Synthesis of 2-[2-hydroxy-3-(vinyloxy)propoxy]benzaldehyde and its cyclization into trans- and cis-2-[(2-methyl-1,3-dioxolan-4-yl)methoxy] benzaldehydes

Full text of DOI:10.1134/S1070428010060242

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 924–925. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © B.F. Kukharev, V.K. Stankevich, N.A. Lobanova, G.R. Klimenko, G.A. Volkov, 2010, published in Zhurnal Organicheskoi Khimii,
2010, Vol. 46, No. 6, pp. 924–925.
SHORT
COMMUNICATIONS
Synthesis of 2-[2-Hydroxy-3-(vinyloxy)propoxy]benzaldehyde
and Its Cyclization into trans- and cis-2-[(2-Methyl-1,3-dioxolan-
4-yl)methoxy]benzaldehydes
B. F. Kukharev, V. K. Stankevich, N. A. Lobanova, G. R. Klimenko, and G. A. Volkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: irk_inst_chem@irioch.irk.ru
Received December 30, 2009
DOI: 10.1134/S1070428010060242
1,3-Dioxolane derivatives exhibit a broad spectrum
of biological activity [1]; in particular, various pesti-
cides were found among these compounds [2]. With
a view to further study pesticidal activity of 1,3-dioxo-
lane derivatives, we have developed a procedure for
the synthesis of 2-[(2-methyl-1,3-dioxolan-4-yl)-
methoxy]benzaldehyde possessing salicylaldehyde and
1,3-dioxolane fragment.
II:III (cis + trans) was 1:0.18, the ratio of isomeric
dioxolanes trans-III and cis-III being 1:1.
No reaction occurred below 190°C. The optimal
temperature was 210–220°C; therefore, the observed
formation of dioxolanes III is likely to result from
known thermal cyclization of vinyl ethers derived from
polyols [4]. In fact, by heating vinyl ether II at 210°C
over a period of 2 h we obtained an equimolar mixture
of isomeric dioxolanes III in 28% yield together with
resinous products.
We previously reported on the synthesis of 2-{2-hy-
droxy-3-[2-(vinyloxy)ethoxy]propoxy}benzaldehyde
by reaction of 2-hydroxybenzaldehyde with ethylene
glycol vinyl glycidyl ether, catalyzed by triethylamine
[3]. The reaction of salicylaldehyde with glycidyl vinyl
ether under analogous conditions, apart from expected
2-[2-hydroxy-3-(vinyloxy)propoxy]benzaldehyde (II),
gave cyclic products, trans- and cis-isomeric dioxo-
Taking into account the poor yield of III in the
thermal cyclization of vinyl ether II, the latter was
subjected to acid-catalyzed cyclization. The reaction in
the presence of a catalytic amount of hydrochloric acid
was accompanied by weak heat evolution (the tem-
perature rose by (2–3°C), and the products were
stereoisomeric dioxolanes III at a ratio of 56 :44
(1H NMR data), the overall yield being 53%. Taking
into account different fraction of the isomers, we suc-
ceeded in assigning with certainty most signals in the
1H and 13C NMR spectra to particular isomers. Pre-
sumably, the major stereoisomer is trans, and the
minor, cis.
1
lanes III. According to the H NMR data, the ratio
OH
CHO
CH2
+
O
O
I
CHO
OH
CH2
O
O
NEt3
2-[2-Hydroxy-3-(vinyloxy)propoxy]benzalde-
hyde (II). A mixture of 26.1 g (0.26 mol) of vinyl
ether I, 30.5 g (0.25 mol) of 2-hydroxybenzaldehyde,
and 0.75 g (0.75 mmol) of triethylamine was quickly
heated to 215°C, cooled, and distilled under reduced
II
O
CHO
pressure. Yield 58%, bp 177–179°C (3 mm), nD20
=
Me
O
O
1.5504. IR spectrum, ν, cm–1: 3444, 3116, 3077, 3042,
2986, 2936, 2878, 2762, 1687, 1678, 1638, 1619,
1600, 1583, 1485, 1458, 1399, 1321, 1304, 1288,
+
III
924

SYNTHESIS OF 2-[2-HYDROXY-3-(VINYLOXY)PROPOXY]BENZALDEHYDE
925
1243, 1198, 1163, 1105, 1082, 1044, 1031, 999, 962,
864, 842, 810, 760, 722, 691, 653, 636, 598, 531, 440.
1H NMR spectrum, δ, ppm: 3.92 m (2H, OCH2, OH),
trum, δC, ppm: 19.79 (Me), 67.12 (ArOCH2), 68.68
(CH2OCHMe), 73.61 (CHOCHMe), 102.02 (OCO),
112.51 (C3), 121.21 (C5), 124.96 (C1), 128.42 (C6),
135.84 (C4), 160.71 (C2), 189.16 (C=O).
2
3
4.03 d.d (1H, cis-HC=CO, J = 2.3, Jcis = 6.8 Hz),
4.15 m (3H, ArOCHAHBCHCHAHB), 4.21 d.d (1H,
trans-HC=CO, 2J = 2.3, 3Jtrans = 14.3 Hz), 4.32 m (1H,
2-[cis-(2-Methyl-1,3-dioxolan-4-yl)methoxy]-
1
benzaldehyde (IIIb). H NMR spectrum, δ, ppm:
3
3
ArOCHAHB), 6.45 d.d (1H, OCH=C, Jcis = 6.8,
1.36 t (3H, Me, J = 4.9 Hz), 3.78–4.55 m (5H,
3Jtrans = 14.3 Hz), 7.02 m (2H, 3-H, 5-H), 7.49 d.d (1H,
4-H, 3J = 7.3, 4J = 1.8 Hz), 7.76 d.d (1H, 6-H, 3J = 7.6,
3
CH2CHCH2), 5.07 q (1H, CHMe, J = 4.9 Hz), 6.88–
7.02 m (2H, 3-H, 5-H), 7.48–7.54 m (1H, 4-H), 7.77–
7.86 m (1H, 6-H), 10.48 s (1H, CHO). 13C NMR spec-
trum, δC, ppm: 19.76 (Me), 67.32 (ArOCH2), 69.19
(CH2OCHMe), 73.83 (CHOCHMe), 102.34 (OCO),
112.64 (C3), 121.14 (C5), 124.99 (C1), 128.25 (C6),
135.81 (C4), 160.79 (C2), 189.35 (C=O).
13
4J = 1.8 Hz), 10.37 s (1H, CHO). C NMR spectrum,
δC, ppm: 68.33 (CHOH), 68.50 (CH2O), 69.63
(ArOCH2), 87.44 (=CH2), 112.92 (C3), 121.21 (C5),
125.01 (C1), 129.41 (C6), 135.99 (C4), 151.33 (OCH=),
160.61 (C2), 189.80 (C=O). Found, %: C 65.00;
H 6.45. C12H14O4. Calculated, %: C 64.85; H 6.35.
1
The H and 13C NMR spectra were recorded at
Cyclization of 2-[2-hydroxy-3-(vinyloxy)pro-
poxy]benzaldehyde (II). Concentrated hydrochloric
acid, 0.05 g, was added under stirring at room tempera-
ture to 11.1 g (0.05 mol) of vinyl ether II, and the mix-
ture was stirred for 1 h and distilled under reduced
pressure to isolate a mixture of trans and cis isomers of
compound III. Yield 53%, bp 187–190°C (4 mm),
nD20 = 1.5431. IR spectrum, ν, cm–1: 3076, 3042, 2989,
2937, 2875, 2788, 2761, 1688, 1657, 1600, 1583,
1486, 1458, 1401, 1368, 1350, 1304, 1287, 1257,
1242, 1225, 1201, 1191, 1160, 1151, 1116, 1106, 1092,
1043, 1033, 979, 959, 938, 930, 899, 862, 845, 807,
761, 729, 693, 648, 634, 597, 531, 515, 441. Found,
%: C 64.91; H 6.40. C12H14O4. Calculated, %: C 64.85;
H 6.35.
26°C on a Bruker DPX-400 spectrometer at 400 and
100 MHz, respectively, using CDCl3 as solvent and
hexamethyldisiloxane as internal reference. The IR
spectra were measured on a Bruker Vertex-70 spec-
trometer from samples prepared as thin films.
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2-[trans-(2-Methyl-1,3-dioxolan-4-yl)methoxy]-
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1
benzaldehyde (IIIa). H NMR spectrum, δ, ppm:
3
1.39 t (3H, Me, J = 4.9 Hz), 3.78–4.55 m (5H,
3
CH2CHCH2), 5.19 q (1H, CHMe, J = 4.9 Hz), 6.88–
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1981, p. 8.
7.02 m (2H, 3-H, 5-H), 7.48–7.54 m (1H, 4-H), 7.77–
7.86 m (1H, 6-H), 10.47 s (1H, CHO). 13C NMR spec-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010