A highly selective synthetic method for distyrenated phenol

Article abstract of DOI:10.1166/jnn.2017.13350

Styrenated phenol is an antioxidant synthesized by catalytic reaction of a Bronsted acid and Lewis acid Composition ratio of compound varies based on the amounts source material and catalyst. In this study the composition of the styrenated phenol of monomer, dimer, trimer product synthesized by designing on experiment for increasing selectively. These styrenated phenol were analyzed using a MALDI-TOF MS, FT/IR Spectrometer, ¹H(¹³C)-NMR, and Gas Chromatography (GC).

Full text of DOI:10.1166/jnn.2017.13350

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Nanoscience and Nanotechnology
Vol. 17, 2703–2706, 2017
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A Highly Selective Synthetic Method for
Distyrenated Phenol
Seokhwan Son1, Jinhyun Kim1, Hogeun Ahn1, Mikyeong Jang2, Wonbong Kwak3,
Sunghun Jung3, and Minchul Chung1ꢀ∗
1Department of Chemical Engineering, Sunchon National University, Sunchon, Jeonnam 540-742, Korea
2Department of Polymer Engineering, Sunchon National University, Sunchon, Jeonnam 540-742, Korea
3SFC. Co., Ltd., 342-42, Yesusandan 1-ro, Yeosu-si, Jeollanam-do, 550-280, South Korea
Styrenated phenol is an antioxidant synthesized by catalytic reaction of a Bronsted acid and Lewis
acid Composition ratio of compound varies based on the amounts source material and catalyst.
In this study the composition of the styrenated phenol of monomer, dimer, trimer product synthesized
by designing on experiment for increasing selectively. These styrenated phenol were analyzed using
a MALDI-TOF MS, FT/IR Spectrometer, 1H(13C)-NMR, and Gas Chromatography (GC).
Keywords: Styrenated Phenol, Antioxidant, Selectivity.
IP: 94.158.23.195 On: Tue, 15 Jan 2019 02:49:50
Copyright: American Scientific Publishers
1. INTRODUCTION
molecular weight better in synthesizing a surfactant than
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mono- or tri-styrenated phenol do. The conventional way
to synthesize DSP has low selection ratio, contains high
mono-styrenated phenol content, and has a possibility to
cause the yellowing of styrenated phenol due to residual
phenol. Therefore, it is required to seek a new synthesis
method using a new catalyst, which will minimize residual
phenol and increase the selection ratio of DSP.
The oxidative aging of rubbers and resin are one of the
most important problems in rubber and resin technology
because the absorption of a small amount of oxygen causes
a considerable changes in their physical and mechanical
properties.1 Such changes can be retarded but not com-
pletely overcome by the addition of antioxidants. The most
common antioxidants are derivatives of aromatic amines
and phenols. Phenol antioxidants are effective stabilizers
that provides excellent long-term heat stability by pre-
venting thermo-oxidative degradation process and service
life.
Styrene phenol is generally synthesized with using
Bronsted acid and Lewis acid catalyst. When styrene
monomer and phenol are reacted under Bronsted acid and
Lewis acid catalyst, mono-, di-, and tri-styrenated phe-
nol compounds are produced.2 These compounds have
different anti-oxidant properties and physical characteris-
tics (e.g., viscosity). Therefore, it is necessary to selec-
tively control the reaction according to the purpose of the
compounds.
In this study the composition of the styrenated phenol
of monomer, dimer, trimer product synthesised by design-
ing on experiment for increasing the amount of selec-
tively. In this study, styrenated phenols of monomer, dimer,
and trimer prod-ucts were synthesized for for increasing
selectively. Reaction of phenol with styrene in the pres-
ence of catalyst yields the mixture of mono-, di-, and
tri-styrenated phenol. We are Di-styrenated phenol (DSP)
from the configuration of the styrenated phenol were
synthesized. Were the Bromination of phenol to selec-
tively synthesize the DSP. Were synthesized DSP by using
a Suzuki-Miyaura coupling using a 2,6-Dibromophenol.
Suzuki-Miyaura coupling is one of the most used cou-
pling reactions for C–C bond formation, mostly due to
the wide variety and accessibility of the starting mate-
rials, as well as the mild reaction conditions used.3
Therefore, DSP synthesis in the Suzuki-Miyaura cou-
pling was used. Finally, was evaluated by analyzing
product.
Among these compounds, Styrenated Phenol alkoxy-
late shows excellent performance as a surfactant. The
Styrenated Phenol alkoxylate (SP-A) is synthesized with
epoxy by using DSP. It is because the DSP controls
∗Author to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2017, Vol. 17, No. 4
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doi:10.1166/jnn.2017.13350
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A Highly Selective Synthetic Method for Distyrenated Phenol
Son et al.
rate, 94 mL/min; ion trap pressure, 1ꢁ8 × 10−2 Pa; col-
lision gas (Ar) flow rate, 43 mL/min; ion accumulation
time, 10 ms; precursor ion selected width, 3.0 m/z units,
and the selected time, 20 ms. MS data was acquired by
using the data-dependent function. Reactant and prod-
uct mixture analyzed by using the gas chromatography
(HP-6890, Hewlett-Packard) with a flame ionization detec-
tor, in which capillary column, HP-5 (30 m ∗ ꢂ0ꢁ32 mm
0.25 ꢃm).
2.2. Synthesis of 2,6-Dibromophenol (1a)
To
a solution of phenol (1.5 g, 16 mmol) in
dichloromethane (10 mL) was added a solution of
N ,N -diisopropylamine (0.44 mL, 3.1 mmol). To this mix-
ture was added a solution of N -brom-osuccinimide (5.7 g,
32 mmol) in dichlor-omethane (150 mL), dropwise over
3 h. After stirring for 1h at room temperature, aque-
ous hydrochloric acid (1M) was added until the solu-
tion became acidic. The organic layer was washed with
water (80 mL), dried over sodium sulfate and concen-
trated in vacuo to produce a colourless residue. The resul-
tant residue was purified by flash column chromatography
using hexanes as eluent, affording the title compound (1a)
as colorless crystals (Yield: 72%).
Figure 1. Synthesis
of
compounds
3.
(a)
CH2Cl2,
N,N-diisopropylamime, N-bromosuccinimide (yield: 72%), (b) THF,
n-BuLi, trimethyborate. (Yield: 58%), (c) Pd (PPh3ꢀ4, K2CO3 in H2O,
EtOH, THF (yield: 77%).
2. EXPERIMENTAL DETAILS
A synthetic strategy for the synthesis of compound 3 is
outlined in Figure 1.
2.1. First Experiment
1H-NMR (400 MHz, CDCl3ꢀꢄ: 5.88 (s, 1H), 6.70 (t, 1H,
J = 8 Hz), 7.45 (d, 2H, J = 8ꢁ4 Hz); 13C-NMR (400 MHz,
CDCl3ꢀꢄ: 111.0, 122.5, 132.1, 149.5; the 1H and 13C
NMR data obtained were in agreement with that reported
in the literature.5 FT-IR(KBr, cm−1ꢀ: 3419.98, 1439.00,
1333.92, 1238.03, 1135.23, 757.65, 707.56 (C–Br).
For this experiment, N ,N -diisopropylamine, N -
bromosuccinimide and (1-bromoethyl)-benzene were
purchased from Alfa Aesar. (1-bromoethyl) benzene was
stored at a low temperature. Phenol, Butyllitium and
Trimethyl borate was purchased from Aldrich. Pd(PPh3ꢀ4
were purchased from Tokyo Chemical Industries (TCI).
K2CO3, MgSO4, CH2Cl2, HCl, THF, EtOH and Hexane
were purchased from Deajung. All solvents were purified
using the method of purification specified in Laboratory
Chemicals (Third Edition) by D. D. Perrin and W. L. F.
Armarego. All syntheses were performed using a Schlenk
tube under an argon atmosphere.
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2.3. Synthesis of Bisboronic Acids (2)
Butyl-lithium (1.6M in hexanes, 4.43 mmol) was added,
dropwise, via syringe to a stirred solution of the starting
2,6-dibromophenol (0.5 mg, 2.011 mmol) in THF (20 mL)
in a dry ice-acetone cold temperature bath. After the mix-
ture was stirred for 30 min in the cold bath, a solution of
trimethyl borate (1.254 g 12.066 mmol) was added. After
the mixture was stirred in the cold bath for 30 min, the
reaction mixture was stirred at ambient temperature for
1 h. The reaction mixture was quenched with 30 mL of
10% HCl. The product was extracted with CH2Cl2. The
product was dried with MgSO4. After dry yield the pure
product (Yield: 58%).
Analytical thin-layer chromatography (TLC) was per-
formed on Merck Alminium oxide-aluminum plates with
F-254 indicator, visualized by irradiation with UV light.
Column chromatography was performed using s Alminium
oxide Merck 90 (particle size 0.063–0.200 mm). In addi-
tion, deuterated CD3OD and CDCl3 were used as the sol-
1
vents H(13C)-NMR.
The 1H(13C)-NMR spectra were determined using
a Bruker AVANCE 400 FT-NMR spectrometer (1H,
400 MHz). A Jasco 600 series FT/IR Spectrometer (FT/IR-
6600) was used for the FT-IR spectrum analysis. The Mass
spectroscopy was carried out using the MALDI-TOF MS
(ABI 4700, Bruker Ultraflex III) at the Korea Basic Sci-
ence Institute (KBSI).
1H-NMR (400 MHz, CDCl3) ꢄ: 7.11 (t, 1H), 7.71
(d, 2H); FT-IR (KBr, cm−1ꢀ: 3382.43, 1603.13, 1273.60
(B–O), 749.64.
2.4. Synthesis of Distyrenated Phenol (3)
A degassed solution of K2CO3 (799 mg, 5.788 mmol) in
H2O (3 ml), ethanol (2 ml), and THF (28 ml) was added
to a flask containing (1-bromoethyl)benzene (535 mg,
2.89 mmol), bisboronic acid (263 mg, 1.44 mmol) and
Pd(PPh3ꢀ4 (92 mg, 0.0804 mmol) in argon gas. The mix-
ture was refluxed for 48 hr. The solvent was removed in a
The analytical conditions were as follows: scan range,
m/z 150–1500; positive spray voltage, +3.0 kV detec-
tor voltage, 1.65 kV; simmer voltage, 9.0 V; pressure of
TOF region, 1ꢁ5 × 10−4 Pa, and temperature, 40 C; ion
ꢀ
ꢀ
source temperature, 200 C; trap cooling gas (Ar) flow
2704
J. Nanosci. Nanotechnol. 17, 2703–2706, 2017

Son et al.
A Highly Selective Synthetic Method for Distyrenated Phenol
Figure 4. FT-IR spectra of 3.
The structure of the synthesized compound was ana-
Figure 2. 1H-NMR analysis of compound 3.
1
lyzed using H (13C)-NMR. Because all of the products
include the same skeleton structure, similar specta between
7.0 ppm and 9.0 ppm from the peak of aromatic proton
were observed. We were unable to obtain the 13C-NMR
data for compounds 2 because their solubility was very.
The compound 3 that are measured at H-NMR are shown
in Figure 2.
The mass spectra of 1a and 1b that are measured at ESI-
TOF MS are shown in Figure 3. In the mass spectrum, the
peak of complex 1a and 1b was observed at 273.398 and
326.453 m/z.
vacuum and the residue was dissolved in CH2Cl2, washed
with a saturated NaCl solution (50 mL), and dried over
MgSO4. The solution was concentrated and MeOH was
added, resulting in the precipitation of a white powder
from the brown solution. The resultant residue was puri-
fied by column chromatography using hexanes as eluent
afforded the title compound (3) (Yield: 77%).
1
1H-NMR (400 MHz, CD3OD) ꢄ: 6.78∼7.19 (m, 13H),
4.53 (m, 1H, J = 8 Hz), 3.93 (m, 2H, J = 7.2 Hz), 1.41 (m,
6H, J = 8.8 Hz); 13C-NMR (400 MHz, CD OD) ꢄ: 21.78,
The FT-IR spectra of 1a are shown in Figure 4. The
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−1
IR spectra of 1a shows additional peaks at 3200 cm
–
39.63, 121.41, 125.73, 126.66, 129.08, 135.17, 147.50,
148.34, 150.33; FT-IR (KBr, cm−1ꢀ: 3445.23(O–H),
1644.60, 1437.23 (aromatic ring C–C stretch), 1120.06.
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3500 cm−1 due to the presence of –OH stretching,
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1585 cm−1–1600 cm−1 corresponds to aromatic ring and
850 cm−1–515 cm−1 due to the presence of C–Br stretch-
ing. This confirms the chemical binding of phenol to
bromo.
3. RESULTS AND DISCUSSION
Were synthesized DSP by using a Suzuki-Miyaura cou-
pling. The first was a brominated phenol. In this case, 2,6-
dibromophenol (1a) are synthesized. The compounds 1a
are colorless crystals. The compound 3 are crude yellow
liquid.
The FT-IR spectra of 1a are shown in Figure 4. The IR
spectra of 1a shows additional peaks at 3382.43 cm−1 due
to the presence of –OH stretching, 1437.23 cm−1 corre-
sponds to aromatic ring. This confirms the chemical bind-
ing of compound 3.
Figure 3. Mass spectra of 1a at ESI–TOF MS.
J. Nanosci. Nanotechnol. 17, 2703–2706, 2017
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A Highly Selective Synthetic Method for Distyrenated Phenol
Son et al.
(a)
(b)
Phenl
DSP
Styrene
DSP
MSP
TSP
Figure 5. GC analysis data. (a) SP samples produced by Kumho Petrochemical. (b) Synthesis DSP.
Table I. Selectivity in accordance with catalyst.
was 77%, which was relatively high, and the conversion
rate was 75.9%. A method to synthesize SP compounds
with using an organometallic catalyst is entirely different
from the conventional method, which synthesizes SP com-
pounds with using the Bronsted acid and Lewis acid cat-
alyst. This method is able to only synthesize DSP among
SP compounds. Moreover, it can exclusively synthesize
TSP by increasing the input ratio of Br, while synthesiz-
ing 2,6-Dibromophenol. It means that we can synthesize a
desired structure among SP compounds and we can change
the composition of SP compounds by adding pure DSP and
TSP to SP compounds. These are the merit of this method.
%Yield (GC area%)
DSP
Catalyst
MSP
TSP
Method 1
Method 2
Method 3
Method 4
H2SO4
p-TSA
MSA
13ꢁ45
3ꢁ42
4ꢁ64
–
43ꢁ55
22ꢁ13
21ꢁ32
75ꢁ9
42ꢁ21
69ꢁ39
66ꢁ58
–
Pd(PPh3ꢀ4
Note: p-TSA (para-toluene sulfonic acid), MSA (methanesulfonic acid).
It was compared with the GC analysis data of a com-
mercial product, manufactured by Kumho Petrochemical
Co. Ltd. (Fig. 5(a)). An identical peak was observed from
both GC results (Fig. 5(b)), which confirmed that DSP was
synthesized.
Acknowledgment: This work was supported by
the Human Resource Training Program for Regional
Innovation and Creativity through the Ministry of
Education and National Research Foundation of Korea
MSP, DSP and TSP was measured at 8∼9.5, 13∼14,
IP: 94.158.23.195 On: Tue, 15 Jan 2019 02:49:50
and 17∼18. It was possible to confirm that the single peak
Copyright: American Scientific Publishers
emerges from 13.8 at the GC measurement of the synthe-
(NRF-2014H1C1A1066844). In addition, this paper was
supported by (in part) Sunchon National University
Research Fund in 2015.
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sized samples (Fig. 5(b)). Synthesized DSP demonstrates
a single sharp peak, indicating isomers to not be present.
The synthesis yield of DSP with utilizing an
organometallic catalyst was 77%, which was relatively
high. The synthesis Selectivity rate of DSP was com-
pared with the patent of Kumho Petrochemical Co.
Ltd. (10-2012-0127150) (Table I). Method 1, 2, and 3
shows the Selectivity rate graphs by using the cata-
lyst of Kumho Petrochemical Co. Ltd. Their Selectiv-
ity rate ranged between 21.32 and 43.55. A synthesis
with using the Pd(PPh3ꢀ4 of Method 4 had a 75.9% of
Selectivity rate. It was because byproducts were not com-
pletely removed after a synthesis and unreacted substances
remained (Fig. 5(b)). The synthesis yield was 77%.
References and Notes
1. W. L. Hawkins, Polymer Degradation and Stabilization; Verlag: Berlin
(1984); J. R. Dunn and J. Scalan, The Chemistry and Physics of Rub-
ber Like Substances; Applied Science: edited by L. Bateman, Essex,
UK (1963), p. 663.
2. N. S. Nametkin, T. G. Veretyakhina, M. V. Kurashev, G. M.
Mamedaliev, Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,
(1975), Vol. 10, p. 2268; P. S. Mamedova, V. M. Farzaliev, F. M.
Velieva, and E. R. Babaev, Neftekhimiya (2007), Vol. 47, p. 58.
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(2011).
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4. CONCLUSION
The objective of this study was to synthesize DSP among
SP compounds with using an organometallic catalyst.
The reaction condition for DSP synthesis was 48 hours
at 80ꢀ with using toluene solvent. Reaction yield rate
Received: 30 December 2015. Accepted: 15 May 2016.
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