Synthesis of 1-(4-isopropenylphenoxy)-bromo-C2-C 4-alkanes and application of their transformation products

Article abstract of DOI:10.1134/S1070427209100243

Reaction of 4-isopropenylphenol with α,ω-dibromo-C ₂-C₄-alkanes by the Willamson reaction in the presence of potassium iodide as promoter, aiming to synthesize the corresponding monobromosubstituted derivatives and to study their som

Full text of DOI:10.1134/S1070427209100243

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 10, pp. 1871−1876.  Pleiades Publishing, Ltd., 2009.
Original Russian Text  A.M. Magerramov, M.R. Bairamov, I.A. Aliev, M.A. Agaeva, M.G. Allakhverdieva, I.G. Mamedov, M.A. Dzhavadov, 2009, published in
Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 10, pp. 1719−1724.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of 1-(4-Isopropenylphenoxy)-bromo-С2С4-alkanes
and Application of Their Transformation Products
A. M. Magerramov, M. R. Bairamov, I. A. Aliev, M. A. Agaeva, M. G. Allakhverdieva,
I. G. Mamedov, and M. A. Dzhavadov
Baku State University, Baku, Republic of Azerbaijan
Received December 3, 2008
Abstract—Reaction of 4-isopropenylphenol with α,ω-dibromo-С2-С4-alkanes by the Willamson reaction in the
presence of potassium iodide as promoter, aiming to synthesize the corresponding monobromosubstituted derivatives
and to study their some chemical transformation. Optimal conditions to obtain 1-(4-isopropenylphenoxy)-2-
bromoethane, 1-(4-isopropenylphenoxy)-3-bromopropane and 1-(4-isopropenylphenoxy)-4-bromobutane were
found. The nitrogen-containing derivatives, inhibitors of a hydrosulfuric corrosion in the water-salt solutions, were
obtained on the basis of the first two compounds. The derivatives involving multiple bond and ester-group were
synthesized from the third compound. Their incorporation into the polystyrene chains in the process synthesis
gives them plasticize properties.
DOI: 10.1134/S1070427209100243
Alkenylphenols and their derivatives are of quiet
various uses [1–6]. Their reactions with halogen-
containing alkanes by Willamson, in particular with
symmetric dihalogenalkanes, promise interesting
resultes. They enable synthesis of new phenol derivatives
containing multiple bond С=С and halogen atom, and as
a result they can be used as intermediate for the further
transformations.
and of studying their some transformations.
The reactions of DBE, DBP and DBB with 4-IP were
carried out by Scheme 1.
Results of performed investigation show, that the
temperatureandmolarratioofreagentsinthemixtureeffect
significantly on formation of the monobromosubstituted
derivatives DBE, DBP and DBB.
Experiments for search of optimal conditions
providing a good yield were conducted by the example
of DBB and 4-IP at the different temperatures and
molar ratio of DBB and 4-IP 1:1. We have found that as
temperature is increased from 20 to 80°С the yield of
monobromine-containing compound grows from 3.4 to
47.8%. Further temperature increase to 100°С leads to
decrease in its yield to 45.1%. The side reaction of 4-IP
dimerization enhances under these conditions.
It was shown in the work [7] that di(4-isopropenyl-
phenoxy)alkanes are dominantly formed by the reaction
of 4-isopropenylphenol (4-IP) with α,ω-dihalogen-
С1–С4-alkanes in the presence of potassium hydroxide.
However, the further investigations showed that, among
them, (4-isopropenylphenoxy)halogens were formed
too. A study of an influence of such various factors
as a temperature and ratio of reagents on the reaction
progress has shown that the molar ratio of the used
substances effects essentially on a composition of end
products.
An obtained dependence of 1-(4-isopropenylphenoxy)-
4-bromobutane yield on the molar ratio DBB : 4-IP at
the found optimal temperature 80°С are given on the
figure.
In this work we present results of studying the reactions
of 1,2-dibromoethane (DBE), 1,3-dibromopropane (DBP)
and 1,4-dibromobutane (DBB) with 4-IP for the purpose
of synthesis of the corresponding bromoalkyl derivatives,
The maximum yield, 64.2%, compound III was
obtained at the molar ratio of DBB and 4-IP 1.5 : 1.
Further increase of DBB amount in the initial mixture
1871

1872
MAGERRAMOV et al.
Scheme 1.
Scheme 2.
n = 2 (I), n = 3 (II), n = 4 (III).
n = 2: 1-(4-isopropenylphenoxy)ethyl-N-pyridinium
bromide IV, n = 3: 1-(4-isopropenylphenoxy)propyl-N-
pyridinium bromide V.
leads to no essential change in the yield of the end
product.
Note that in the course of this reaction under the
optimal conditions product III forms along with formation
of approximately 18% of a disubstitution product, 1,4-
di(4-isopropenylphenoxy)butane, and also little amounts
of dimer derivatives of 4-IP (~4%).
Scheme 3.
The presence of the halogen atom in the structure of
compounds I–III enables their further transformation
with pyridine and organic acids.
Quaternization of I and II with pyridine at 110°С for
5 h results in the corresponding quaternary salts IV and
V (Scheme 2).
RCOOH – C8H17COOH; naphthene acids frac-tion.
Synthesis of compound III derivatives containing
ester-group was carried out by reaction of III with
pelargonic acid and commercial fraction of naphthene
acids. The reaction proceeds in acetone in the presence
of triethylamine as acceptor of HBr at room temperature
(Scheme 3).
sulfide, even in minimum concentration (25–50 mg l–1)
provides a protecting effect: 63.0 and 73.3% for IV,
and 76.5 and 82.3% for V. A concentration increase to
150–200 mg l–1 make it possible to decrease essentially
the corrosion rate and to increase the protecting degree
on average to 95–99%. Compound V exceeds IV in
an efficiency of the protection.
Studying of the esterification reaction of compound
III with pelargonic acid makes it possible to establish,
as one would expected, that this process occurs with
participation of the bromine-containing fragment to form
compounds containing ester-group and multiple bond
simultaneously.
The investigation of compounds IV and V as corrosion
inhibitors for steel St.3 showed that they possessed high
inhibiting properties in the examined aggressive media
(see the table).
It is known [8] that the presence of multiple bond and
quaternary pyridinium fragments in the inhibitor structure
contributes to their surface activity on a metal to form the
sufficiently fast adsorption layers protecting its against
corrosion. Addition of the aforementioned compounds
to the aqueous-saline solution, saturated with hydrogen
Effect of the ratio DBB and 4-IP (A) on the yield of 1-(4-iso-
propenylphenoxy)-4-bromobutane B (%) (temperature 80°С).
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SYNTHESIS OF 1-(4-ISOPROPENYLPHENOXY)-BROMO-С2–С4-ALKANES
1873
Results of tests of 1-(4-isopropenylphenoxy)ethyl- (IV) and 1-(4-isopropenylphenoxy)propyl-N-pyridinium bromides (V) as
SRB bactericides and hydrosulfuric corrosion inhibitors for steel St.3
a 3% NaCl + white spirit + 500 mg l–1 H2S, pH 5.3, t 25°C.
Research of compounds IV and V in the different
concentrations as bactericides suppressing growth of
sulfate-reducing bacteria (SRB) showed that the bacteria
growth is virtually suppressed when compound IV is used
in the concentration of 150 mg l–1, V, in the concentration
of 100 mg l–1. Their applying in the lower concentrations
allows canceling no fully a bacteria growth: compound
IV (50–75 mg l–1) decreases SRB growth on average
by 50% and product V in the same concentration, by
8093.5%.
isopropenyl and ester-groups simultaneously, we studied
reaction of their copolymerization with styrene in the
ratios from 5 : 95 to 30 : 70 (wt %). The process was
carried out in a camera in the presence of 0.5% of di-
tert-butylperoxide as initiator at 120°С for 20 h. It was
found that the ratio of the taken monomers in the initial
mixture effected essentially on the yield of the end
copolymer. The copolymer yield was 97.6, 94.2, 88.3
and 71.0% at the ratio 5 : 95, 10 : 90, 20 : 80 and 30 :
70 (wt %), respectively. The obtained results testify that
styrene is more reactive than the derivatives of compound
III involving ester-group. If their fraction in the starting
For search of possible ways for practical use of
compounds VII as comonomer-plasticizer containing
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MAGERRAMOV et al.
Quaternization reaction of I and II with pyridine
were carried out in toluene medium. Compound I or
II (0.06 mol) was dissolved in 40 ml of toluene; this
solution was added dropwise into a flask charged with
7.1 g (0.09 mol) of the freshly distilled pyridine. The
mixture was refluxed for 5 h at 110°С. The reaction
product was precipitated. It was filtered off, washed
carefully with acetone and evacuated. Yields 70.2 (IV)
and 74.0% (V), pale yellow substances, very soluble
in water.
mixture is increased from 5 to 30%, the copolymerization
rate decreases. Total quantity of the unreacted monomers
is about 29%.
Values of a characteristic viscosity of 0.4% solutions
of copolymers in toluene are decreased from 0.45 to 0.33
by the same sequence, i.e. in the case of the growth of
the quantity of monomers VII in the initial mixture the
chain-breaking reactions intensify.
According to results of preliminary tests of the
obtained copolymers, an introduction of small amounts
of monomer VII into the polystyrene chains gives
to them the plasticizing properties (an elasticity of
film on the metal 35 mm, against 10 mm for the
polystyrene).
The compound III derivatives containing ester-
group were obtained by reaction of III with pelargonic
acid and commercial fraction of naphthene acids in
acetone in the presence of triethylamine as HBr acceptor
at room temperature. To 10.1 g (0.1 mol) of triethylamine
dissolved in 20 ml of acetone was added pelargonic acid to
a weak-acidic medium. This stirred mixture was added to
a solution of 13.45 g (0.05mol) of compound III in 60 ml
of acetone and was maintained at room temperature for
5 h. This solution was filtered off from triethylammonium
bromide and diluted with 100 ml of the distilled water to
form a precipitate. The latter was dissolved into benzene
and washed carefully with aqueous solution of 5% sodium
bicarbonate to neutral medium. Benzene solution was
dried over anhydrous sodium sulfate, concentrated and
distilled to form 1-(4-isopropenylphenoxy)butylpelargo-
nate VI as a transparent viscous pale yellow substance.
Yield 73.4%.
Hence, the conducted researches allow conclusion
that the compounds I–III containing bromine atom
and isopropenyl group may be used as semi-products
for realization of various chemical transformations for
preparation new chemically important products with
useful properties.
EXPERIMENTAL
1
The Н and 13С NMR spectra were recorded on a
Bruker 300 spectrometer (operating frequency 300 and
75 MHz respectively, internal standard TMS. IR spectra
were registered on a Varian 3600 FT-IR spectrometer.
Compounds I–III. Potassium 4-isopropenylphenolate
obtained by the reaction of 0.1 mol of 4-IP with 0.1 mol
of KОН alcohol solution, at 80°C was added dropwise
to 0.15 mol of dibromo-С2–С4-alkane containing several
grains of KI as promoter. The weight ratio KОН :
isopropanol was 1 : 20. This mixture was stirred at the
same temperature for 0.5 h. In the course of reaction the
white crystalline precipitate of di(4-isopropenylphenoxy)-
С2–С4-alkane was formed along with a side inorganic salt.
The target compound 1-(4-isopropenylphenoxy)bromo-
С2–С4-alkane I–III remained in the isopropanol solution.
It was extracted from alcohol by treatment with distilled
water. In this case viscous pale yellow mass formed. It was
dissolved into benzene and washed with water to neutral
reaction. Benzene and unreacted dibromo-С2–С4-alkane
were evaporated. Compounds I–III were extracted with
hexane to remove admixtures. Yields of compounds I–III
were 31.6, 51.8, and 64.2%, respectively. They are white
substances, very soluble in acetone, benzene, CCl4 and
alcohols, mp 32, 35 and 37°С, respectively.
The product III derivative VII with ester group
was obtained under the found conditions using III
and commercial fraction of naphthene acids (bp 150–
170°С/15 mm Hg) in yield of 68%; d20 971.8 kg m–3,
nD20 1.4935.
1-(4-Isopropenylphenoxy)-2-bromoethane (I).
1H NMR spectrum (DMSO-d6, δ, ppm): 2.08 s (3Н,
СН3), 3.78 t (2Н, СН2Вr), 4.32 t (2Н, СН2О), 4.99 and
5.35 s (2Н, =СН2), 6.93 and 7.45 d (4Н, Ar). 13С NMR
spectrum (DMSO-d6, δ, ppm): 23.4, 33.2, 68.4, 112.8,
114.7, 127.4, 138.6, 143.5, 157.8.
1-(4- Isopropenylphenoxy)-3-bromopropane (II).
1Н NMR spectrum (ССl4, δ, ppm): 2.1 s (3Н, СН3), 2.3 m
(2Н, СН2), 3.38 t (2Н, СН2Вr), 4.19 t (2Н, СН2О), 4.97
and 5.2 s (2Н, =СН2), 6.85 d (2Н, Ar), 7.35 d (2Н, Ar).
13С NMR spectrum (ССl4, δ, ppm): 22.8, 27.5, 34.3, 67.9,
112.5, 115.2, 128.5, 135.4, 144.3, 156.7. IR spectrum, ν,
(cm–1): 2960, 2871, 1471, 1384, 743 (CH3; CH2); 827
(1,4–Ar); 1255, 1030 (Ph–O–C); 1645, 887 (C=CH2);
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SYNTHESIS OF 1-(4-ISOPROPENYLPHENOXY)-BROMO-С2–С4-ALKANES
1875
549 (С–Вr).
1-(4- Isopropenylphenoxy)-4-bromobutane (III).
activity was estimated by determining of suppression
degree of SRB growth by the known procedure [9].
Accumulating cultures isolated from oil stratal water (sea
petroleum deposit Gyuneshli) were used in the study.
1Н NMR spectrum (ССl4, δ, ppm): 1.88–2.1 m (4Н,
2СН2), 2.12 s (3Н, СН3), 3.42 t (2Н, СН2Вr), 3.95 t (2Н,
СН2О), 4.92 and 5.22 s (2Н, =СН2), 6.75 d (2Н, Ar),
7.31 d (2Н,Ar). 13С NMR spectrum (ССl4, δ, ppm): 21.9,
27.5, 28.8, 32.4, 66.6, 110.5, 113.4, 126.5, 134.6, 142.2,
145.1, 156.9. IR spectrum, ν, (cm–1): 2944, 2873, 1473,
1385, 744 (СН3; СН2); 1646, 886 (С=СН2); 3041, 1575,
1473, 837 (Ar); 1247, 1043 (С–О–С); 548 (С–Вr).
Some quantity of the tested reagent was added into
produced water and was kept for 24 h at 32°С. Further the
samples by 12 ml were taken and charged into bottles
with the Postgate nutrient medium, which also were
kept for a long time (15 days) at 32°С. Hydrogen sulfide
content was determined at the end of the experiment.
Experiments with samples without reagents, inhibitors,
were conducted under the same conditions to compare.
An efficiency of sulfate-reduction was evaluated by the
samples darkening and the suppression degree of SRB
growth.
1-(4- Isopropenylphenoxy)ethyl-N-pyridinium
bromide (IV). 1Н NMR spectrum (D2О, δ, ppm): 1.79 s
(3Н, СН3), 2.47 m (2Н, СН2) 4.36 t (2Н, ОСН2), 4.75 and
5.05 s (2Н, =СН2), 4.9 t (2Н, NCH2), 6.94 and 7.38 d (4H,
arom.), 8.27, 8.75 and 9.55 (5 H, Py). 13С NMR spectrum
(ССl4, δ, ppm): 21.7, 29.7, 61.2, 67.6, 110.1, 114.9, 126.9,
127.4, 124.8, 142.8, 144.3, 146.4, 157.2.
Inhibiting properties of compounds IV and V were
examined in the system containing 3% NaCl aqueous
solution and white spirit (the ratio 7 : 1 vol.) saturated
with hydrogen sulfide (500 mg l–1). These researches
were performed by gravimetric method in a dynamic
mode at 25°С.
1-(4- Isopropenylphenoxy)propyl-N-pyridinium
1
bromide (V). Н NMR spectrum (D2О, δ, ppm): 1.79
s (3Н, СН3), 4.35 t (2H, ОCH2), 4.75 and 5.05 s (2Н,
=СН2), 4.78 t (2Н, NCH2), 6.7 d (2H,Ar), 7.15 d (2Н,Ar),
7.79 t (2Н, Py), 8.35 t (1 H, Py), 8.8 d (2H, Py). 13C NMR
spectrum (ССl4, δ, ppm): 21.7, 61.8, 66.7, 111.9, 114.5,
127.3, 128.4, 134.4, 142.6, 146.2, 156.8.
CONCLUSIONS
(1) 1-(4-Isopropenylphenoxy)-2-bromethane,
1-(4-isopropenylphenoxy)-3-bromopropane and 1-(4-
isopropenylphenoxy)-4-bromobutane were obtained
by reaction of 4-isopropenylphenol with α,ω-dibromo-
С2–С4-alkanes in yield of 31.5, 51.8 and 64.2%
respectively.
1-(4- Isopropenylphenoxy)butylpellargonate (VI).
1Н NMR spectrum (ССl4, δ, ppm): 0.89 t (3Н, СН3),
1.25 m (10Н, 5СН2), 1.59 m (2Н, СН2), 2.09 m (4Н,
2СН2), 2.1 s (3Н, СН3), 2.25 t (2Н, СН2–С=О), 3.93 t
(2Н, СН2О), 4.12 t (2Н, СН2О), 4.92 and 5.23 s (2Н,
=СН2), 6.78 d (2Н, Ar), 7.32 d (2Н, Ar). 13С NMR
spectrum (ССl4, δ, ppm): 14.1, 21.9, 22.6, 25.2, 25.7,
27.4, 28.8, 29.3, 30.9, 34.6, 61.2, 66.7, 111.3, 114.8,
126.7, 134.8, 142.7, 156.8, 164.8.
(2) On the basis of the reaction with pyridine and
organic acids was prepared number of the new compounds
containing in the structure multiple С=С bond and
nitrogen atom or multiple bond С=С and ester group
simultaneously.
In the IR spectrum of compound VII following
characteristic bands were found (cm–1): 3050, 2944,
2880, 1456, 1376, 744 (CH3; CH2); 1648, 884 (C=CH2);
3045, 1584, 1492, 832 (Ar); 1248, 1084, 1043 (C–O–C);
1740 (С=О). They confirm that esterification product
was formed.
(3) Compounds with multiple bond С=С and
nitrogen atom possess high protective properties and can
be used as inhibitors of hydrosulfuric corrosion of steel.
Compounds containing multiple bond С=С and ester
group may be used as plasticizing monomers for styrene
polymers.
Copolymers structures were also determined using IR
spectra containing characteristic absorption bands (cm–1):
2972, 2850, 1452, 1375, 756 (CH3; CH2); 3060, 1583,
1492, 827, 756, 695 (Ar); 1245, 1068, 1028 (C–O–C);
1734 (С=О).
REFERENCES
1. German Patent 19946136.
2. US Pattent 6767687.
Compounds IV and V were tested as corrosion
inhibitors for steel St.3 in aggressive media containing
H2S, SRB, salts and others substances. The bactericide
3. US Pattent 6899989 USA.
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MAGERRAMOV et al.
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