Synthesis of 1,3-dioxolanes from substituted benzaldehydes of the vanillin series

Article abstract of DOI:10.1134/S1070363212090149

Abstract-Condensation of substituted benzaldehydes of the vanillin series with propane-1,2-diol and 3- chloropropane-1,2-diol in boiling benzene in the presence of FIBAN K-1 sulfonated cation exchanger as catalyst gave the corresponding substituted 1,3-di

Full text of DOI:10.1134/S1070363212090149

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 9, pp. 1537–1539. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.A. Dikusar, V.I. Potkin, T.D. Zvereva, N.A. Zhukovskaya, Yu.S. Zubenko, A.V. Kletskov, R.M. Zolotar’, O.P. Chepik, 2012,
published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 9, pp. 1501–1504.
Synthesis of 1,3-Dioxolanes from Substituted Benzaldehydes
of the Vanillin Series
E. A. Dikusara, V. I. Potkina, T. D. Zverevaa, N. A. Zhukovskayaa, Yu. S. Zubenkoa,
A. V. Kletskova, R. M. Zolotar’b, and O. P. Chepikb
a Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: dikusar@ifoch.bas-net.by
b Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus,
ul. Akademika Kuprevicha 5/2, Minsk, 220141 Belarus
Received July 21, 2011
Abstract—Condensation of substituted benzaldehydes of the vanillin series with propane-1,2-diol and 3-
chloropropane-1,2-diol in boiling benzene in the presence of FIBAN K-1 sulfonated cation exchanger as
catalyst gave the corresponding substituted 1,3-dioxolanes.
DOI: 10.1134/S1070363212090149
Vanillin and its closest homologs and analogs, such
as o-vanillin, isovanillin, vanillal, anisaldehyde, and
veratraldehyde, are convenient and accessible sub-
strates for chemical modification and starting materials
for the preparation of biologically active compounds
with a broad spectrum of practical uses [1–5]. We
previously reported on the synthesis of substituted 1,3-
dioxolanes that are derivatives of propane-1,2-diol [6].
Some 1,3-dioxolane derivatives were found to exhibit
strong biological activity [7–9].
R1
O
O
R1
OH
CHO
HO
R2
R2
I
IIа, IIb
IIIa_IIIq, IVa_IVm
II, R1 = Me (a), ClCH2 (b); III, R1 = Me, R2 = 2-HO-3-MeO (a), 3-HO-4-MeO (b), 3-AcO-4-MeO (c), 3,4-(MeO)2 (d), 3-
MeO-4-Me(CH2)8COO (e), 3-MeO-4-Me(CH2)11COO (f), 3-MeO-4-Me(CH2)16COO (g), 3-MeO-4-PhCOO (h), 3-MeO-4-
(2,4-Cl2C6H3COO) (i), 3-MeO-4-(3-O2NC6H4COO) (j), 3,4-(MeO)2-5-Br (k); 3-EtO-4-MeO (l), 3-EtO-4-(4-MeC6H4COO)
(m), 4-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (n), 4-methoxy-3-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (o), 3-
methoxy-4-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (p), 3-ethoxy-4-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (q); IV,
R1 = ClCH2, R2 = H (a), 3-HO-4-MeO (b), 3-AcO-4-MeO (c), 3-MeO-4-HO (d), 3,4-(MeO)2 (e), 3-MeO-4-AcO (f), 3-
MeO-4-(2,4-Cl2C6H3COO) (g), 3,4-(MeO)2-5-Br (h), 3-EtO-4-MeO (i), 4-(4,5-dichloro-1,2-tjiazol-3-ylcarbonyloxy) (j), 4-
methoxy-3-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (k), 3-methoxy-4-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (l), 3-
ethoxy-4-(4,5-dichloro-1,2-thiazol-3-ylcarbonyloxy) (m).
In the present article we describe a preparative proce-
dure for the synthesis of new substituted 1,3-di-
oxolanes IIIa–IIIq and IVa–IVm, including those
containing a 4,5-dichloroisothiazole fragment (com-
pounds IIIn–IIIq and IVj–IVm). The procedure is
based on the condensation of substituted benzal-
dehydes I of the vanillin series with propane-1,2-diol
(IIa) or 3-chloropropane-1,2-diol (IIb) in boiling
benzene in the presence of FIBAN K-1 sulfonated
cation exchanger as catalyst [6, 10]. Water liberated
1537

1538
DIKUSAR et al.
Yields, densities and refractive indices or melting points, elemental analyses, and molecular weights of substituted 1,3-
dioxolanes IIIa–IIIq and IVa–IVm
20
d
nD20
Found, %
Calculated, %
M
20
Comp. Yield,
Formula
C11H14O4
no.
%
mp, °С
C
H
C
H
found
calculated
86
88
90
92
84
80
82
84
91
92
88
90
88
86
86
84
86
88
90
92
89
89
90
86
87
85
88
1.0567
1.2598
1.2501
1.1442
1.1429
1.0633
1.5368
1.5320
1.5162
1.5302
1.4912
1.4908
63.12
63.10
62.28
64.56
69.71
71.19
73.46
69.12
56.80
60.37
47.82
65.76
70.43
46.88
46.85
46.28
47.90
60.84
54.42
54.73
54.35
55.94
54.80
52.13
42.97
57.20
42.88
6.79
6.85
6.46
7.34
9.02
9.48
10.27
5.90
4.39
4.93
5.16
7.68
6.67
3.20
3.54
3.50
3.91
5.67
5.58
5.39
5.40
6.05
5.50
3.78
4.38
6.36
2.69
62.85
62.85
61.90
64.27
69.20
70.90
73.07
68.78
56.41
60.17
47.54
65.53
70.16
46.68
46.17
46.17
47.54
60.46
45.00
54.46
45.00
55.71
54.46
51.76
42.69
57.25
42.61
6.71
6.71
6.39
7.19
8.85
9.42
202
204
243
209
354
397
462
304
372
345
288
230
331
348
381
377
390
192
232
278
238
244
281
404
328
260
387
210
210
252
224
364
406
477
314
383
359
303
238
342
360
390
390
404
199
245
287
245
259
287
418
338
273
395
IIIa
IIIb
IIIc
IIId
IIIe
C11H14O4
C13H16O5
C12H16O4
C21H32O5
C24H38O5
IIIf
33–34
83–84
1.3622
C29H48O5
10.15
IIIg
IIIh
IIIia
IIIjb
IIIkc
IIIl
C18H18O5
5.77
4.21
4.77
4.99
7.61
6.48
3.08
3.36
3.36
3.74
5.58
5.36
5.27
5.36
5.84
5.27
3.62
4.18
6.28
2.55
1.5672
1.5574
1.5568
C18H16Cl2O5
C18H17NO7
C12H15BrO4
C13H18O4
1.3411
1.4549
32–33
1.1253
1.3625
1.3512
1.3540
1.3520
1.3086
1.2325
1.2655
1.2149
1.2479
1.3266
1.3785
1.5125
1.2294
1.5458
1.5718
1.5728
1.5745
1.5708
1.5312
1.5455
1.5270
1.5489
1.5462
1.5301
1.5649
1.5622
1.5372
C20H22O5
IIIm
IIInd
IIIoe
IIIpf
IIIqg
IVah
IVbi
IVcj
IVdk
IVel
IVfm
IVgn
IVho
IVip
IVjq
IVkr
C14H11Cl2 NO4S
C15H13Cl2 NO5S
C15H13Cl2 NO5S
C16H15Cl2 NO5S
C10H11ClO2
C11H13ClO4
C13H15ClO5
C11H13ClO4
C12H15ClO4
C13H15ClO5
C18H15Cl3O5
C12H14BrClO4
C13H17ClO4
C14H10Cl3 NO4S
64–65
85
85
86
1.3638
88–89
1.3445
43.02
42.67
44.12
3.06
2.94
3.28
C15H12Cl3 NO5S
C15H12Cl3 NO5S
C16H14Cl3 NO5S
42.42
42.42
43.80
2.85
2.85
3.22
405
416
422
425
425
439
IVls
IVmt
a
Found Cl, %: 18.11. Calculated Cl, %: 18.50. b Found N, %: 3.58. Calculated N, %: 3.90. c Found Br, %: 25.92. Calculated Br, %: 26.36.
Found, %: Cl 19.36; N 3.49; S 8.45. Calculated, %: Cl 19.68; N 3.89; S 8.90. Found, %: Cl 17.90; N 3.22; S 7.89. Calculated, %: Cl
d
e
f
g
18.17; N 3.59; S 8.22. Found, %: Cl 17.87; N 3.34; S 7.81. Calculated, %: Cl 18.17; N 3.59; S 8.22. Found, %: Cl 17.09; N 3.00; S
h
I
7.35. Calculated, %: Cl 17.54; N 3.46; S 7.93. Found Cl, %: 17.38. Calculated Cl, %: 17.85. Found Cl, %: 14.15. Calculated Cl, %:
14.49. j Found Cl, %: 11.99. Calculated Cl, %: 12.37. k Found Cl, %: 14.08. Calculated Cl, %: 14.49. l Found Cl, %: 13.35. Calculated Cl,
m
n
o
%: 13.70. Found Cl, %: 12.06. Calculated Cl, %: 12.37. Found Cl, %: 25.16. Calculated Cl, %: 25.46. Found [Cl+Br], %: 33.87.
p
q
Calculated [Cl+Br], %: 34.17. Found Cl, %: 12.85. Calculated Cl, %: 13.00. Found, %: Cl 26.58; N 3.18; S 7.66. Calculated, %: Cl
r
s
26.95; N 3.55; S 8.12. Found, %: Cl 24.86; N 2.87; S 7.18. Calculated, %: Cl 25.04; N 3.30; S 7.55. Found, %: Cl 24.77; N 2.82; S
6.97. Calculated, %: Cl 25.04; N 3.30; S 7.55. t Found, %: Cl 24.03; N 2.86; S 6.81. Calculated, %: Cl 24.24; N 3.19; S 7.31.
during the process was removed from the reaction
mixture by azeotropic distillation using a Dean–Stark
trap. The reaction time was 16–18 h, and the yields
ranged from 80 to 92% (see table). The selected
conditions allowed to completely avoid hydrolysis or
alcoholysis of ester groups present in compounds IIIc,
IIIe–IIIj, IIIm–IIIq, IVc, IVf, IVg, and IVj–IVm.
1,3-Dioxolanes IIIa–IIIq and IVa–IVm were
isolated as colorless or slightly colored liquids or
crystalline substances which contained no impurities of
initial compounds and required no additional purifica-
tion. Their structure was confirmed by elemental analysis,
1
IR and H NMR spectroscopy, and determination of
their molecular weights by cryoscopy (see table).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012

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–
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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
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012