Ionic telomerization of 1-chloro-2,3-epoxypropane with allyl alcohol and properties of products obtained

Article abstract of DOI:10.1134/S1070427213090084

Ionic telomerization of 1-chloro-2,3-epoxypropane with allyl alcohol in the presence of boron trifluoride etherate as a route to halogenated epoxy oligoethers was studied. Selective chlorination or bromination of the intermediate oligo(chlorohydrin), followed by dehydrochlorination (epoxidation) of the intermediate oligohalohydrins with NaOH, was performed. The synthesized products are effi cient as active diluents for a compound based on ED-20 resin.

Full text of DOI:10.1134/S1070427213090084

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 9, pp. 1364−1369. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.Kh. Kerimov, A.T. Orudzheva, Kh.A. Mamedova, U.A. Alieva, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 9,
pp. 1394−1400.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Ionic Telomerization of 1-Chloro-2,3-epoxypropane
with Allyl Alcohol and Properties of Products Obtained
A. Kh. Kerimov, A. T. Orudzheva, Kh. A. Mamedova, and U. A. Alieva
Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgayit, Azerbaijan
e-mail: ipoma@science.az
Received August 24, 2012
Abstract—Ionic telomerization of 1-chloro-2,3-epoxypropane with allyl alcohol in the presence of boron trifluo-
ride etherate as a route to halogenated epoxy oligoethers was studied. Selective chlorination or bromination of
the intermediate oligo(chlorohydrin), followed by dehydrochlorination (epoxidation) of the intermediate oligoha-
lohydrins with NaOH, was performed. The synthesized products are efficient as active diluents for a compound
based on ED-20 resin.
DOI: 10.1134/S1070427213090084
The reaction of alkanols with 1-chloro-2,3-epoxy- oligoether alcohol III obtained and of its bromination
and chlorination products (ІV and V, respectively) with
NaOH in diethyl ether (Scheme 1).
propane (1-Сl-2,3-EP) in the presence of aprotic acids,
followed by epoxidation of the intermediate oligochloro-
hydrin with alkali, belongs to the well studied field of or-
ganic chemistry. Nevertheless, this reaction attracts steady
researchers’attention, because many of its products have
valuable technical properties and are used both them-
selves and as intermediates in organic synthesis [1, 2].
We studied in detail the reaction of the starting al-
cohol I with 1-Cl-2,3-EP and developed a procedure
for determining the composition of halogenated epoxy
oligoethers VI, X, and XІІІ by vacuum fractionation and
identification of separate components.
The reaction of alkenols, including allyl alcohol, with
1-Cl-2,3-EPhas been studied insufficiently. Furthermore,
available data on the order of the epoxy ring opening in
1-Cl-2,3-EP with allyl alcohol are contradictory [3–5].
Except a few papers [6, 7], the authors, as a rule, restrict
themselves only to isolation of the primary reaction
Previously we studied [2] the reaction of 1-Cl-2,3-EP
with sterically hindered halohydrins and found that an
increase in the process selectivity (restriction of telom-
erization) is possible only at five- to sixfold excess of the
starting halohydrin, because the ether alcohols formed in
the reaction compete with the starting halohydrin in the
product [8, 9]. It is known, however, that the reaction, epoxy ring opening. However, as expected in accordance
irrespective of the catalysis type (cationic or anionic), is with [12], the chlorohydrins formed in the reaction of allyl
accompanied by telomerization. Its restriction is difficult, alcohol with 1-Cl-2,3-EP are considerably less reactive
because successive addition of ether alcohols formed in than the starting alcohol in the epoxy ring opening in
the course of the reaction to 1-Cl-2,3-EP leads to accu- 1-Cl-2,3-EP, which somewhat simplifies the telomeriza-
mulation of the telomeric product in the system [2, 10, tion suppression.
11]. It should be noted that the lack of information on
the composition of the telomeric product and on the ef-
fect of various factors on the telomerization complicate
optimization of the reaction conditions.
In particular, we found that, at the I : II ratio of (3.5–
4) : 1, the yield of VІІ (Scheme 1) is 72–75%, whereas at
the ratio of (2.5–3) : 1, the chlorinated unsaturated epoxy
oligoether (CUEOE, VI) formed is an oligomer of the fol-
This study deals with the reaction of allyl alcohol with lowing composition: n = 0 (VІІ) 53%, n = 1 (VІІІ) 27%,
1-Cl-2,3-EP in the presence of boron trifluoride etherate, n = 2 (ІХ) 17%. Similar pattern is observed with the bro-
followed by dehydrochlorination (epoxidation) of the mochlorinated unsaturated epoxy oligoether (BCUEOE,
1364

IONIC TELOMERIZATION OF 1-CHLORO-2,3-EPOXYPROPANE
1365
Scheme 1.
XII, XIII,
R = BrCH2CH(Br)CH2 (IV), ClCH2CH(Cl)CH2 (V); R1 = CH2=CHCH2, n = 0, 1, 2 (VI), n = 0 (VII), n = 1 (VIII), n =
2 (IX); R1 = CH2=C(Br)CH2, n = 0, 1 (X), n = 0 (XI), n = 1 (XII); R1 = ClCH2CH(Cl)CH2 (XIII), n = 0 (XIV).
X) (Scheme 1), and from chlorinated epoxy oligoether
(CEOE, XІІІ) we were able to isolate and identify only
compound XІV. Analysis of the nondistillable fraction
of CEOE (XІІІ) showed that it was a highly viscous
oligomer. The compositions of individual compounds
XII–IX, XI, and XII, isolated from CUEOE (VІ) and
BCUEOE (Х), was confirmed by elemental analysis, and
their structures were proved by МRD determination, by
the IR and 1H NMR data, and by independent synthesis
of VІІІ by the reaction of ether alcohol ХV with 1-Cl-
2,3-EP (at 5 : 1 ratio), followed by dehydrochlorination
with alkali (Scheme 2).
opening (regioselectivity). These notions are identical
only without telomerization, which inevitably contributes
to the overall process. In particular, it was found that the
reaction of allyl alcohol with 1-Cl-2,3-EP in the pres-
ence of boron trifluoride etherate under the conditions
reducing to a minimum the contribution of successive
reactions [at the ratio І : ІІ = (3.5–4) : 1 and temperature
not exceeding 20–25°С] yields products of normal (XV,
1-chloro-3-allyloxy-2-propanol) and abnormal (XVІІ,
3-chloro-2-allyloxy-1-propanol) opening of the epoxy
ring in approximately 9 : 1 ratio [14]. Compounds XV and
XVІІ were synthesized under the conditions of [14] and
were identified by GLC. Hence, in catalysis of the reac-
tion of allyl alcohol with 1-Cl-2,3-EPby aprotic acids [5],
including anhydrous magnesium perchlorate [15], there
are no deviations in the process regioselectivity compared
to the reaction of alkanols with the same substrate.
The properties of the samples of VІІІ prepared by
Scheme 2 and isolated from CUEOE (VІ) are identical.
In the IR spectra of VІІІ, there are absorption bands at the
following positions (cm–1): 750 (С–Сl); 1030, 1120, and
1220 (С –О–С); 1645–1650 (С=С stretching); 660–670
(С=С bending); 881, 903, and 1250 (epoxy group) [13].
Then we showed that intermediate adduct ІІІ under the
conditions of [16] undergoes selective (without replace-
ment of hydroxy group) bromination and chlorination
[17] to form the corresponding dibromo (ІV) and dichloro
(V) derivatives.
It should be noted that, in reactions of alcohols with
1-Cl-2,3-EP (and with unsymmetrically substituted
α-oxides as a whole), the process selectivity should ap-
parently be distinguished from the order of the epoxy ring
Scheme 2.
BF3 O(C2H5)2
NaOH
VIII.
CH2=CHCH2OCH2CHOH
CH2=CHCH2OCH2CHOCH2CHOH
CH2Cl
+ II
O(C2H5)2
CH2Cl
CH2Cl
XVI
XV
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 9 2013

1366
KERIMOV et al.
We found that the dehydrochlorination (epoxidation
some characteristics of the epoxy oligoethers are given
in Tables 1 and 2.
with alkali) of bromochlorinated oligoether alcohol ІV
is inevitably accompanied by dehydrobromination of its
2,3-dibromopropoxy moiety to form BCUEOE (X). This
result is well consistent with the known ease of trans elim-
ination [18]. Hence, the synthesis of BCUEOE (X) and of
individual compounds XІ and XІІ with preservation of
the 2,3-dibromopropoxy moiety is practically impossible
under these conditions (Scheme 1), because equal prob-
ability of these two reactions extremely complicates their
separate analysis. However, dehydrochlorination of V,
irrespective of the excess of the alkali, occurs selectively,
with only the chlorohydrin moiety being involved, and
yields chlorinated epoxy oligoether XIII, which was also
confirmed by a model reaction (Scheme 3).
Because the development of high-performance
composite materials based on commercial epoxy resins
becomes more and more topical with the progress of
engineering, some of the products that we prepared, in
particular, oligoethers VI and X and compound XIV,
were tested in a laboratory as plasticizers for a compound
based on ED-20 epoxy–4,4'-isopropylidenediphenol resin
cured with polyethylenepolyamine (PEPA).
The modification was performed as follows. With
each product being tested, we prepared three formulations
with the following proportions of the major components
(parts): ED-20 resin, 90, 80, and 70; additive, 10, 20,
and 30, respectively; PEPA, 20. Each formulation was
cured separately in standard molds at room temperature
for 24 h, after which the specimens were heat-treated for
2 h at 80°С and for 2 h at 120°С, and their physicom-
echanical characteristics were determined. The dielectric
constant and the dielectric loss tangent were measured
with a TR-9701 ac bridge. The electrical strength of the
materials was determined with sphere–plane electrodes
at a specimen thickness of 0.4 mm. The results of the
tests (arithmetic mean of five determinations) are given
in Table 3. The corresponding parameters for ED-20
resin cured with PEPA without modifier are given for
comparison.
Hence, the dehydrochlorination selectivity in the case
of oligoether alcohol V and compound XIX (Table 1) is
apparently due, on the one hand, to less stereoselective
arrangement of chlorine atoms in the 2,3-dichloropropoxy
moiety [19] and, on the other hand, to higher strength of
the С–Cl bond compared to the C–Br bond [19].
1
In the H NMR spectrum of compound XІ isolated
from BCUEOE (X) and prepared by Scheme 3, the
ОСН2 protons give a multiplet at 2.40–2.70 ppm. The
methine proton in the epoxy group, –СН–СН2О, gives a
multiplet at 3.00–3.20 ppm, and the CH2O protons give
a multiplet at 3.15–3.80 ppm. The =С(Br)CH2O protons
give a singlet at 4.05 ppm. The presence of a doublet at
5.50–5.90 ppm (2Н, СН2=С) in the 1H NMR spectrum
confirms the selectivity of dehydrobromination of the
2,3-dibromopropoxy moiety in XVIIІ with proton elimi-
nation from the secondary carbon atom.
As seen from Table 3, on introducing 10–20 wt parts
of each of the products being tested (VI, X, XIV), the
ultimate strength of the compound increases relative to
unmodified ED-20 compound by a factor of 2–2.5; the
elasticity, by a factor of 10–14; the softening point, by
a factor of 1.5; and the electrical strength, by a factor of
2–2.5. These data confirm that the additives used partici-
pate in the cross-linking in the course of curing of the
compound with PEPA, which is apparently responsible for
the enhancement of the main parameters of the compound.
The synthesized halogenated epoxy oligoethers VІ,
X, and XІІІ and individual compounds VІІ–ІX, XІ,
XІІ, XІV, XVІ, XVІІI, and XIX are almost odorless
transparent liquids insoluble in water and readily soluble
in organic solvents (acetone, ether, ethanol, etc.). The
physicochemical characteristics, analytical data, and
molecular refractions of the individual compounds and
Thus, the materials obtained have good physicom-
echanical and dielectric properties and can be used in
Scheme 3.
X = Br (XVIII), Cl (XIX); R = CH2=C(Br)CH2 (XI), ClCH2CH(Cl)CH2 (XIV).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 9 2013

IONIC TELOMERIZATION OF 1-CHLORO-2,3-EPOXYPROPANE
1367
Table 1. Physicochemical characteristics of the synthesized compounds and halogenated epoxy oligoethers
Epoxy number, %
Tb, °C/P, mm
Yield,
%
Compound or polyether
nD20
d420
Hg
found
24.48
calculated
24.31
Chlorinated unsaturated epoxy oligoether (VI)
1,2-Epoxy-3-(allyloxy)propane (VII)
–
1.4700
1.1443
–
66–67/28
1.4343
1.4650
0.9678
1.1247
36.98
20.65
37.70
20.83
72.0
79.0
1,2-Epoxy-3-(1-chloromethyl-2-allyloxy)ethoxypro-
107–108/1
pane (VIII)
1-Chloro-3-allyloxy-2-(2'-chloromethyl-2'-glycidyl)
ethoxypropane (IX)
165–168/1
–
1.4748
1.5190
1.1945
1.7189
14.11
18.19
14.39
18.68
–
–
Bromochlorinated unsaturated epoxy oligoether (X)
1,2-Epoxy-3-(2-bromo-2-propenyloxy)propane (XI)
58–60/2
1.4860
1.5100
1.4512
1.4622
22.23
15.13
22.29
15.07
78.0
–
1-Chloro-2-glycidyl-3-(2'-bromo-2'-propenyloxy)
141–143/1
propane (XII)
Chlorinated epoxy oligoether (ХIII)
–
1.4682
1.4730
1.4630
1.4780
1.1980
1.2490
1.1120
1.2025
15.28
23.09
–
16.15
23.26
–
1,2-Epoxy-3-(2,3-dichloropropoxy)propane (XIV)
1-Chloro-3-allyloxy-2-propanol (XV)
104–106/1
73–74/1
135–137/1
76.0
86.0
68.0
1-Chloro-3-(1'-chloromethyl-2'-allyloxy)ethoxy-2-
–
propanol (XVI)
3-Chloro-2-allyloxy-1-propanol (XVII)
90–91/1
1.4570
1.5360
1.1149
1.8299
–
–
64.0
91.0
1-Chloro-3-(2,3-dibromopropoxy)-2-propanol (XVIII) 146–148/1
1-Chloro-3-(2,3-dichloropropoxy)-2-propanol (XIX)
126–128/1
1.4950
1.3345
–
83.0
various fields, in particular, as high-performance casting
formulations for sealing of electric units in electrical
engineering.
0.2 mL of BF3·O(C2H5)2, 37 g (0.4 mol) of 1-chloro-
2,3-epoxypropane was added over a period of 60 min
at 30–35°С, after which the mixture was stirred for an
additional 60 min.After cooling to room temperature, the
catalyst was removed by washing with a 5% aqueous so-
dium carbonate solution, excess allyl alcohol was distilled
off in a vacuum, and the residue was added from a drop-
ping funnel into a three-necked flask charged with 20 g
(0.5 mol) of NaOH and 80 mL of diethyl ether (with stir-
ring). In the process, the mixture warmed up to 30–35°С.
The suspension was stirred for an additional 40–60 min at
40–45°С.After cooling to room temperature, the organic
phase was separated, and the salt precipitate was dissolved
in water and extracted with ether. The combined extracts
were washed with 5% aqueous acetic acid and water and
dried over MgSO4. The ether was distilled off, and the
residue was kept in a vacuum to constant weight (65 g).
EXPERIMENTAL
The IR spectra were recorded with a UR-20 device
from thin films. The 1H NMR spectra of the compounds
synthesized (in particular, of XI) in ССl4 were taken
with a Теsla BS-487 B spectrometer (80 MHz, internal
reference HMDS). The chromatograms of the glycidyl
ethers were obtained with a Сhrom-4 device (thermal
conductivity detector, 2400 × 4-mm stainless steel col-
umn, on Chromaton N-AW-DMCS, carrier gas He, flow
rate 30 ml min–1, detector current 80 mA).
Chorinated unsaturated epoxy oligoether (VІ). To
a stirred mixture of 58.1 g (1.0 mol) of allyl alcohol and
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 9 2013

1368
KERIMOV et al.
Table 2. Analytical and molecular refraction data for the compounds
MRD
calculated
Found, %
Calculated, %
Compound
Formula
found
50.79
70.50
39.38
58.41
40.73
57.24
52.89
C
H
Cl
C
H
Cl
VIII
IX
50.89
71.25
38.29
58.66
41.56
57.84
53.59
52.14
48.04
37.25
37.79
38.87
44.18
23.11
7.38
6.68
4.61
4.90
5.35
6.67
3.49
16.88
23.48
C9H15ClO3
52.30
48.17
34.33
37.85
38.94
44.46
23.21
7.32
6.74
4.69
4.90
5.44
6.63
5.57
17.15
23.69
C12H20Cl2O4
C6H9BrO2
XIa
XIIb
XIV
XVI
XVIII
C9H14BrClO3
C9H10Cl2O2
C9H16Cl2O3
C6H11Br2ClO2
38.46
29.11
38.31
29.16
XIX
48.40
47.68
32.49
4.94
48.16
C6H11Cl3O2
32.53
4.89
48.01
a Br. Found, %: 41.23. Calculated, %: 41.39.
b Br + Cl. Found, %: 40.12. Calculated, %: 40.39.
Table 3. Physicomechanical and dielectric properties of the epoxy compounds
Ultimate ten- Relative elon-
Electrical
strength,
kV mm–1
Dielectric
permittivity
at 50 Hz
Content,
wt parts
Vicat softening
Dielectric loss
tangent at 50 Hz
Modifier
sile strength,
MPa
gation
at break, %
point, °С
VI
10
20
30
10
63.3
71.5
76.4
62.9
17
17
19
17
127
170
175
155
41.9
40.14
43.30
38.30
0.0169
0.080
4.13
4.28
4.82
4.19
0.0140
0.0168
X
20
30
94.2
63.3
20
12
170
130
42.83
36.28
0.0210
0.0186
4.76
4.84
XIV
10
68.1
20
160
39.15
0.0210
4.70
20
30
–
71.4
82.4
36.0
20
20
1.5
170
175
100
40.33
44.85
15–20
0.0270
0.0200
0.03
4.90
4.67
3.8
ED-20 +
PEPA (refer-
ence)
The constants of the CUEOE obtained (VI) are given
in Table 1. By vacuum fractionation of VI, we isolated
and identified compounds VІІ (34.5 g, yield 53%), VІІІ
(17.5 g, yield 27%), and ІX (11.0 g, yield 17%) (Tables 1,
2). Similar procedure was used for preparing BCUEOE
(X) and determining its composition by vacuum frac-
tionation (Table 1).
Independent synthesis of VІІІ. To a mixture of 75.3 g
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 9 2013

IONIC TELOMERIZATION OF 1-CHLORO-2,3-EPOXYPROPANE
1369
neftekhimicheskaya konferentsiya (V Int. Petrochemical
Conf.), Baku, 2002, p. 50.
(0.5 mol) of compound XV prepared from allyl alcohol
and 1-chloro-2,3-epoxypropane following the procedure
described in [20] and of 0.2 mLof boron trifluoride ether-
ate, 9.3 g (0.1 mol) of 1-chloro-2,3-epoxypropane was
added dropwise with stirring over a period of 60 min at
20–22°С.After adding the whole amount of 1-chloro-2,3-
epoxypropane, the mixture was stirred for an additional
2 h. The catalyst was removed by washing with a 5%
aqueous sodium carbonate solution, excess chlorohydrin
XV was distilled off at 73–75°С (1 mm Hg), and the
residue (66 g) was added dropwise into a flask charged
with 6.0 g (0.15 mol) of powdered NaOH and 80 mL
of diethyl ether. The mixture was stirred for 3.5–4 h at
35–40°С. Then, the ether phase was separated, and the
salt precipitate was dissolved in water and extracted with
ether. The combined extracts were washed with 5% aque-
ous acetic acid and water and dried over MgSO4. The
ether was distilled off, and the residue was distilled in a
vacuum to obtain 14.9 g (72.0%) of VІІІ (Tables 1, 2).
Compounds VII, XІ, and XІV were synthesized similarly
(Tables 1, 2).
2. Kerimov, A.Kh., Plast. Massy, 2005, no. 3, p. 31.
3. Vladimirova, M.G. and Petrov, A.A., Zh. Obshch. Khim.,
1947, vol. 17, no. 1, p. 51.
4. Mamishov, A.Kh., Cand. Sci. Dissertation, Baku, 1976.
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Chernyak, S.V., Zh. Org. Khim., 2004, vol. 40, no. 6, p. 810.
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Mezhdunarodnaya nauchnaya konferentsiya “Tonkii or-
ganicheskii sintez i kataliz” (III Int. Scientific Conf. “Fine
Organic Synthesis and Catalysis”), Baku, 2005, p. 34.
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(Ionic Telomerization), Moscow: Khimiya, 1968.
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khimiyu (Introduction to Theoretical Organic Chemistry),
Moscow: Vysshaya Shkola, 1974.
CONCLUSIONS
(1) Ionic telomerization of 1-chloro-2,3-epoxypropane
with allyl alcohol was studied, and conditions allowing
synthesis of halogenated unsaturated epoxy oligoethers
or of individual compounds of this type were found.
13. Nakanishi, K., Infrared Absorption Spectroscopy, Tokyo:
Nankido, 1962.
14. Pishnamazzadeh, B.F. and Mamishov, A.Kh., Zh. Org.
Khim., 1973, vol. 9, no. 7, p. 1365.
(2) The synthesized products are well compounded
with ED-20 epoxy–4,4'-isopropylidenediphenol resin,
and composite materials prepared on their basis exhibit
high physicomechanical and dielectric properties and can
find use in various branches of electrical engineering.
15. USSR Inventor’s Certificate no. 658132, 1977.
16. USSR Inventor’s Certificate no. 1129870, 1983.
17. Japan Patent 62-26243, 1985.
18. Potapov, V.M., Stereokhimiya (Stereochemistry), Moscow:
Khimiya, 1976.
19. Sykes, P., A Guidebook to Mechanism in Organic
Chemistry, New York: Longman, 1986.
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Orudzheva, A.T., Plast. Massy, 2011, no. 5, p. 27.
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 9 2013