryl Ethers
with Alcohols
L. A. Oparina, O. V. Vysotskaya, A. V. Stepanov, N. K. Gusarova, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: boris_trofimov@irioch.irk.ru
Received March 27, 2012
Abstract—Furfuryl and tetrahydrofurfuryl vinyl ethers reacted with various alcohols under mild conditions
(20–25°C, 1–3 h, 1 wt % of CF3COOH) with high chemo- and regioselectivity to give the corresponding
Markovnikov adducts at the vinyl group in up to 93% yield.
DOI: 10.1134/S1070428012090023
Persistent exhaust of natural gas and oil resources
increases the role of renewable sources of organic
materials [1–3], primarily of plant biomass. For ex-
ample, furfural and furfuryl alcohol that are readily
obtainable from natural oligo- and polysaccharides,
have received growing application in organic synthesis
[1, 4–7]. Large-scale solvents [8, 9], fuel additives
[10, 11], and biodegradable polymers [12] have
already been created on the basis of furfural. Furfuryl
alcohol is a starting material in large-scale syntheses of
furan resins [13], adhesives, and paints [14]. Tetra-
hydrofurfuryl alcohol is used as nontoxic (“green”)
solvent in the manufacture of acrylates and epoxy
resins, as well as in the preparation of plasticizers like
tetrahydrofurfuryl oleate [1].
furfuryl acetals, in 20–40% yield. The low yield is
likely to be related to facile disproportionation of the
resulting acetals, leading to symmetric dialkyl and
difurfuryl acetals. It was also reported that furan ring
undergoes acid-catalyzed cleavage with formation of
1,4-dicarbonyl compounds [23–26]. The reactions of
tetrahydrofurfuryl vinyl ether with allyl and propargyl
alcohols in the presence of a catalytic amount of hy-
drochloric acid were more selective, and the resulting
mixed acetals (yield up to 70%) were more resistant to
symmetrization [21]. 2-{[1-(Furan-2-ylmethoxy)-
ethoxy]methyl}furan and 2-{[1-(2-methoxyethoxy)-
ethoxy]methyl}furan obtained from vinyl ether I and
furfuryl alcohol or 2-methoxyethanol under acidic con-
ditions were used as effective dopes to electrolyte in
lithium–sulfur batteries [15].
Vinyl ethers derived from alcohols of the furan
series have become accessible due to development of
a convenient and efficient procedure for their synthesis
by vinylation of furfuryl and tetrahydrofurfuryl alco-
hols with acetylene under atmospheric pressure in the
presence of special superbasic catalytic systems
[15, 16]. They are now regarded as base building
blocks for the preparation of new furan derivatives,
i.e., they can be used as “anchor carriers” of furan
functionality [17, 18]. A promising line in the synthetic
application of vinyl ethers of the furan series is their
reaction with alcohols. It was shown previously that
alkanols and allyl and propargyl alcohols in the pres-
ence of hydrochloric [19–21] or p-toluenesulfonic acid
[22] add at the double bond of furfuryl vinyl ether I to
produce the corresponding Markovnikov adducts, alkyl
The goal of the present study was to develop a con-
venient and efficient procedure for the synthesis of
acetals containing furan and tetrahydrofuran rings via
chemo- and regioselective addition of various alcohols
at the double bond of furfuryl vinyl ether [I, 2-(vinyl-
oxymethyl)furan] and tetrahydrofurfuryl vinyl ether
[II, 2-(vinyloxymethyl)tetrahydrofuran] under acidic
conditions.
We found that 2-(vinyloxymethyl)furan (I) and
2-(vinyloxymethyl)tetrahydrofuran (II) reacted with
various alcohols [saturated alcohols III–VI, unsaturat-
ed alcohols VII and VIII, fluorinated alcohol IX,
2-methoxyethanol (X), and furfuryl alcohol (XI)] in
the presence of a catalytic amount of trifluoroacetic
acid (1 wt %) to produce acetals XIIa–XIIp with high
1162

CHEMO- AND REGIOSELECTIVE REACTION OF VINYL FURFURYL ETHERS
1163
Scheme 1.
Reaction of furfuryl vinyl ethers I and II with alco-
hols III–XI
H+, 20–25°C
R1
O
R1
O
Me
CH2
+
R2OH
Reactants
Reaction time, h Product (yield, %)
OR2
XIIa–XIIp
I + III
I + IV
I + V
3
XIIa (68)
XIIb (64)
XIIc (65)
XIId (68)
XIIe (82)
XIIf (93)
XIIg (87)
XIIh (74)
XIIi (92)
XIIj (62)
XIIk (61)
XIIl (70)
XIIm (74)
XIIn (86)
XIIo (83)
XIIp (85)
I, II
III–XI
3
I, R1 = furan-2-yl; II, R1 = tetrahydrofuran-2-yl; III, R2 =
Me; IV, R2 = Et; V, R2 = i-Pr; VI, R2 = t-Bu; VII, R2 =
CH2=CHCH2; VIII, R2 = CH≡CCH2; IX, R2 = CHF2CF2CH2;
X, R2 = MeOCH2CH2; XI, R2 = furan-2-ylmethyl.
2
I + VI
I + VII
I + VIII
I + IX
3
2
chemo- and regioselectivity (Scheme 1). The reactions
were complete in 1–3 h at room temperature (see
table). No products of furan ring opening, which might
be expected under acidic conditions [23–26], were
detected in the reaction mixtures.
2
2
I + X
2
I + XI
II + III
II + IV
II + V
II + VI
II + VII
II + VIII
II + IX
2
0.1.5
0.1.5
0.1.5
0.1.5
1
The progress of reactions was monitored by IR and
1H NMR spectroscopy. In the IR spectra of the reaction
mixtures we observed gradual disappearance of ab-
sorption bands typical of vinyloxy (3030, 1640–1618,
1320, 1200, 960, 817 cm–1) and hydroxy groups
(3450 cm–1), and spectral pattern in the region of
C–O–C absorption (1050–1205 cm–1) changed. The
1H NMR spectra contained signals characteristic of
furfuryl and alkoxy groups, and signals from the
OCHO proton (δ 4.6–4.9 ppm, q) and methyl group
(δ ~1.3 ppm, d) appeared.
1
1
reactions we examined electrophilic addition of allyl
alcohol (VII) and prop-2-yn-1-yl alcohol (VIII) to the
above substrates, the molar ratio I–II–VII (VIII) being
1:1:1 (room temperature, 3 h, 1 wt % of CF3COOH).
The ratio of acetals XIIe/XIIn and XIIf/XIIo in the
reaction mixture was estimated by the intensities of the
When the reaction was complete, calcined potas-
sium carbonate was added to the reaction mixture to
neutralize the catalyst, and the mixture was kept for
0.5–1 h and filtered. Neutralization of the catalyst was
also achieved in a different way, by passing the mix-
ture through a thin layer of basic alumina and subse-
quent washing of the sorbent with diethyl ether.
1
OCHO signals in the H NMR spectrum (δ 4.81/4.76
for XIIe/XIIn and 4.92/4.87 ppm for XIIf/XIIo).
Unsaturated alcohols VII and VIII were selected
taking into account that acetals XII derived therefrom
are stable (no disproportionation occurred during their
synthesis). It was found that the concentration of the
adducts obtained from tetrahydrofurfuryl vinyl ether
was greater by a factor of 2.2–2.4 than the concen-
tration of the corresponding adducts derived from
furfuryl vinyl ether, i.e., saturated ether II is more
reactive than furan-containing ether I.
The proposed conditions (room temperature and the
use of trifluoroacetic acid instead of aggressive p-tol-
uenesulfonic or hydrochloric acid) made it possible
to largely avoid disproportionation of unsymmetrical
acetals XII. The stability of acetals XII to dispropor-
tionation depended on the nature of the R2 group in the
alcohol fragment. Acetals XIIe–XIIg and XIIn–XIIp
having electron-withdrawing organyloxy groups
almost did not undergo disproportionation during their
synthesis and subsequent distillation (after neutraliza-
tion of the catalyst), and they were isolated in fairly
high yields 82–93% (see table). Alkoxy acetals XIIa–
XIId, XIIh, and XIIj–XIIm were isolated in a lower
yield (61–74%) due to greater contribution of dispro-
portionation leading to the corresponding symmetrical
acetals.
The choice of trifluoroacetic acid as catalyst for
electrophilic addition of hydroxy compounds to fur-
furyl vinyl ethers was not fortuitous. It is known that
perfluorinated carboxylic acids are specific and mild
selective catalysts of electrophilic addition to vinyloxy
group [27–29]. In fact, the reaction of vinyl ether I
with tert-butyl alcohol in the presence of p-toluenesul-
fonic acid (1 wt %) was accompanied by considerable
heat evolution, and the yield of acetal XIId was as
poor as 12%. Under these conditions, appreciable
The reactivities of vinyl ethers I and II were com-
pared by the competing reaction technique. As model
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

OPARINA et al.
1164
amounts of symmetric acetals and tarry products were
obtained; the latter could be formed as a result of
cleavage of the furan ring.
and acetals XIIa–XIIp were isolated by vacuum
distillation.
2-[(1-Methoxyethoxy)methyl]furan (XIIa).
Colorless liquid. Yield 1.06 g (68%), bp 60°C (8 mm),
nD20 = 1.4551; published data [21]: bp 50°C (3 mm),
n2D0 = 1.4610. IR spectrum, ν, cm–1: 3150, 3120, 2990,
2935, 2831, 1504, 1452, 1390, 1366, 1339, 1281,
1268, 1224, 1209, 1150, 1126, 1092, 1045, 1027,
1015, 989, 920, 897, 885, 867, 813, 743, 601. 1H NMR
spectrum, δ, ppm: 1.34 d (3H, Me, J = 5.4 Hz), 3.34 s
(3H, OMe), 4.47 d and 4.55 d (1H each, OCH2, J =
12.7 Hz), 4.76 q (1H, OCHO, J = 5.4 Hz), 6.32 s and
6.34 s (1H each, 3-H, 4-H), 7.41 s (1H, 5-H). 13C NMR
spectrum, δC, ppm: 18.99 (Me), 51.92 (OMe), 59.02
(CH2), 99.53 (CH), 108.94 (C4), 110.23 (C3), 142.67
(C5), 151.81 (C2). Found, %: C 61.30; H 7.54.
C8H12O3. Calculated, %: C 61.51; H 7.74.
The structure of acetals XIIa–XIIp was proved by
IR and 1H and 13C NMR spectroscopy. The presence of
a chiral center in molecules XIIa–XIIi makes protons
in the OCH2 group nonequivalent, and their signals
1
appear in the H NMR spectrum as two doublets with
equal intensities at δ 4.60–4.70 ppm. Acetals XIIj–
XIIp obtained from 2-(vinyloxymethyl)tetrahydro-
furan were isolated as mixtures of two diastereoiso-
mers. Signals from the C3H2 protons in the tetrahydro-
furan ring and from the OCH2 group were observed
separately [δ, ppm: 1.9 and 1.5 (3-H), 3.5 and 3.3
(OCH2)], and each signal, apart from geminal coupling
2
constant J, displayed additional couplings, so that
complex multiplets were observed. In the 13C NMR
spectra of XIIj–XIIp double sets of signals from all
carbon atoms in the tetrahydrofurfuryl and acetal frag-
ments, as well as from the alkoxy carbon atom neigh-
boring to the asymmetric center, were present. Acetals
containing furan (XIIa–XIIi) and tetrahydrofuran
rings (XIIj–XIIp) are readily soluble in most organic
solvents and insoluble in water.
2-[(1-Ethoxyethoxy)methyl]furan (XIIb). Color-
less liquid. Yield 1.09 g (64%), bp 45°C (1 mm), nD20 =
1.4501; published data [21]: bp 54°C (1 mm), nD20
=
1.4500. IR spectrum, ν, cm–1: 3147, 3121, 2979, 2933,
2900, 2879, 1504, 1445, 1384, 1281, 1272, 1225,
1150, 1126, 1079, 1013, 989, 920, 897, 885, 867, 813,
1
787, 601. H NMR spectrum, δ, ppm: 1.18 t (3H, Me,
J = 7.1 Hz), 1.30 d (3H, Me, J = 5.4 Hz), 3.42 d.q and
3.57 d.q (1H each, OCH2, J = 7.1, 11.8 Hz), 4.46 d and
4.55 d (1H each, OCH2, J = 12.7 Hz), 4.78 q (1H,
OCHO, J = 5.4 Hz), 6.32 s and 6.34 s (1H each, 3-H,
To conclude, by trifluoroacetic acid-catalyzed ad-
dition of alcohols to the vinyloxy group of furfuryl and
tetrahydrofurfuryl vinyl ethers we have demonstrated
the possibility of using them as anchor carriers of furan
(tetrahydrofuran) functionality in the synthesis of
furan-containing acetals.
13
4-H), 7.40 s (1H, 5-H). C NMR spectrum, δC, ppm:
15.33 (Me), 19.06 (Me), 58.66 and 59.12 (CH2), 98.53
(CH), 108.84 (C4), 110.09 (C3), 142.47 (C5), 151.46
(C2). Found, %: C 63.91; H 8.42. C9H14O3. Calculated,
%: C 63.51; H 8.29.
EXPERIMENTAL
The NMR spectra were recorded from solutions in
CDCl3 at room temperature on a Bruker DPX-400
spectrometer operating at 400.13 (1H) and 100.62 MHz
(13C). The IR spectra (400–4000 cm–1) were measured
from thin films on a Bruker JFS-25 spectrometer.
2-[(1-Isopropoxyethoxy)methyl]furan (XIIc).
Colorless liquid. Yield 1.20 g (65%), bp 58–60°C
(4 mm), nD20 = 1.4446. IR spectrum, ν, cm–1: 3148,
3119, 2974, 2935, 2875, 1504, 1466, 1455, 1448,
1391, 1380, 1370, 1332, 1280, 1268, 1225, 1186,
1151, 1131, 1086, 1028, 1016, 989, 950, 920, 901,
General procedure for the addition of alcohols to
furfuryl vinyl ethers I and II. A catalytic amount
(1 wt %) of trifluoroacetic acid was added to a mixture
of 10 mmol of vinyl ether I or II and 10 mmol of
alcohol III–XI, and the mixture was stirred for 1–3 h
at room temperature on a magnetic stirrer. The prog-
ress of the reaction was monitored by IR spectroscopy.
When the reaction was complete (absorption bands
typical of vinyloxy and hydroxy groups disappeared
completely from the IR spectrum of the reaction
mixture), the mixture was neutralized by treatment
with K2CO3 (~2–3 wt %, 0.5–1 h, room temperature),
1
886, 860, 812, 737, 600. H NMR spectrum, δ, ppm:
1.10 d and 1.18 d (3H each, Me, J = 6.2 Hz), 1.39 d
(3H, Me, J = 5.4 Hz), 3.87 d.q (1H, OCH, J = 6.2 Hz),
4.45 d and 4.49 d (1H each, OCH2, J = 12.6 Hz),
4.83 q (1H, OCHO, J = 5.4 Hz), 6.24 d and 6.34 d.d
(1H each, 3-H, 4-H, J = 3.2, 1.8 Hz), 7.34 d.d (1H,
5-H, J = 1.8, 1.0 Hz). 13C NMR spectrum, δC, ppm:
20.14 (Me), 21.86 and 22.86 (Me), 57.70 (CH2), 67.60
(CH), 97.00 (CH), 108.62 (C4), 109.85 (C3), 142.29
(C5), 151.38 (C2). Found, %: C 65.11; H 8.49.
C10H16O3. Calculated, %: C 65.19; H 8.75.
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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–
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OPARINA et al.
1166
100°C (20 mm), nD20 = 1.4411. IR spectrum, ν, cm–1:
2976, 2932, 2872, 1459, 1445, 1381, 1339, 1284,
1273, 1135, 1089, 1052, 994, 919, 891, 838, 818, 700,
2976, 2935, 2873, 1473, 1461, 1390, 1381, 1365, 1334,
1260, 1236, 1200, 1132, 1091, 1051, 969, 951, 919,
897, 856, 823. 1H NMR spectrum, δ, ppm: 1.21 s (9H,
t-Bu), 1.25 d and 1.26 d (3H, Me, J = 5.3 Hz), 1.60 m
(1H, 3-H), 1.84–1.90 m (3H, 3-H, 4-H), 3.45 m (2H,
OCH2), 3.73 m and 3.86 m (1H each, 5-H), 3.98 m
(1H, 2-H), 4.92 q and 4.96 q (1H, OCHO, J = 5.3 Hz).
13C NMR spectrum, δC, ppm: 22.16 and 22.24 (Me),
25.47 and 25.76 (C4), 28.00 and 28.09 (C3), 28.05
(CMe3), 64.81 and 64.96 (CH2), 67.55 and 67.80 (C5),
73.28 (CMe3), 75.40 and 75.50 (C2), 96.84 and 96.91
(CH). Found, %: C 65.09; H 10.82. C11H22O3. Calcu-
lated, %: C 65.31; H 10.96.
1
537. H NMR spectrum, δ, ppm: 1.18 d and 1.19 d
(3H, Me, J = 5.3 Hz), 1.50 m (1H, 3-H), 1.76 m (2H,
4-H), 1.82 m (1H, 3-H), 3.30 s (3H, OMe), 3.35 m and
3.44 m (1H each, OCH2), 3.64 m and 3.70 m (1H each,
5-H), 3.91 m (1H, 2-H), 4.57 q (1H, OCHO, J =
5.3 Hz). 13C NMR spectrum, δC, ppm: 18.62 (Me),
25.12 and 25.22 (C4), 27.78 (C3), 51.73 and 51.90
(OMe), 66.77 and 67.20 (OCH2), 67.73 and 67.76 (C5),
77.37 and 77.50 (C2), 99.97 and 100.03 (OCHO).
Found, %: C 59.62; H 10.27. C8H16O3. Calculated, %:
C 59.97; H 10.07.
2-{[1-(Allyloxy)ethoxy]methyl}tetrahydrofuran
(XIIn). Colorless liquid. Yield 1.60 g (86%), bp 62°C
(3 mm), nD20 = 1.4420; published data [21]: bp 82°C
(4 mm), nD20 = 1.4444. IR spectrum, ν, cm–1: 3081,
2985, 2936, 2870, 1647, 1460, 1450, 1423, 1407,
1389, 1367, 1334, 1285, 1269, 1249, 1138, 1100,
2-[(1-Ethoxyethoxy)methyl]tetrahydrofuran
(XIIk). Colorless liquid. Yield 1.06 g (61%), bp 54°C
(4 mm), nD20 = 1.4394. IR spectrum, ν, cm–1: 2985,
2937, 2872, 2831, 1460, 1449, 1388, 1367, 1349,
1339, 1283, 1209, 1137, 1089, 1046, 994, 919, 891,
1
1
838, 818, 700, 537. H NMR spectrum, δ, ppm: 1.18 t
1081, 1046, 993, 921, 902, 835. H NMR spectrum, δ,
(3H, Me, J = 7.1 Hz), 1.28 d and 1.29 d (3H, Me, J =
5.3 Hz), 1.58 m (1H, 3-H), 1.84–1.90 m (3H, 3-H,
4-H), 3.42–3.65 m (4H, OCH2), 3.71 m and 3.84 m
(1H each, 5-H), 3.96 m (1H, 2-H), 4.94 q and 4.96 q
(1H, OCHO, J = 5.3 Hz). 13C NMR spectrum, δC, ppm:
15.33 (Me), 19.91 and 19.96 (Me), 25.69 and 25.76
(C4), 28.00 and 28.09 (C3), 60.60 and 64.96 (CH2),
68.52 and 68.55 (C5), 75.19 and 75.24 (C2), 98.80 and
98.81 (OCHO). Found, %: C 61.81; H 10.19. C9H18O3.
Calculated, %: C 62.04; H 10.41.
ppm: 1.34 d and 1.35 d (3H, Me, J = 5.2 Hz), 1.55 m
(1H, 3-H), 1.64 m (2H, 4-H), 1.83 m (1H, 3-H), 3.55–
3.65 m (2H, OCH2), 3.66 m and 3.81 m (1H each,
5-H), 4.01 d.d (1H, 2-H, J = 5.3, 13.1 Hz), 4.09 m and
4.16 m (1H each, OCH2), 4.78 q and 4.80 q (1H,
OCHO, J = 5.2 Hz), 5.13 d (1H, CH2=, J = 10.4 Hz),
5.36 d (1H, CH2=, J = 17.2 Hz), 5.96 m (1H, CH=).
13C NMR spectrum, δC, ppm: 19.45 and 19.51 (Me),
25.46 and 25.55 (C4), 28.05 and 28.11 (C3); 65.98,
66.08, 66.42, and 66.84 (CH2); 68.16 and 68.28 (C5);
77.72 and 77.84 (C2); 99.08 and 99.24 (CH); 116.42
(CH2=), 134.67 (CH=). Found, %: C 64.94; H 9.40.
C10H18O3. Calculated, %: C 64.49; H 9.74.
2-[(1-Isopropoxyethoxy)methyl]tetrahydrofuran
(XIIl). Colorless liquid. Yield 1.32 g (70%), bp 55°C
(4 mm), nD20 = 1.4379. IR spectrum, ν, cm–1: 2973,
2934, 2872, 1464, 1380, 1371, 1330, 1284, 1186, 1135,
2-{[1-(Prop-2-yn-1-yloxy)ethoxy]methyl}tetra-
hydrofuran (XIIo). Colorless liquid. Yield 1.53 g
(83%), bp 80°C (4 mm), nD20 = 1.4548; published data
[21]: bp 95°C (2 mm), nD20 = 1.4542. IR spectrum, ν,
cm–1: 2985, 2937, 2872, 2831, 1460, 1449, 1388, 1367,
1349, 1339, 1283, 1209, 1137, 1089, 1046, 994, 919,
1
1085, 1050, 986, 951, 919, 897, 856, 823. H NMR
spectrum, δ, ppm: 1.08 d and 1.13 d (3H each, Me, J =
6.1 Hz), 1.24 d and 1.25 d (3H, Me, J = 5.3 Hz), 1.52–
1.62 m (1H, 3-H), 1.79–1.94 m (3H, 3-H, 4-H), 1.40 m
and 3.48 m (2H, OCH2), 3.71 m (1H, 5-H), 3.80–
3.86 m (2H, CH, 5-H), 3.96 m (1H, 2-H), 4.76 q and
1
891, 838, 818, 700, 537. H NMR spectrum, δ, ppm:
13
4.77 q (1H, OCHO, J = 5.3 Hz). C NMR spectrum,
1.29 d and 1.30 d (3H, Me, J = 5.4 Hz), 1.56 m (1H,
3-H), 1.84 m (2H, 4-H), 1.90 m (1H, 3-H), 2.37 m (1H,
HC≡), 3.46 m and 3.53 m (1H each, OCH2), 3.73 m
and 3.82 m (1H each, 5-H), 3.99 m (1H, 2-H), 4.17 s
(2H, OCH2), 4.86 q and 4.87 q (1H, OCHO, J =
5.4 Hz). 13C NMR spectrum, δC, ppm: 19.36 and 19.40
(Me), 25.51 and 25.63 (C4), 28.01 and 28.11 (C3),
52.54 and 52.67 (OCH2), 67.04 and 67.49 (OCH2),
68.17 and 68.23 (C5), 73.84 (HC≡), 77.67 and 77.80
(C2), 79.93 (C≡), 98.72 and 98.82 (OCHO), Found, %:
δC, ppm: 19.91 and 20.09 (Me); 21.59, 21.67, 22.73,
and 22.78 (Me); 25.04 and 25.12 (C4), 27.70 and 27.77
(C3), 65.63 and 66.12 (CH2), 67.40 (CH), 67.45 and
67.70 (C5), 77.40 and 77.50 (C2), 97.36 and 97.56
(OCHO). Found, %: C 64.01; H 10.39. C10H20O3. Cal-
culated, %: C 63.80; H 10.71.
2-{[1-(tert-Butoxy)ethoxy]methyl}tetrahydro-
furan (XIIm). Colorless liquid. Yield 1.49 g (74%),
bp 65°C (4 mm), nD20 = 1.4376. IR spectrum, ν, cm–1:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

CHEMO- AND REGIOSELECTIVE REACTION OF VINYL FURFURYL ETHERS
1167
12. Okada, M., Tachikawa, K., and Aoi, K., J. Polym.
Sci. A: Polym. Chem., 1997, vol. 35, p. 2729.
13. Gandini, A. and Belgacem, M.N., Prog. Polym. Sci.,
C 65.51; H 8.57. C10H16O3. Calculated, %: C 65.19;
H 8.75.
2-{[1-(2,2,3,3-Tetrafluoropropoxy)ethoxy]-
methyl}tetrahydrofuran (XIIp). Colorless liquid.
Yield 2.21 g (85%), bp 80°C (3 mm), nD20 = 1.3941. IR
spectrum, ν, cm–1: 2985, 2937, 2872, 2831, 1460,
1449, 1388, 1367, 1349, 1339, 1283, 1209, 1137,
1089, 1046, 994, 919, 891, 838, 818, 700, 537.
1H NMR spectrum, δ, ppm: 1.34 d (3H, Me, J =
5.2 Hz), 1.59 m (1H, 3-H), 1.91 m (2H, 4-H), 1.97 m
(1H, 3-H), 3.44 m and 3.59 m (1H each, OCH2), 3.76–
3.89 m (4H, CH2, 5-H), 4.03 m (1H, 2-H), 4.88 q and
4.87 q (1H, OCHO, J = 5.2 Hz), 5.91 t.t (1H, CHF2,
1997, vol. 22, p. 1203.
14. Kottke, R.H., Kirk-Othmer Encyclopedia of Chemical
Technology, New York, Wiley, 1998, vol. 12, p. 259.
15. Oparina, L.A., Vysotskaya, O.V., Stepanov, A.V.,
Rodionova, I.V., Myachina, G.F., Gusarova, N.K., and
Trofimov, B.A., Russ. J. Org. Chem., 2008, vol. 44,
p. 120.
16. Oparina, L.A., Vysotskaya, O.V., Stepanov, A.V., Gusa-
rova, N.K., and Trofimov, B.A., Russ. J. Org. Chem.,
2009, vol. 45, p. 131; Trofimov, B.A., Gusarova, N.K.,
Oparina, L.A., Vysotskaya, O.V., and Stepanov, A.V.,
Russian Patent no. 2359965, 2009; Byull. Izobret.,
2009, no. 18.
13
J = 53.3, 5.0 Hz). C NMR spectrum, δC, ppm: 19.02
and 19.40 (Me), 25.60 and 25.74 (C4), 28.02 and 28.15
(C3), 61.21 t and 61.29 t (CH2CF2, J = 27.4 Hz), 67.26
and 68.87 (OCH2), 68.33 and 68.37 (C5), 77.64 and
77.79 (C2), 100.08 and 100.14 (OCHO), 109.27 t.t
(HCF2, J = 249.2, 34.3 Hz), 115.26 t.t (CF2, J = 249.2,
26.2 Hz). Found, %: C 46.41; H 6.08; F 29.12.
C10H16F4O3. Calculated, %: C 46.15; H 6.20; F 29.20.
17. Stepanov, A.V., Cand. Sci. (Chem.) Dissertation,
Irkutsk, 2010.
18. Oparina, L.A., Malysheva, S.F., Gusarova, N.K.,
Vysotskaya, O.V., Stepanov, A.V., Belogorlova, N.A.,
Albanov, A.I., and Trofimov, B.A., Synthesis, 2009,
no. 20, p. 3427.
19. Rychkova, A.G. and Keller, R.E., Zh. Obshch. Khim.,
1961, vol. 31, p. 1849.
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