Formation of diol divinyl diethers in the synthesis of 1,2-epoxy-3-(vinyloxyalkoxy)propanes

Full text of DOI:10.1023/A:1019687828252

Russian Journal of Organic Chemistry, Vol. 38, No. 5, 2002, pp. 754 755. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 5, 2002,
pp. 790 791.
Original Russian Text Copyright
2002 by Raskulova, Volkova, Danilevich, Shainyan, Khaliullin.
SHORT
COMMUNICATIONS
Formation of Diol Divinyl Diethers
in the Synthesis of 1,2-Epoxy-3-(vinyloxyalkoxy)propanes
T. V. Raskulova, L. I. Volkova, Yu. S. Danilevich,
B. A. Shainyan, and A. K. Khaliullin
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Received January 9, 2002
According to the data of [1], monovinyl ethers I
derived from diols react with epichlorohydrin in the
presence of alkali to give 1,2-epoxy-3-(vinyloxy-
alkoxy)propanes II and 1,3-bis(vinyloxyalkyl)
glycerol ethers III.
determined from the CH CH O and CH CH signal
2 2 2
intensity ratio in the H NMR spectra.
1
Formally, the formation of diethers IV is the result
of intermolecular dehydration of the initial monovinyl
ethers. However, the X group in IVa IVc is shorter
than the double X group in Ia Ic; these findings
suggest that the reaction is accompanied by elimina-
tion processes.
Vinyl ethers are known to be inert toward nucleo-
philes [2]. On the other hand, Trofimov et al. [3]
showed that monovinyl ethers derived from diols are
capable of undergoing transformations involving
the vinyloxy group by the action of alkali metal
hydroxides [3]. Diol divinyl diethers, e.g., 1,2-bis-
(
vinyloxy)ethane, lose acetaldehyde molecule in
superbasic medium (KOH DMSO) at 130 C under
pressure [4]. Probably, other divinyl diethers behave
similarly. Moreover, these reactions can occur under
considerably milder conditions (atmospheric pressure,
While attempting to obtain by the same procedure
[
1] a series of compounds II [X = (CH CH O) ,
2 2 n
where n = 2 (a), 3 (b), 4 (c) as monomers for radical
copolymerization, we have found that this reaction is
very sensitive to temperature. Ethers II were formed
only at 50 55 C, whereas at room temperature divinyl
diethers CH2 CHOXCH CH [IV, X = (CH CH O)
5
0 C) than those reported in the literature due to
increased mobility of the side chain in monovinyl
ether and greater probability for elimination of acet-
aldehyde. Thus the formation of diol divinyl ethers in
the reaction of monovinyl ethers of diols with alkali
may be explained by concurrent elimination of vinyl
alcohol and intermolecular dehydration.
2
2
2
2
(
a), (CH CH O) (b), (CH CH O) (c)] were obtained.
2 2 5 2 2 4
Moreover, compounds IV were also formed in the
absence of epichlorohydrin. No products III were
detected.
Preparation of diol monovinyl ethers I. A high-
pressure reactor was charged with 0.75 mol of diol
and solid KOH (5 wt % with respect to the diol). The
reactor was purged with nitrogen and acetylene, and
acetylene was supplied at a pressure of 14 15 atm.
The mixture was kept for 3 4 h at 120 C, cooled, and
distilled under reduced pressure. The purity of the
products was checked by GLC.
The structure of compounds IV was proved by the
NMR spectra. We observed no CH signals other than
from the vinyl CH group in the J-modulated spin echo
Preparation of 2,3-epoxypropyl ethers II. Ether
I, 0.5 mol, and freshly distilled epichlorohydrin,
1
3
C NMR spectra. The length of the X chain was
1
070-4280/02/3805-0754$27.00 2002 MAIK Nauka/Interperiodica

FORMATION OF DIOL DIVINYL DIETHERS
755
2
mol, were added to a solution of 0.63 mol of NaOH
in 100 150 of water. The mixture was stirred for
5 h at 50 55 C and filtered, excess epichlorohydrin
, ppm: 3.72 m (4H, CH OCH ), 3.84 m (4H,
2
2
CHOCH ), 3.97 d.d (2H, CH , J = 4.8 Hz), 4.20 d.d
2
2
4
(2H, CH , J = 12.8 Hz), 6.47 d.d (2H, CH, J =
2
1
3
was distilled off, and the residue was distilled under
reduced pressure. The purity of the products was
checked by GLC.
6
(
(
.4 Hz). C NMR spectrum, C, ppm: 68.25
CHOCH ), 70.11 (CH OCH ), 86.80 (CH ), 152.66
2
2
2
2
CH ). Found, %: C 60.52; H 8.75. C H O . Cal-
8 14 3
1
1,12-Epoxy-3,6,9-trioxa-1-dodecene (IIa). Yield
culated, %: C 60.74; H 8.92.
2
0
1
6
1%, bp 130 C (5 mm), n = 1.4510. H NMR spec-
D
3,6,9,12,15,18-Hexaoxa-1,19-eicosadiene (IVb).
trum, , ppm: 2.55 d.d (1H, 12-Htrans, J = 2.8, 5.2 Hz),
20
1
Yield 22%, bp 125 C (1 mm), nD = 1.4540. H NMR
2
1
3
2
6
.72 d.d (1H, 12-H , J = 5.0, 5.2 Hz), 3.08 m (1H,
cis
spectrum, , ppm: 3.57 m (16H, 5-H, 7-H, 8-H, 10-H,
1-H, 13-H, 14-H, 16-H), 3.79 m (4H, 4-H, 17-H),
.92 d.d (2H, 1-H, 20-H, J = 4.8 Hz), 4.15 d.d (2H,
1-H), 3.36 d.d (1H, 10-H , J = 6.4, 11.6 Hz), 3.40
.85 m (9H, 10-H , OCH ), 3.98 d.d (1H, 1-H , J =
A
1
3
1
B
2
cis
.0, 6.8 Hz), 4.20 d.d (1H, 1-Htrans, J = 2.0, 14.4 Hz),
-H, 20-H, J = 10.8 Hz), 6.48 d.d (2H, 2-H, 19-H,
1
3
.51 d.d (1H, 2-H, J = 6.8, 14.4 Hz). C NMR spec-
13
J = 7.2 Hz). C NMR spectrum, , ppm: 70.16,
1
2
10
4
trum, , ppm: 43.88 (C ), 50.97 (C ), 68.20 (C ),
4
17
1
20
C
7
(
0.62, 71.23, 71.87 (C C ), 86.74 (C , C ), 152.87
5
7
8
9
6
9.99 (C ), 71.04 (C ), 71.10 (C ), 72.61 (C ), 86.73
2
19
C , C ). Found, %: C 57.41; H 8.95. C H O .
1
2
14 26 6
(C ), 152.62 (C ). Found, %: C 57.55; H 8.49.
Calculated, %: C 57.91; H 9.02.
C H O . Calculated, %: C 57.43; H 8.56.
9
16
4
3
,6,9,12,15-Pentaoxa-1,16-heptadecadiene (IVc).
1
4,15-Epoxy-3,6,9,12-tetraoxa-1-pentadecene
2
0
1
2
0
Yield 20%, bp 145 C (4 mm), n = 1.4548. H NMR
D
(
IIb). Yield 58%, bp 135 C (5 mm), n = 1.4532.
D
spectrum, , ppm: 3.56 m (8H, 7-H, 8-H, 10-H,
1
3
15
C NMR spectrum,
, ppm: 43.91 (C ), 51.04
C
1
(
1-H), 3.64 d.d (4H, 5-H, 13-H, J = 2.0 Hz), 3.78 d.d
4H, 4-H, 14-H, J = 2.0 Hz), 3.91 d.d (2H, 1-H, 17-H,
J = 4.8 Hz), 4.14 d.d (2H, 1-H, 17-H, J = 12.4 Hz),
1
4
4
5
7
10
(C ), 68.24 (C ), 70.04 (C ), 71.06 (C ), 71.07 (C ),
8
13
11
1
7
1.12 (C ), 71.17 (C ), 72.68 (C ), 86.68 (C ),
2
1
3
1
52.69 (C ). Found, %: C 56.46; H 8.80. C H O .
1
1
20
5
6.45 d.d (2H, 2-H, 16-H, J = 7.2 Hz). C NMR spec-
Calculated, %: C 56.88; H 8.68.
8
10
7
11
trum, , ppm: 68.16 (C , C ), 69.99 (C , C ), 71.05
C
13
1
7,18-Epoxy-3,6,9,12,15-pentaoxa-1-octadecene
5
4
14
1
17
2
0
(C , C ), 71.08 (C , C ), 86.65 (C , C ), 152.61
(
IIc). Yield 59%, bp 140 C (5 mm), n = 1.4545.
H NMR spectrum, , ppm: 2.52 d.d (1H, 18-Htrans
D
2
16
1
(C , C ). Found, %: C 58.37; H 8.89. C H O .
12 22 5
,
Calculated, %: C 58.52; H 9.00.
J = 2.8, 5.2 Hz), 2.70 d.d (1H, 18-H , J = 5.0,
cis
The NMR spectra were obtained on a Varian VXR-
5
6
.2 Hz), 3.06 m (1H, 17-H), 3.33 d.d (1H, 16-H , J =
A
1
5
00S instrument at 500 MHz for H and 125 MHz for
.4, 11.6 Hz), 3.57 3.69 m (14H, OCH ), 3.73 d.d
2
13
C; acetone-d was used as solvent, and HMDS, as
(1H, 16-H , J = 3.0, 11.6 Hz), 3.81 m (2H, 4-H),
6
B
internal reference. GLC analysis was performed on
an LKhM-8 chromatograph equipped with a thermal
conductivity detector; carrier gas helium; 3000 3-mm
columns packed with 5% of SE-30 on Chromaton
N-AW-DMCS.
3
1
1
.95 d.d (1H, 1-H , J = 2.0, 6.8 Hz), 4.18 d.d (1H,
cis
-Htrans, J = 2.0, 14.3 Hz), 6.49 d.d (1H, 2-H, J = 6.8,
4.3 Hz). C NMR spectrum, , ppm: 43.89 (C ),
1
3
18
C
1
7
4
5
5
1.00 (C ), 68.20 (C ), 69.99 (C ), 71.01 71.07
7
13
16
14
1
(
C C ), 71.12 (C ), 72.62 (C ), 86.68 (C ), 152.65
2
(C ). Found, %: C 56.42; H 8.61. C H O . Cal-
1
3
24
6
REFERENCES
culated, %: C 56.51; H 8.75.
Preparation of diol divinyl diethers IV. Epi-
chlorohydrine, 0.1 mol, was added to a mixture of
.1 mol of ether I and 0.12 mol of KOH. The mixture
1
.
Shostakovskii, M.F., Atavin, A.S., Vyalykh, E.P.,
Trofimov, B.A., and Tatarinova, A.F., Zh. Org. Khim.,
1967, vol. 3, no. 11, pp. 1972 1976.
0
was stirred for 5 h at room temperature, diluted with
an ice water mixture, and extracted with diethyl ether.
The extract was washed with ice water, dried over
2
3
4
.
.
.
Shostakovskii, M.F., Vinilovye efiry (Vinyl Ethers),
Moscow: Akad. Nauk SSSR, 1952.
Trofimov, B.A., Oparina, L.A., and Parshina, L.N.,
Zh. Org. Khim., 1986, vol. 22, no. 8, pp. 1583 1585.
Na SO , and subjected to fractional distillation. The
2
4
purity of the products was checked by GLC.
Trofimov, B.A., Oparina, L.A., Parshina, L.N.,
Vins, V.V., and Lavrov, V.I., Izv. Akad. Nauk SSSR,
Ser. Khim., 1989, no. 12, pp. 2873 2874.
Bis(2-vinyloxyethyl) ether (IVa). Yield 32%,
2
0
1
bp 110 C (2 mm), n = 1.4531. H NMR spectrum,
D
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002