Regioselectivity of the methanolysis of polychlorinated biphenyls

Article abstract of DOI:10.1134/S1070363216100121

Regioselectivity of the methanolysis of lower polychlorinated biphenyls with sodium methoxide in a mixture of methanol and DMSO at 100–130°С was studied. It was found that 2,4,4'-tricholobiphenyl is much more reactive than 2,4-dichlorobiphenyl. This results in different mechanisms of substitution. 2,4-Dichlorobiphenyl reacts with sodium methoxide by the elimination–addition mechanism to form four monosubstitution products in comparable quantities. 2,4,4'-Trichlorobiphenyl reacts with the methodixe ion by the classical SNAr mechanism, with preferential substitution of the 2-chlorine atom.

Full text of DOI:10.1134/S1070363216100121

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 10, pp. 2318–2324. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © T.Sh. Khaibulova, I.A. Boyarskaya, V.A. Polukeev, V.P. Boyarskii, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86,
No. 10, pp. 1670–1677.
Regioselectivity of the Methanolysis of Polychlorinated Biphenyls
T. Sh. Khaibulovaa, I. A. Boyarskayaa, V. A. Polukeevb, and V. P. Boyarskiia*
a St. Petersburg State University, Universitetskaya nab. 7–9, St. Petersburg, 199034 Russia
*e-mail: v.boiarskii@spbu.ru
b Institute of Experimental Medicine, St. Petersburg, Russia
Received August 4, 2016
Abstract—Regioselectivity of the methanolysis of lower polychlorinated biphenyls with sodium methoxide in
a mixture of methanol and DMSO at 100–130°С was studied. It was found that 2,4,4'-tricholobiphenyl is much
more reactive than 2,4-dichlorobiphenyl. This results in different mechanisms of substitution. 2,4-Dichloro-
biphenyl reacts with sodium methoxide by the elimination–addition mechanism to form four monosubstitution
products in comparable quantities. 2,4,4'-Trichlorobiphenyl reacts with the methodixe ion by the classical SNAr
mechanism, with preferential substitution of the 2-chlorine atom.
Keywords: polychlorinated biphenyls, aromatic nucleophilic substitution, regioselectivity, methanolysis
DOI: 10.1134/S1070363216100121
The vigorous progress of chemical industry in the
middle of the XX century has raised the problem of
liquidation of persistent organic pollutants (POPs) which
are a threat to human health and the environment. The
initial list of POPs in the Stockholm Convention put in
force in 2001 [1, 2] comprised 12 substances,
including polychlorinated biphenyls (PCBs).
nucleophilic substitution of chlorine atoms: car-
bonylation to form biphenylcarboxylic acids and their
salts and esters, hydrolysis, and alcoholysis [9]. It
however should be noted that if the mechanism and
regioselectivity of the carbonylation of these aromatic
halides are studied to sufficient detail [11–13],
research works on their solvolysis have been mainly
focused on applied issues [14–17]. It has not been until
recently that Gorbunova et al. [18, 19] have made an
attempt to describe the reactivity of some PCB
congeners toward methoxide anion, but the results of
the cited works give no more than a general view of
the reactivity of the studied compounds in this reaction
and allow no conclusions on its regioselectivity and
mechanism.
Commercial PCBs are complex mixtures including
50−70 individual compounds differing from each other
by the number and positions of chlorine substituents
(congeners and isomers). Due to their unique
physicochemical properties, PCBs have found wide
application in industry [3]. According to international
treaties, all PCB uses should be ceased by 2025, and
complete environmentally sound management of PCBs
should be achieved by 2028. At present a lot of effort
is being devoted to the decontamination of PCB-
contaminated wastewater and soil by microbial de-
gradation [4–7] and by oxidative degradation under the
action of light, air oxygen, and peroxides in the
presence of iron ions [8]. However, no reasonable
technology for the utilization of hundreds of thousands
of tons of PCBs still stored in stockpiles is available
[9, 10]. Therefore, research into ways of PCB pro-
cessing remains urgent.
A convenient method to study the mechanism of
reactions involving PCBs is to determine the reactivity
in such reactions of PCB congeners containing no
more than 2 chlorine substituents in each phenyl ring.
This approach we previously used to success in
studying radical anion reactions of PCBs [11–13, 20–
22] (including carbonylation which, too, occurs by the
mechanism of radical anion nucleophilic substitution
[13, 23]). Therefore, to gain insight into the
regularities of the base-catalyzed solvolysis of PCBs,
we have studied the regioselectivity of the metha-
nolysis of two lower PCB congeners: 2,4-di-chloro-
One of the most perspective approaches to the
utilization of PCBs involves their functionalization via
2318

2319
REGIOSELECTIVITY OF THE METHANOLYSIS OF POLYCHLORINATED BIPHENYLS
Scheme 1.
Cl
MeO
Cl
NaOMe
Cl
X
X
DMSO−MeOH
100–130oC
1, 2
X = H (1), Cl (2).
Scheme 2.
Cl
Cl
[Pd]
+
Cl
I
(HO)2B
X
Cl
X
K2CO3
EtOH
80oC
1, 2
3
4, 5
Cl
Cl
C
HN C6H4-4-NO2
(6),
X = H (1, 4), Cl (2, 5).
[Pd]:
Pd
NH
C
N
NH
Cy
Cy
biphenyl (1) and 2,4,4'-trichlorobiphenyl (2) (Scheme 1).
The reaction was performed until incomplete conver-
sion so that to determine what of the monosubstitution
products is a major product.
commercial PCB mixtures and, therefore, presents a
greater interest, we first of all focused on the
regioselectivity of the methanolysis of this compound.
GC‒MS analysis of the reaction mixture showed that
at a 95% conversion the major reaction products are
two isomeric dichloromethoxybiphenyls 7 and 8 (2 : 1).
Along with them, minor amounts (<1%) of chloro-
dimethoxybiphenyl and about 6% of hydrolysis pro-
ducts (phenols) are formed.
Individual congeners 1 and 2 required for this work
were synthesized by the Suzuki reaction [24] from 2,4-
dichloroiodobenzene (3) and corresponding aryl-
boronic acids 4 and 5 (Scheme 2). As the catalyst in
these reactions we used the previously synthesized
acyclic diaminocarbene palladium complex 6 [25–27].
Isomeric dichloromethoxybiphenyls 7 and 8 were
Methanolysis was performed by the procedure
proposed in [15] using as the solvent a boiling MeOH–
DMSO mixture at 100–130°С. Since the process was
carried out at atmospheric pressure, a mixture of 3 М
methanolic NaOMe and DMSO (1 : 2 v/v) was
preliminarily partially evaporated until the bottom
temperature reached the desired point. The conversion
of the starting substrates as different temperatures was
determined by GLC with internal standard (aceta-
phthene or 1,4-di-tert-butylbenzene). The resulting
data are listed in Table 1.
both isolated and separated by column chromato-
1
graphy. One-dimensional H and 13С NMR spectro-
scopy did not allow unequivocal structural assessment
of these products; the only conclusion that could be
drawn from these data is that both products are formed
by substitution of one chlorine atom by MeO in the
more substituted phenyl ring. At the same time, using
NOESY NMR spectroscopy we could determine the
structure of these products to obtain evidence for the
preferential formation of ortho-methoxy-substituted
isomer 7 (Scheme 3). To confirm the structure of
product 8, we obtained it by independent synthesis
(Scheme 4).
As seen from the data in Table 1, both congeners
react under the used conditions. As would be expected,
2,4,4'-trichlorobiphenyl (2) is more reactive than 2,4-
dichlorobiphenyl (1).
The spectral data of the synthesized compound and
its GLC retention time were coincident with the res-
pective parameters of isomer 8, which gave evidence
for the correctness of the structural assessment of the
Taking into account that congener 2, unlike
dichlorobiphenyl 1, is one of the components of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 10 2016

2320
KHAIBULOVA et al.
Table 1. Dependence of the conversion of of congeners 1
and 2 on reaction time and temperature
Congener 1 reacts with sodium methoxide in quite
a different way. GC‒MS analysis of the sample of the
reaction mixture, taken when the conversion had
reached 97%, revealed the presence of four rather than
two isomeric products with the brutto formula
C13H11ClO (products М1–М4, Table 2), which are the
major reaction products and formed by the substitution
of one chlorine atom by MeO. The М1–М4 products
are formed in comparable quantities.
Substrate
Т, °С
110
120
130
100
110
110
110
Time, h
Conversion, %a
1
1
1
2
2
2
2
5
5
5
1
1
2
8
0
0
97
18
31
42
95
This unexpected fact can be explained by a change
of the substitution mechanism in this case. As we
already mentioned, congener 1 is much less reactive
than congener 2, as the second phenyl ring in the
former is less acceptor and, therefore, may prove
insufficiently activated for the realization of the SNAr
mechanism. Moreover, the reaction with the less active
congener 1 required that the temperature is raised by
20°С. This in itself makes the reaction conditions
harsher, but, what is more, the higher temperature
decreases the МеОН/DMSO ratio in the reaction
mixture and, therefore, increases the basicity of the
methoxide ion. Harsher conditions increase the
probability that the aromatic nucleophilic substitution,
instead of following the SNAr mechanism, will involve
take the way of cine substitution involving inter-
mediate formation of dehydrobenzene [28]; in the
latter case, the incoming nucleophile can occupy not
a By GLC.
isomeric products formed by the methanolysis of
congener 2.
The observed regioselectivity can be explained in
terms of the SNAr mechanism. We suggested that the
reason of the higher reactivity of the ortho position in
this case lies in the higher stability of the corres-
ponding Meisenheimer complex (intermediate 14)
compared to intermediate 15 (Scheme 5). The higher
stability of intermediate 14 is associated with its more
planar geometry, which allows a greater involvement
of the second phenyl ring in the delocalization of the
negative charge and the stabilization of the anion.
Scheme 3.
Cl
Cl
8 (30%)
Cl
OMe
NaOMe
+
Cl
Cl
Cl
MeO
Cl
Cl
DMSO−MeOH
110oC
2
7 (58%)
Scheme 4.
N2+
MeO
HO
Cl
HO
Cl
CH3I
N
N
N
N
K2CO3
NaOH
DMF
45oC
11 (85%)
9
10 (90%)
Cl
(1) HCl
NaNO2
(HO)2B
Cl
MeO
Cl
MeO
Cl
I
H2 (20 bar)
MeO
Cl
(2) KI
Ni, 60oC
6, K2CO3, EtOH, 80oC
NH2
12 (65%)
13
8 (96 %)
(45%)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 10 2016

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REGIOSELECTIVITY OF THE METHANOLYSIS OF POLYCHLORINATED BIPHENYLS
Table 2. Composition of the mixture of the methanolysis
products of congener 1a
only the position of the leaving groups but also the
neighboring positions. Therefore, it is not surprising
that the methanolysis of congener 1 gives rise to four
monosubstitution products, since hydrogen is more
likely eliminated from the 3position in view of its
higher acidity (Scheme 6).
Concentration in the
Product
Brutto formula
mixture, %b
М1
М2
М3
М4
М5
М6
М7
C13H11ClO
C13H11ClO
C13H11ClO
C13H11ClO
C14H14O2
13
12
9
Thus, in the present work we found that lower PCB
congeners can undergo methanolysis in a solution of
sodium methoxide in a methanol–DMSO mixture at
100–130°С. As would be expected, the more chlo-
rinated 2,4,4'-trichlorobiphenyl is appreciably more
reactive than 2,4-dichlorobiphenyl, and, as a result,
these compounds react by different mechanisms. 2,4-
Dichlorobiphenyl reacts with sodium methoxide by the
elimination–addition mechanism to form four mono-
substitution products in comparable quantities. 2,4,4'-
Trichlorobiphenyl reacts with the methoxide anion by
the classical SNAr mechanism with preference for
chlorine substitution in the 2 position. The possible
reason for the observed regioselectivity is a higher
planarity of the intermediate Meisenheimer complex
14 compared to the parent biphenyl 2.
15
6
C12H9ClO
C12H9ClO
28
14
а 130°С, reaction time 5 h, conversion of 1 97%. b By GC‒MS.
performed on a Khromatek Kristal 5000.2 instrument
[flame ionization detector, column Optima (1.25 m ×
0.32 mm × 0.35 µm)].
2-Chloro-4-hydroxyazobenzene (10) was pre-
pared by the procedure in [29], yield 90%, mp 112–
1
114°С (ethanol). Н NMR spectrum, δ, ppm: 5.65 s
(1H, OH), 6.82 d.d (1H, J = 8.9, 2.5 Hz), 7.07 d (1H,
J = 2.5 Hz), 7.38–7.62 m (3H), 7.76 d (1H, J =
8.9 Hz), 7.91–8.00 m (2H).
EXPERIMENTAL
Commercial (Aldrich) starting materials and solvents
were used as received.
2-Chloro-4-methoxyazobenzene (11). A mixture
of 0.2 mol of compound 10, 0.42 mol of К2СO3,
0.24 mol of MeI, and 120 mL of DMF was stirred at
45–50°С for 3 h. After cooling to room temperature,
the mixture was diluted with 200 mL of water and
stirred until the oil that formed solidified. The
precipitate was filtered off, washed with water, dried,
and recrystallized. Yield 85%, mp 55–57°С (MeOH–
1
The H and 13С NMR spectra were measured on a
Bruker Avance II+ spectrometer [400.13 (1Н),
100.61 МHz (13C)] at room temperature, solvent СDCl3.
Gas chromatography‒mass spectrometry was per-
formed on a Shimadzu GCMS QP-2010 SE instrument
(electron ionization, 70 eV, scan range m/z 35–500, ion
source temperature 200°С, column Rtx-5MS (30 m×
0.32 mm×0.25 µm), carrier gas argon (flow rate
0.8 mL/min); oven temperature program 50°C, 2 min,
25 deg/min, 250°C, 20 min). Gas chromatography was
1
H2O). Н NMR spectrum, δ, ppm: 3.91 s (3H, OСH3),
6.90 d.d (1H, J = 9.0, 2.7 Hz), 7.11 d (1H, J = 2.7 Hz),
7.45–7.58 m (3H), 7.81 d (1H, J = 9.0 Hz), 7.92–8.03
m (2H).
Scheme 5.
Cl
Cl
Cl
Cl
Cl
+ −OMe
+ −OMe
– Cl−
– Cl−
Cl
Cl
OMe
OMe
Cl
Cl
Cl
Cl
Cl
OMe
OMe
Cl
15
7
2
8
14
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 10 2016

2322
KHAIBULOVA et al.
Scheme 6.
base
– HCl
base
– HCl
Cl
Cl
Cl
Cl
1
+ −OMe
+ H+
+ −OMe
+ H+
Cl
Cl
OMe
+
+
OMe
OMe
Cl
OMe
Cl
2-Chloro-4-methoxyaniline (12) [30]. A mixture
of 0.12 mol of compound 11, 250 mL of propan-2-ol,
and Raney nickel was hydrogenated at 60°С in a
stainless-steel autoclave under a hydrogen pressure of
20 bar for 1 h. The resulting solution of filtered to
remove the catalyst, the solvent was evaporated, and
the residue was distilled in a vacuum, and the fraction
110–130°С (20 mmHg) was collected. This fraction
was distilled again to collect the product boiling at 128–
NMR spectrum, δ, ppm: 3.80 s (3H, OCH3), 6.59 d.d
(1H, J = 8.8, 2.9 Hz), 7.04 d (1H, J = 2.9 Hz), 7.68 d
(1H, J = 8.8 Hz).
Synthesis of PCB congeners 1 and 2 and
chloromethoxybiphenyl 8 by the Suzuki reaction. A
2×10–3 М solution of complex 6 [27] in 8×10–7 mol of
ethanol (0.4 mL) was added with stirring to a hot (80°С)
mixture of 5–10 mL of ethanol, 1.0–3.0 mmol of aryl
iodide, 1.1 equiv of arylboronic acid, and 1.5 equiv of
K2СО3. The reaction mixture was heated on an oil bath
at 80°С for 2 h and then cooled to room temperature
and diluted with 10 mL of water. The reaction product
was extracted with a hexane‒dichloromethane mixture
(5 : 1, 3×20 mL), the organic layer was dried over
anhydrous Na2SO4, the solvent was evaporated, and
the residue was weighed and analyzed by 1H NMR and
GLC. When necessary, the product was additionally
purified by column chromatography (eluent hexane).
1
130°С (20 mmHg). Yield 65%. Н NMR spectrum, δ,
ppm: 3.75 s (3H, OСH3), 6.69–6.73 m (2H), 6.88 d.d
(1H, J = 1.8, 1.2 Hz).
3-Chloro-4-iodoanisole (13) [31]. To 80 mmol of
compound 12 we added in succession 40 mL of water
and 20 mL of conc. HCl. The suspension that formed
was cooled on an ice bath, after which a solution of
85 mmol of NaNO2 in 40 mL of water was added to it
under stirring over the course of 1 h. The solution was
stirred for 15 min, and urea was then added until
nitrogen no longer evolved. The resulting diazonium
salt solution was added in small portions to a stirred
solution of 120 mmol of KI in 40 mL of water at 0–5°С.
To bring the reaction to completion, the mixture was
heated at 60°С for 10 min, cooled, 20% NaOH was
then added, and the product was extracted with
dichloromethane (3×50 mL). The organic layer was
successively washed with 5% NaHSO3 (50 mL) and
water (50 mL), dried over MgSO4, and distilled in a
2,4-Dichlorobiphenyl (1) [32] was prepared from
1.0 mmol of 2,4-dichloro-1-iodobenzene. Yield
1
138 mg (62%), light yellow oily liquid. Н NMR
spectrum, δ, ppm: 7.29−7.49 m (7H), 7.52 d (1H, Н3,
J = 1.2 Hz). Mass spectrum, m/z (Irel, %): 222 (100)
[М]+, 152 (75) [M – 2Cl]+.
2,4,4'-Trichlorobiphenyl (2) [33] was prepared
from 3.0 mmol of 2,4-dichloro-1-iodobenzene. Yield
1
495 mg (73%), light yellow solid, mp 88°С. Н NMR
1
spectrum, δ, ppm: 7.26 d (1H, J = 8.4 Hz), 7.32 d.d
vacuum. Yield 45%, mp 136–138°С (20 mmHg). Н
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REGIOSELECTIVITY OF THE METHANOLYSIS OF POLYCHLORINATED BIPHENYLS
(1H, J = 8.4, 2.1 Hz), 7.36 d (2H, J = 9.1 Hz), 7.43 d
(2H, J = 9.1 Hz), 7.52 d (1H, J = 2.1 Hz).
133.23, 134.35, 135.92, 156.94. Mass spectrum, m/z
(Irel, %): 252 (100) [М]+, 202 (95) [M – Cl – Me]+.
2,4'-Dichloro-4-methoxybiphenyl (8) [34] was
prepared from 1.0 mmol of 2-chloro-1-iodo-4-meth-
oxybenzene 13. Yield 242 mg (96%), white solid, mp
92–94°С. 1H NMR spectrum, δ, ppm: 3.86 s (3H), 6.90
d.d (1H, J = 2.6 Hz), 7.05 d (1H, J = 2.5 Hz), 7.25 d
2,4'-Dichloro-4-methoxybiphenyl (8). Yield 41 mg
(34%), white crystals. The analytical data are
coincident with respective characteristics of sample 8
obtained by independent synthesis.
13
ACKNOWLEDGMENTS
(1H, J = 8.5 Hz), 7.33−7.45 m (4H). C NMR spec-
trum, δС, ppm: 55.60, 113.17, 115.23, 128.15, 128.23,
130.94, 131.74, 132.94, 133.32, 137.58, 159.60. Mass
spectrum, m/z (Irel, %): 252 (100) [М]+, 237 (40) [M –
Me]+, 209 (30).
The PCB methanolysis study was financially sup-
ported for the St. Petersburg State University (project
no. 12.37.214.2016). The synthesis of individual PCB
congeners and the independent synthesis of one of the
methanolysis products were performed under funding
of the Russian Science Foundation (project no. 14-43-
00017). The research was performed using the
equipment of the Resource Center for Magnetic
Resonance Research and the Educational Resource
Center of Chemistry, St. Petersburg State University.
Methanolysis of PCB congeners. A tube with a
screw cap was charged with 1 mL of a 3 М solution of
NaOMe in 2 mL of methanol and DMSO, and the
mixture was partially evaporated with stirring on an oil
bath until the bottom temperature reached a desired
temperature (100–130°С). Congener 1 or 2 and
corresponding standard for GCL quantification (aceta-
phthene or 1,4-di-tert-butylbenzene, respectively) were
then added to a cooled reaction mixture, after which it
was heated with stirring at a desired temperature for a
required time period. After cooling and adding 1 mL of
1 М НCl, the reaction products were extracted with a
hexane–dichloromethane mixture (5 : 1, 3×2 mL), and
the organic layer was dried over anhydrous Na2SO4
and analyzed by GC‒MS.
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