Chemistry of dioxacycloalkanes: VII. Synthesis and properties of substituted 1,3-dioxolanes derived from carbocyclic aldehydes

Article abstract of DOI:10.1023/A:1012350122851

Reactions of 3-cyclohexenecarbaldehyde, 6-methyl-3-cyclohexenecarbaldehyde, bicyclo[2.2.1]-hept-5-ene-endo-2-carbaldehyde, and benzaldehyde with 1,2-propanediol and 3-chloro-1,2-propanediol gave the corresponding 2,4-substituted 1,3-dioxolanes. Their reactions with peroxyacetic acid, bromine, dichlorocarbene, and nucleophiles were studied. The effect of the substituents in the diol and aldehyde on their relative reactivity is discussed.

Full text of DOI:10.1023/A:1012350122851

Russian Journal of Organic Chemistry, Vol. 37, No. 1, 2001, pp. 136 140. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 1, 2001,
pp. 144 147.
Original Russian Text Copyright
2001 by Kerimov.
Chemistry of Dioxacycloalkanes: VII.* Synthesis
and Properties of Substituted 1,3-Dioxolanes Derived
from Carbocyclic Aldehydes
A. Kh. Kerimov
Institute of Polymeric Materials, Academy of Sciences of Azerbaidjan,
ul. S. Vurguna 124, Sumgait, 373204 Azerbaidjan
Received August 30, 1999
Abstract Reactions of 3-cyclohexenecarbaldehyde, 6-methyl-3-cyclohexenecarbaldehyde, bicyclo[2.2.1]-
hept-5-ene-endo-2-carbaldehyde, and benzaldehyde with 1,2-propanediol and 3-chloro-1,2-propanediol gave
the corresponding 2,4-substituted 1,3-dioxolanes. Their reactions with peroxyacetic acid, bromine, dichloro-
carbene, and nucleophiles were studied. The effect of the substituents in the diol and aldehyde on their relative
reactivity is discussed.
In the preceding communications we reported on
the results of studying reactions of 3-(2-chloroethoxy)-
1,2-epoxypropane with various alcohols [2] and of
The initial rates (W0 104) of formation of 1,3-di-
oxolanes I and V from 3-cyclohexenecarbaldehyde
1
were 2.76 and 5.60 mol l 1 s , respectively. These
, -unsaturated aldehydes [3] and trichloroacetalde- reactions were considerably faster than those with
hyde [4] with 3-chloro-, 3-(2-chloroethoxy)-, and
3-(2-chloro-1-chloromethylethoxy)-1,2-propanediols.
1,3-Dioxolane derivatives are used as tranquilizers
[5] and plasticizers [6] and are also promising as
monomers for polymerization and polycondensation
[7]. However, there are very limited published data on
the synthesis and properties of 1,3-dioxolanes derived
from aldehydes with a carbocyclic radical.
bicyclo[2.2.1]hept-5-ene-endo-2-carbaldehyde to form
1
dioxolanes III and VII (1.75 and 2.40 mol l 1 s ) and
with benzaldehyde to form dioxolanes IV and VIII
1
(1.80 and 2.46 mol l 1 s , respectively). The same
conclusion follows from the yields of the target prod-
ucts; according to the GLC data, no other products
were formed in the above reactions.
Scheme 1.
The present article describes the synthesis of
2,4-disubstituted 1,3-dioxolanes by reactions of
3-cyclohexenecarbaldehyde, 6-methyl-3-cyclohexene-
carbaldehyde, bicyclo[2.2.1]hept-5-ene-endo-2-carb-
aldehyde, and benzaldehyde with 1,2-propanediol and
3-chloro-1,2-propanediol in toluene in the presence of
KU-2 cation exchanger (Scheme 1). The progress of
the reactions was monitored by GLC. The products
were quantitated by the internal standard technique [8]
using dimethyl or diethyl phthalate (the peak areas
were corrected on the basis of artificial calibration
mixtures). GLC analysis of compounds I VIII
showed the presence of two isomers at a ratio of
55:45. We failed to isolate pure isomers from the
reaction mixtures, but the 1H NMR spectra of isomeric
mixtures also indicated formation of cis and trans
structures (see Experimental).
I IV, R = H; V VIII, R = Cl; I, V, R = 3-cyclohexenyl;
II, VI, R = 6-methyl-3-cyclohexenyl; III, VII, R = bi-
cyclo[2.2.1]hept-5-en-endo-2-yl; IV, VIII, R = Ph.
The relatively high yields of dioxolanes I and V
may be due to better accessibility of the equatorial
aldehyde group in 3-cyclohexenecarbaldehyde for
nucleophilic attack, as compared with the endo-alde-
hyde group in the norbornene derivative [9]. Benzene
____________
*
For communication VI, see [1].
1070-4280/01/3701-0136$25.00 2001 MAIK Nauka/Interperiodica

CHEMISTRY OF DIOXACYCLOALKANES: VII.
137
Scheme 2.
IX, n = 0, R1 = R2 = H; X, n = 0, R1 = H, R2 = CH3; XI, n = 0, R1 = Cl, R2 = H; XII, n = 1, R1 = R2 = H; XIII, n = 1, R1 = Cl,
R2 = H; XIV, n = 0, Nu = CH3O; XV, n = 0, Nu = C3H7S; XVI, n = 1, Nu = (C2H5)2N; XVII, R = H; XVIII, R = CH3;
XIX, R1 = H, R2 = CH3, X = Cl; XX, R1 = Cl, R2 = H, X = Br.
ring is also known to reduce electrophilic properties
of the carbonyl group attached thereto [10].
and XX (Scheme 2). The structure of dioxolanes
I VIII and products of their transformations was
proved by elemental analyses, determination of MRD,
The presence of chlorine atom in the initial diol
favors its reaction with aldehydes and increases the
yield of the product. Taking into account that the
rate-determining stage is nucleophilic attack on the
protonated aldehyde group by the hydroxy group
which is remote from the chlorine atom, the latter is
likely to exert through-space effect on the reaction
center. Consideration of the Newman projections
shows that among three possible conformations of
1
and H NMR and IR spectra. Compound VII was also
synthesized in 19% yield by the procedure described
in [12] from 3-chloro-1,2-epoxypropane in the pres-
ence of H2SO4 (d = 1.84). The IR spectra of I VIII
contained absorption bands at 1050, 1140, and
1
1240 cm due to vibrations of the C O C frag-
1
ments, a weak band in the region 1645 1650 cm
1
(C C), a band at 945 cm (trans-C CH), and
a strong band at 3030 3040 cm ( C H). Com-
1
3-chloro-1,2-propanediol the most energetically favor-
3
able is transoid
[11] which gives rise to hydrogen
pounds IV and VIII also showed a strong IR band
1
bonding between the chlorine atom and the primary
hydroxy group. Such a structure facilitates approach
at 1590 cm belonging to stretching vibrations of
1
the aromatic ring. The band at 750 cm in the spectra
of the reagent and subsequent migration of proton to
of V VIII corresponds to the C Cl bond. Epoxy
derivatives IX XIII are characterized by absorption
+
the leaving group ( OH2).
1
Oxidation of compounds I III and V VII with
50% peroxyacetic acid afforded the corresponding cis-
2-(1,2-epoxy-4-cyclohexyl)- and cis-2-(5,6-epoxybi-
cyclo[2.2.1]hept-endo-2-yl)-1,3-dioxolanes IX XIII
in good yield. Treatment of compounds I and II with
bromine resulted in formation of dibromo derivatives
XVII and XVIII. The chlorine atom in the 4-chloro-
methyl group of V and VII is readily replaced by
methoxy, propylthio, and diethylamino group to form
products XIV XVI. Dichloro- and dibromocarbenes
add to compounds II and V, yielding products XIX
at 850 and 920 cm , typical of oxirane ring. The
presence of epoxy group in XII was confirmed by
reaction with hydrogen chloride in diethyl ether,
which afforded the corresponding chlorohydrin XXI.
EXPERIMENTAL
The IR spectra were measured on a UR-20 instru-
1
ment from samples prepared as thin films. The H
NMR spectra of solutions of 2,4-disubstituted 1,3-di-
oxolanes in CCl4 were obtained on a Tesla BS-487B
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001

138
KERIMOV
Yields, constants, and elemental analyses of compounds I XXI
MRD
Found, %
Calculated, %
Comp. Yield,
bp,
(p, mm)
C
d240
n2D0
Formula
no.
%
found calcd.
C
H
C
H
I
II
III
IV
V
VI
VII
VIII
IX
78
59
63
68
88
70
76
80
80
82
81
68
70
37
36
70
69
63
75
40
70
58 59 (2)
95 97 (5)
69 71 (1)
53 54 (2)
110 112 (2)
96 98 (2)
85 87 (2)
105 106 (2)
89 90 (3)
1.0092 1.4690 46.42 46.79 71.08 9.50 C10H16O2
0.9942 1.4680 50.96 51.41 72.14 9.86 C11H18O2
1.0437 1.4780 49.02 49.21 73.04 8.87 C11H16O2
1.0948 1.5060 44.28 44.76 73.38 6.62 C10H11O2
1.1272 1.4910 52.07 51.66 58.95 7.60 C10H15ClO2b
1.1158 1.4915 56.28 56.24 60.72 7.81 C11H17ClO2c
1.1717 1.5010 53.97 54.08 61.25 7.16 C11H15ClO2d
1.2139 1.5280 50.39 50.73 60.15 5.48 C10H11ClO2
1.1044 1.4710 46.62 46.70 65.32 8.66 C10H16O3
71.39 9.58
72.48 9.95
73.30 8.94
73.60 6.79
59.26 7.46
60.97 7.91
61.53 7.03
60.46 5.57
65.19 8.74
66.64 9.15
54.92 6.91
67.32 8.21
57.27 6.54
66.63 9.14
66.41 9.14
71.67 10.02
36.61 4.91
38.62 5.30
52.18 7.16
a
X
XI
145 147 (25) 1.0858 1.4700 50.94 51.32 66.18 8.97 C11H18O3
e
f
125 126 (1)
104 106 (2)
140 142 (5)
89 90 (3)
142 146 (2)
107 108 (2)
127 128 (2)
160 162 (3)
140 142 (3)
180 185 (2)
140 142 (2)
1.2437 1.4940 51.18 51.56 54.75 6.80 C10H15ClO3
1.1399 1.4850 49.33 49.12 67.11 8.09 C11H16O2
1.2610 1.5070 54.44 53.94 57.09 6.38 C11H15ClO3
1.5042 1.4720 53.06 52.66 66.49 8.98 C11H18O3
1.0497 1.5022 69.13 68.14 64.12 9.26 C13H22O2Sg
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
XXI
h
1.0211 1.4950 71.78 71.62 71.59 9.88 C15H25NO2
i
1.6610 1.5420 62.15 62.79 36.32 4.87 C10H16Br2O2j
1.5869 1.5330 66.90 67.41 38.36 5.49 C11H18Br2O2k
1.2114 1.4980 61.25 61.61 52.04 6.94 C11H18Cl2O3
1.6789 1.5470 70.73 69.71 35.04 3.98 C11H15Br2ClO2 35.27 4.03
1.5090 1.2483 55.66 56.07 56.59 7.28 C11H17ClO3
l
m
56.77 7.36
a
b
c
Found, %: Cl 17.35; calculated, %: Cl 17.49.
Found, %: Cl 16.15; calculated, %: Cl 16.36. Found, %: Cl 16.04; calculated, %:
d
e
f
Cl 16.51.
calculated, %: Cl 15.36.
Found, %: Cl 17.07; calculated, %: Cl 17.84. Found, %: Cl 16.05; calculated, %: Cl 16.21. Found, %: Cl 14.94;
g
h
i
Found, %: S 12.75; calculated, %: S 13.22.
Found, %: N 5.14; calculated, %: N 5.57. Found, %:
Found, %: Cl 28.82; calculated, %: Cl 28.00.
Found, %: Cl 14.88; calculated, %: Cl 15.23.
j
k
Br 48.28; calculated, %: Br 48.72. Found, %: Br 45.64; calculated, %: Br 46.42.
l
m
Found, %: Cl+Br 51.87; calculated, %: Cl+Br 52.13.
spectrometer at 80 MHz using HMDS as internal
reference. Gas liquid chromatography was performed
on a Chrom-4 instrument equipped with a thermal-
conductivity detector (2400 4-mm stainless steel
column packed with 5% of XE-60 on Chromaton
N-AW-DMCS; oven temperature 190 C; carrier gas
helium, flow rate 30 ml/min; detector current 80 mA).
2-(3-Cyclohexenyl)-4-methyl-1,3-dioxolane (I).
a. A mixture of 55.1 g (0.5 mol) of 3-cyclohexene-
carbaldehyde, 45.6 g (0.6 mol) of 1,2-propanediol,
70 ml of toluene, and 0.17 g (0.3% relative to the
aldehyde) of KU-2 cation exchanger was stirred for
5 h at 130 C with azeotropic distillation of water.
The mixture was filtered, the filtrate was evaporated
under reduced pressure, and the residue was purified
by vacuum distillation. Yield 63.8 g (76%) (see table).
The progress of the reaction was monitored by GLC.
1H NMR spectrum (CCl4), , ppm: 0.9 1.20 m (5H,
CH3CHCH2), 1.45 2.25 m (7H, CH2CH2CHCH2),
3.15 4.25 m (3H, CH2O, CHO), 4.55 d (1/2H,
OCHO-trans), 4.63 d (1/2H, OCHO-cis), 5.48 s (2H,
CH CH). Compounds II VIII were synthesized in
a similar way.
b. A mixture of 36.6 g (0.3 mol) of bicyclo[2.2.1]-
hept-5-ene-endo-2-carbaldehyde, 29.6 g (0.32 mol) of
3-chloro-1,2-epoxypropane, 50 ml of toluene, and
3.3 g (9 wt % with respect to the aldehyde) of H2SO4
(d = 1.84) was refluxed for 5 h. The mixture was
then cooled to 18 20 C and washed with a 5% solu-
tion of alkali and with water. The aqueous phase was
extracted with toluene, the combined extracts were
dried over MgSO4 and evaporated, and the residue
was distilled under reduced pressure. Yield of VII
12.3 g (19%), bp 84 85 C (2 mm), d240 = 1.1683,
n2D0 = 1.4940.
2-(3,4-Epoxycyclohexyl)-4-methyl-1,3-dioxolane
(IX). To a mixture of 25.2 g (0.15 mol) of compound
I and 70 ml of chloroform we added with stirring
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001

CHEMISTRY OF DIOXACYCLOALKANES: VII.
139
at 18 20 C 30.4 g of 50% peroxyacetic acid over
a period of 60 min. The mixture was stirred for
an additional 1.5 h and treated with a 5% solution of
sodium carbonate. The organic phase was washed
with water, dried over MgSO4, and evaporated, and
the residue was distilled under reduced pressure to
and the residue was subjected to vacuum distillation
to isolate product XVI (see table).
2-(3,4-Dibromocyclohexyl)-4-methyl-1,3-dioxo-
lane (XVII). Bromine, 25.6 g (0.16 mol), was added
dropwise to a mixture of 25.2 g (0.15 mol) of com-
pound I and 50 ml of chloroform, stirred at 5 to
10 C. The mixture was stirred for an additional
1.5 2 h and washed with a 5% solution of sodium
hydroxide and water. The aqueous phase was ex-
tracted with chloroform, and the extract was combined
with the organic phase, washed with water, dried
over CaCl2, and evaporated. The residue was distilled
under reduced pressure to isolate 33.8 g (69%) of
product XVII (see table). Compound XVIII was
obtained in a similar way.
2-(7,7-Dichloro-4-methylbicyclo[4.1.0]hept-3-yl)-
4-methyl-1,3-dioxolane (XIX). Chloroform, 15 ml,
was added dropwise with stirring to a mixture of
25 ml of 50% aqueous sodium hydroxide, 10 ml of
benzene, 0.2 g of benzyltriethylammonium chloride,
and 9.2 g (0.05 mol) of compound II. The mixture
spontaneously warmed up to 30 C. It was stirred for
an additional 3 h, diluted with ether, washed with
a 1% aqueous solution of acetic acid and with water,
dried over MgSO4, and evaporated. Vacuum distilla-
tion of the residue gave 21.5 g (63%) of product XIX.
1H NMR spectrum (CCl4), , ppm: 0.9 1.20 d (3H,
CH3), 1.45 2.25 m (7H, cyclohexane), 4.46 d (1/2H,
OCHO-trans, J = 7 Hz), 4.59 d (1/2H, OCHO-cis,
J = 7 Hz).
1
isolate compound IX (see table). H NMR spectrum
(CCl4), , ppm: 1.25 2.25 m (7H, CH2CH2CHCH2),
2.95 d (2H, 2CH, oxirane), 3.25 4.30 m (3H, CH2O,
CHO), 4.55 d (1/2H, OCHO-trans), 4.65 d (1/2H,
OCHO-cis). Compounds X XIII were obtained in
a similar way (see table).
2-(3-Cyclohexenyl)-4-methoxymethyl-1,3-dioxo-
lane (XIV). A mixture of 9.6 g (0.3 mol) of methanol
and 4 g of powdered sodium hydroxide was stirred for
60 min at 65 70 C, 20.3 g (0.1 mol) of compound V
was added, and the mixture was heated to 75 80 C
and stirred for 4 h at that temperature. It was then
cooled, diluted with ether, neutralized with acetic
acid, washed with water, dried over MgSO4, and
evaporated. Vacuum distillation of the residue gave
product XIV (see table).
2-(3-Cyclohexenyl)-4-propylthiomethyl-1,3-di-
oxolane (XV). a. To 18.7 g (0.25 mol) of propane-
thiol we added dropwise 15 ml of a 40% solution of
sodium hydroxide, and the mixture was stirred for
60 min at 85 90 C. The mixture was cooled to room
temperature, 48.6 g (0.24 mol) of compound V was
added in one portion, and the mixture was stirred for
3 4 h at 125 C. The product was isolated as described
above for compound XIV and was purified by vacuum
distillation (see table).
4-Chloromethyl-2-(7,7-dibromobicyclo[4.1.0]-
hept-3-yl)-1,3-dioxolane (XX) was synthesized in
a similar way (see table).
b. A mixture of 55.1 g (0.5 mol) of 3-cyclohexene-
carbaldehyde, 76 g (0.5 mol) of 3-propylthio-1,2-
propanediol, 70 ml of toluene, and 0.16 g (0.3 wt %
with respect to the aldehyde) of KU-2 cation ex-
changer was stirred for 5 h at 130 C with azeotropic
distillation of water. The mixture was filtered, and
the solvent was distilled off. Vacuum distillation of
the residue gave 79.5 g (66%) of compound V with
2-[2(3)-Chloro-3(2)-hydroxybicyclo[2.2.1]hept-5-
yl]-4-methyl-1,3-dioxolane (XXI). Gaseous hydrogen
chloride was passed at 10 to 15 C through a mix-
ture of 11.8 g (0.06 mol) of compound XII and 50 ml
of diethyl ether until a required amount was absorbed
(by weight). The mixture was kept for 3 4 h, washed
with a 2% solution of sodium carbonate and with
water, dried over MgSO4, and evaporated. Vacuum
distillation of the residue gave 9.8 g (70%) of com-
pound XXI (see table).
bp 139 141 C (1 mm), d240 = 1.0486, nD20 = 1.5016.
2-(Bicyclo[2.2.1]hept-5-en-endo-2-yl)-4-diethyl-
aminomethyl-1,3-dioxolane (XVI). A mixture of
21.5 g (0.1 mol) of compound VII, 27.6 g of potas-
sium carbonate, and 36.5 g (0.5 mol) of diethylamine
was stirred for 3 h at 125 130 C. Excess diethylamine
was distilled off, and the mixture was cooled, diluted
with water, and stirred until dissolution of mineral
salts. The organic phase was separated, and the
aqueous phase was extracted with ether. The com-
bined extracts were dried over MgSO4 and evaporated,
The author is grateful to M.G. Babaev for his help
in determining the reaction rates and preparing the
manuscript.
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