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.
REFERENCES
1. Elderfield, R.C. and Short, F., Heterocyclic Compounds,
Elderfield, R.C., Ed., New York: Wiley, 1957, vol. 5.
Translated under the title Geterotsiklicheskie soedineniya,
Moscow: Inostrannaya Literatura, 1961, vol. 5, p. 7.
2. Mel’nikov, N.N., Pestitsidy. Khimiya, tekhnologiya i pri-
menenie (Pesticides. Chemistry, Technology, and Ap-
plication), Moscow: Khimiya, 1987, p. 530.
2-[trans-(2-Methyl-1,3-dioxolan-4-yl)methoxy]-
3. Kukharev, B.F., Stankevich, V.K., Klimenko, G.R., Ku-
khareva, V.A., and Bragin, E.V., Russ. J. Org. Chem.,
2008, vol. 44, p. 1494.
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–
4. Trofimov, B.A., Geteroatomnye proizvodnye atsetilena
(Heteroatom Acetylene Derivatives), Moscow: Nauka,
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