SYNTHESIS OF 1,3-DIOXOLANES FROM SUBSTITUTED BENZALDEHYDES
1539
The IR spectra of IIIa–IIIq and IVa–IVm con-
tained the following absorption bands, ν, cm–1: 3080–
3000 and 870–720 (C–Harom), 2970–2870 (C–Haliph),
1765–1720 (C=Oester), 1600±5 and 1510±5 (C=Carom),
and 1275–1008 cm–1 (C–O); no absorption band was
observed at 1695–1680 cm–1, i.e., in the frequency
range typical of stretching vibrations of the carbonyl
group in initial aldehydes.
R2
R2
R1
H
3
O
O
4
R1
H
H
O
O
C
H
C2
H
H
1
5
H
H
(2R,4S)-2-Aryl-4-R1-1,3-dioxolane
(2R,4R)-2-Aryl-4-R1-1,3-dioxolane
As followed from the 1H NMR spectra, the
products were formed as mixtures of approximately
equal amounts of (2R,4S)- and (2R,4R)-diastereoisomers.
Signals from protons in the 1,3-dioxolane ring
appeared as two singlets at δ (ppm) 5.40–6.10 (2-H)
and multiplets at δ 3.90–4.55 (5-H) and 3.20–3.95
(4-H). Protons in the R1 group gave rise to two
doublets at δ 1.10–1.60 (R1 = CH3, IIIa–IIIq) or a
Dean–Stark trap (about 0.2 ml). The catalyst was
removed by filtration through a porous glass filter, the
filtrate was washed with water to remove excess of
propanediol IIa and IIb and with a saturated solution
of sodium chloride, and the solvent was distilled off
under reduced pressure. The residue was finally
purified by column chromatography on silica gel (60–
100 μm) using benzene as eluent.
multiplet at δ 3.95–4.20 ppm
(R1 = CH2Cl, IVa–
REFERENCES
IVm). Aromatic protons resonated in the region δ
7.30–7.90 ppm; signals from protons in MeO (δ 3.70–
3.90 ppm, s) and EtO groups (δ 0.85–1.40, t, and 3.60–
4.40 ppm, q) were also present. In addition, 1,3-
dioxolanes IIIa–IIIq and IVa–IVm displayed in the IR
1. Pershina, L.A. and Efanov, M.V., Khim. Rastit.
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1
and H NMR spectra absorption bands and proton
signals corresponding to the ester fragments.
3. Nair, M.S. and Joseyphus, R.S., Spectrochim. Acta, Part
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EXPERIMENTAL
4. Potkin, V., Zubenko, Y., Bykovetz, A., and Zolotar, R.,
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The IR spectra were recorded from films or KBr
pellets on a Nicolet Protégé-460 spectrometer with
Fourier transform. The 1H NMR spectra were
measured on a Tesla BS-587A instrument (100 MHz)
from 5% solutions in chloroform-d using tetra-
methylsilane as internal reference. The molecular
weights were determined by cryoscopy in benzene.
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Substituted 1,3-dioxolanes IIIa–IIIq and IVa–
IVm (general procedure). A 100-ml one-neck round-
bottom flask equipped with a Dean–Stark trap and a
reflux condenser was charged with 0.01 mol of the
corresponding substituted benzaldehyde I, 0.025 mol
of propane-1,2-diol (IIa) or 3-chloropropane-1,2-diol
(IIb), 0.2 g of FIBAN K-1 cation exchanger, and
75 ml of benzene. The mixture was heated for 16–18 h
under reflux, the progress of the reaction being
monitored by the amount of water separated in the
8. Rehman, A., Soni, A., Naik, K., Nair, S., Palle, V.P.,
Dastidan, S., Ray, A., Alam, M.S., Salman, M., Cliffe, I.A.,
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Khim. Inter. Ustoich. Razv., 2001, vol. 9, no. 3, p. 417.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012
Dikusar, E. A.
