Regularities of Pd/C-catalyzed reduction of trichlorobiphenyls with 2-propanol in basic medium

Article abstract of DOI:10.1134/S1070363217080023

Reduction of a series of trichlorobiphenyls with 2-propanol in basic medium catalyzed by Pd/C has been studied. Regioselectivity of the reduction has been determined. In the studied cases, the chlorine atom in para or meta positions of the more substituted ring has been more reactive. Using isotope labeling, it has been demonstrated that the reaction occurs via the stage of 2-propanol dehydration on palladium catalyst, followed by catalytic hydrogenation of the polychlorinated biphenyls.

Full text of DOI:10.1134/S1070363217080023

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 8, pp. 1656–1662. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © E.A. Kostenko, E.V. Eliseenkov, A.A. Petrov, 2017, published in Zhurnal Obshchei Khimii, 2017, Vol. 87, No. 8, pp. 1239–1246.
Regularities of Pd/C-Catalyzed Reduction
of Trichlorobiphenyls with 2-Propanol in Basic Medium
E. A. Kostenkoa, E. V. Eliseenkovb, and A. A. Petrovb*
a St. Petersburg State Institute of Technology (Technical University), St. Petersburg, Russia
b St. Petersburg State University, Universitetskaya nab. 7–9, St. Petersburg, 199034 Russia
*e-mail: aap1947@yandex.ru
Received June 15, 2017
Abstract—Reduction of a series of trichlorobiphenyls with 2-propanol in basic medium catalyzed by Pd/C has
been studied. Regioselectivity of the reduction has been determined. In the studied cases, the chlorine atom in
para or meta positions of the more substituted ring has been more reactive. Using isotope labeling, it has been
demonstrated that the reaction occurs via the stage of 2-propanol dehydration on palladium catalyst, followed
by catalytic hydrogenation of the polychlorinated biphenyls.
Keywords: polychlorinated biphenyls, catalytic hydrogenation, relative reactivity, regioselectivity, isotope
labeling, reduction mechanism
DOI: 10.1134/S1070363217080023
Polychlorinated biphenyls (substituted biphenyls
containing 1 to 10 chlorine atoms, С12Н10–nCln with n =
1–10) belong to the class of synthetic organochlorine
compounds. 209 known individual polychlorinated
biphenyls (congeners) are different in the number and
positions of chlorine atoms in the biphenyl structure.
Commercial biphenyls are complex mixtures of 50–70
congeners. They have been recognized for a set of
unique physicochemical properties such as thermal
stability, resistance to oxidation, poor solubility in
water, and good solubility in hydrocarbons and fats,
due to which polychlorinated biphenyls are widely
used in many industrial fields [1–3].
concentrated polychlorinated biphenyls remains an
open issue. Their transformation into safer chemicals
has been found advantageous over combustion. The
transformation methods include nucleophilic substitu-
tion of chlorine atoms with hydroxyl or alkoxy groups
[5–11], carbonylation affording diphenylpolycarbo-
xylic acids [12–14], and reduction into biphenyl
[15–23]. It should be noted that mechanism and
regioselectivity of carbonylation [24, 25], solvolysis
[11, 26, 27], and anion-radical reduction [28–30] have
been studied in detail for certain individual congeners,
whereas the studies of the catalytic reduction have
been limited to applied research on reduction of the
technical mixtures.
Unfortunately, these compounds are toxic. They
can be transferred to a far location via air, water, or
food chains and can get into an organism via contact
with skin (absorption), inhalation (breathing), or
ingestion, causing damage of immune, endocrine, and
nervous systems and some other diseases. Since
polychlorinated biphenyls are water-insoluble and
resistant against chemical and biological degradation,
they are accumulated in the environment for years.
Production of polychlorinated biphenyls has been
banned but they still pollute the environment, mainly
due to leakages from old hardware and liquid industrial
wastes dumping [4]. Therefore, development of
efficient and cheap methods of chemical utilization of
The available reference data on the mechanism of
palladium-catalyzed hydrodechlorination of aryl
chlorides with 2-propanol in basic medium are
controversial. The anion-radical mechanism has been
suggested, at least in the presence of triethylamine as
the base [31]. Alternatively, dehydration of 2-propanol
into acetone on Pd catalyst, followed by hydrogenation
of aryl chloride with the released hydrogen has been
postulated [32–36].
Determination of the reaction regioselectivity using
low-chlorinated congeners as substrate is a convenient
method of elucidation of the mechanism of poly-
chlorinated biphenyls reactions. Herein, we studied
1656

REGULARITIES OF Pd/C-CATALYZED REDUCTION
1657
Scheme 1.
Pd/C (10%)
ArH + Me2CO + NaCl + H2O
ArCl + i-PrOH + NaOH
1_4
i-PrOH_H2O
83°C
Cl
Cl
Cl
Cl
Cl
X
Cl
Cl
Cl Cl
Cl
Cl
Cl
1
2
3
4
Scheme 2.
[Pd]
+
Cl
(HO)2B
[Pd]:
Cl
K2CO3
EtOH
80°C
Cl2
Cl2
6
5a–5c
2–4
Cl
Cl
HN C6H4-4-NO2
NH
Pd
C
C
N
NH
Cy
Cy
7
X = Br, Cl2 = 2,4-Cl2 (5a); X = I, Cl2 = 2,5-Cl2 (5b); X = I, Cl2 = 3,4-Cl2 (5c).
regioselectivity of reduction of trichlorobiphenyls 1–4
with 2-propanol in basic medium catalyzed by Pd/C
(Scheme 1).
competing hydrodechlorination of one of the three
nonequivalent chlorine atoms in the substrate to form
three isomeric dichlorobiphenyls (DCB). The second
hydrodechlorination stage yields isomeric monochloro-
biphenyls (CB). The final product of hydrodechlori-
nation is biphenyl.
The choice of the substrates was based on the fact
that they were the least chlorinated components of
Sovol and Sovtol commercial mixtures and the major
components of the Trikhlorbifenil mixture. Moreover,
trichlorinated biphenyls always contain differently
substituted benzene rings which is important for the
investigation of regularities of catalytic reduction of
polychlorinated biphenyls. The reaction was stopped at
incomplete conversion to determine the major product
of the reduction of a single chlorine group.
Reduction of isomeric trichlorobiphenyls with 10%
palladium on active carbon (Pd/C) was performed
under conditions adopted from [32], the first report to
describe the use of such system for hydrodechlorina-
tion of polychlorinated biphenyls. The experiments at
low conversion of the substrates were used to elucidate
the regioselectivity of the first stage of hydro-
dechlorination, whereas the experiments at high
conversion served to optimize the conditions of
complete reduction of the substrates into biphenyl. The
conversion was adjusted by changing the reaction
duration or the catalyst amount.
Individual congeners of polychlorinated biphenyls
2–4 were synthesized via the Suzuki reaction [11] from
polyhalogenated benzenes 5 and 4-chlorophenyl-
boronic acid 6 (Scheme 2). Acyclic diaminocarbene
complex of palladium (complex 7) was used as the
catalyst [37–40].
Chromato–mass spectrometry (GLC–MS) was used
as the primary method to investigate the regio-
selectivity. That highly sensitive method allowed
group identification of the peaks corresponding to
isomeric di- and monochlorinated biphenyls. Identifica-
tion of the individual isomers involved comparison of
Hydrodechlorination reactions of isomeric trichloro-
biphenyls are illustrated in Scheme 3 by these of
compound 2. The considered reactions are complex
processes involving several sequential and parallel
stages. The first stage of the process consists in the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 8 2017

1658
KOSTENKO et al.
Scheme 3.
Cl
Cl
Cl
2
Cl
Cl
Cl
Cl
Cl
Cl
2,4'-DCB
2,4-DCB
4,4'-DCB
Cl
Cl
2-CB
4-CB
the retention times of the reaction mixture components
with those of the references (either commercially
available or synthesized).
the reaction occurs predominantly at the halogen atom
in the ortho position to the substituent, irrespectively
of the sign of the substituent electronic effects [25, 29,
30, 41]. At the same time, the opposite regioselectivity
has been revealed for the metal-catalyzed reactions
involving the coordinated oxidative addition of the aryl
halide to the metal: the ortho-substituents decelerate
the process [41, 42] (as was observed in this study).
Hence, it was suggested that Pd/C-catalyzed hydro-
dechlorination of polychlorinated biphenyls with 2-pro-
panol in basic medium occurred via dehydration of
2-propanol on the catalyst, followed by catalytic
hydrogenation of the chlorinated substrate.
Regioselectivity of hydrodechlorination of trichloro-
biphenyls is the ratio of the accumulation rates of the
corresponding dichlorobiphenyls in the reaction mix-
ture under conditions preventing their deeper reduction
(for example, at low conversion, 3–7% in this work). It
was determined from the areas of the peaks of the
corresponding dichlorobiphenyls. That method could
not be applied for 2,4,5-trichlorobiphelyl 1 and 3,4,4'-
trichlorobiphenyl 4, since some of the formed products
(2,4- and 2,5-dichlorobiphenyls for compound 1; 3,4-
and 3,4'-dichlorobiphenyls for compound 4) exhibited
practically equal retention times. The attempts to
elaborate the conditions of their separation by chro-
matography failed. Therefore, the data on regio-
selectivity of hydrodechlorination of isomeric trichloro-
biphenyls were limited to congeners 2 and 3 (Scheme 4).
That was additionally confirmed by the investiga-
tion of reduction of congener 3 with 2-propanol
enriched with deuterium at the hydroxy group (i.e. a
mixture of i-PrOH and i-PrOD). Mass-spectrometric
analysis of the isotopic distribution of hydrogen in the
reduction products revealed that the content of
deuterium in the hydrodechlorination reaction products
exceeded its natural occurrence. The enrichment of
2,4',5-trichlorobiphenyl hydrodechlorination products
with deuterium was calculated as follows:
The obtained results suggested that chlorine atoms
in the para or meta position of the more substituted benzene
ring were the most reactive sites of the substrate.
The obtained data contradicted the common regula-
rities of anion-radical reactions. In the case of inter-
mediate formation of anion-radicals of polyhaloarenes,
Irel(D) – Irel(Н)
% D = –————— × 100%,
(1)
100 – Irel(Н)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 8 2017

REGULARITIES OF Pd/C-CATALYZED REDUCTION
1659
Scheme 4.
Cl
Cl
Cl
2
Cl
Cl
Cl
Cl
+
+
Pd/C
i-PrOH, 83oC, 1 h
Cl
Cl
2,4-DCB
2,4'-DCB
4,4'-DCB
0.6 : 2.1 : 1.0
Cl
Cl
Cl
3
Cl
Cl
Cl
Cl
Cl
Pd/C
i-PrOH, 83oC, 1 h
+
+
Cl
3,4'-DCB
2,4'-DCB
2,5-DCB
3.3 : 5.4 : 1.0
where Irel(D) and Irel(Н) being the relative intensities of
the [M + 1]/[М] peaks for the compounds prepared
using deuterium-enriched and conventional 2-pro-
panol, respectively.
and 100.61 MHz (13C)] in CDCl3. The chemical shifts
were measured relative to the residual protons and carbon
atoms of the solvent. Gas-liquid chromatography (GLC)
analysis was performed using a Khromatel Kristall
5000.2 instrument equipped with a flame ionization
detector and a VRKh-1 capillary column (10 m ×
0.53 mm × 2.65 μm). Chromato–mass spectrometry
analysis was performed using a Shimadzu GCMS QP-
2010 SE instrument under the following conditions: EI
at 70 eV, scanning over m/z 50–500, detector tempera-
ture 220°С, Rtx-5MS column (30 m × 0.32 mm ×
0.25 µm), argon as the carrier gas (0.8 mL/min).
Enrichment of 2-propanol with deuterium was
performed using two different procedures (cf. Experi-
mental). The data on the reduction products analysis
are collected in Tables 1 and 2. The enrichment of the
reduction products with deuterium contained exclusi-
vely in the hydroxy group of the alcohol confirmed the
reaction pathway via the dehydration of 2-propanol.
EXPERIMENTAL
Inorganic chemicals (“chemically pure or “analy-
tically pure” grade) were purchased from Vekton and
Merck. Solvents (“chemically pure or “analytically
1H and 13С NMR spectra were recorded using a
Bruker Avance II+ spectrometer [400.13 MHz (1Н)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 8 2017

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KOSTENKO et al.
Table 1. Calculation of enrichment with deuterium of the products of congener 3 reduction with i-PrOD prepared via method aa,b
Reduction product
Irel(D)
Irel(Н)
Irel(D) – Irel(Н)
% D
2,5-Dichlorobiphenyls
24.09±0.16
12.45±0.08
11.64±0.18
13.3±0.2
2,4'- Dichlorobiphenyls
3,4'- Dichlorobiphenyls
28.80±0.90
36.40±1.09
13.23±0.41
14.57±0.44
15.57±0.99
21.83±1.18
17.9±1.1
25.6±1.3
a Deuterium-enriched 2-propanol was prepared using method a. b Conversion of congener 3 was 0.6%.
Table 2. Calculation of enrichment with deuterium of the products of congener 3 reduction with i-PrOD prepared via method ba,b
Reduction product
2,5-Dichlorobiphenyls
2,4'-Dichlorobiphenyls
Biphenyl
Irel(D)
Irel(Н)
Irel(D) – Irel(Н)
3.41±0.13
3.91±0.67
10.43±0.74
% D
3.9±0.2
4.5±0.8
12.0±0.8
15.86±0.10
17.14±0.90
23.62±0.73
12.45±0.08
13.23±0.41
13.19±0.13
a Deuterium-enriched 2-propanol was prepared using method a. b Conversion of congener 3 was 97%.
pure” grade) were used as received. Commercial halo-
genated benzenes, 4-chlorophenylboronic acid, 4,4'-
dibromobiphenyl, 2,4-dichlorobiphenyl, 3,4-dichloro-
biphenyl, and 2,4,5-trichlorobiphenyl (Vekton) were
0.5 mL of ethanol was added. The tube was tightly
screwed and stirred during 2.5 h at 83°C. The mixture
was then cooled to ambient, 10 mL of water was
added, and the reaction product was extracted with a
2 : 1 hexane–dichloromethane mixture (3×20 mL), the
organic layer was dried over anhydrous Na2SO4, the
solvent was evaporated, and the residue was weighed
1
used as received; their purity was confirmed by H
NMR and GLC. The catalyst for Suzuki reaction was
prepared as described elsewhere [37–40]. The catalyst
for hydrodechlorination reactions (10% palladium on
active carbon) was purchased from Acros Organics.
1
and analyzed by H NMR and GLC. Yield 252 mg
1
(98%), mp 56°C (methanol). H NMR spectrum, δ,
ppm: 7.25 d (1Н, H6, J = 8.2 Hz), 7.32 d.d (1H, H5, J =
4,4'-Dichlorobiphenyl [43]. A mixture of 624 mg
(2 mmol) of 4,4'-dibromobiphenyl and 2 g (20 mmol)
of CuCl in 10 mL of anhydrous DMF was refluxed
during 8 h at stirring. The solvent was distilled off at a
water-jet pump vacuum, and the residue was extracted
with chloroform. The extract was dried over anhydrous
Na2SO4, and the solvent was evaporated. The obtained
crystals were recrystallized from 96% ethanol. Yield
8.2, 2.0 Hz), 7.37 and 7.43 (4H, AA'XX' system,
H
2',3',5',6', J = 8.5 Hz), 7.51 d (1H, H3, J = 2.0 Hz).
2,5,4'-Trichlorobiphenyl [45] was prepared similarly
from 546 mg (2 mmol) of 1-iodo-2,5-dichlorobenzene
and 344 mg (2.2 mmol) of 4-chlorophenylboronic acid.
Yield 508 mg (98.6%), crude product was
recrystallized from methanol, yield 420 mg (81.5%),
purity >99.6% (GLC–MS), mp 66°C. 1H NMR
spectrum, δ, ppm: 7.30 d.d (1H, H4, J = 8.5, 2.5 Hz),
7.33 d (1H, H6, J = 2.5 Hz), 7.39 and 7.43 (4H,
AA'XX' system, H2',3',5',6', J = 8.6 Hz), 7.42 d (1H, H3,
J = 8.6 Hz). 13C NMR spectrum, δ, ppm: 128.48
(C2',6'), 128.82 (C4), 130.63 (C3',5'), 130.79 (C2), 130.99
(C6), 131.14 (C3), 132.73 (C5), 134.31 (C4'), 136.55
(C1'), 140.76 (C10).
1
63% (290 mg), colorless crystals, mp 151–152°C. H
NMR spectrum, δ, ppm: 7.43 and 7.50 (8H, AA'XX'
system, J = 8.6 Hz). 13C NMR spectrum, δС, ppm:
128.19 (C2,6,2',6'), 129.08 (C3,5,3',5'), 133.80 (C4,4'), 138.47
(C1,1').
2,4,4'-Trichlorobiphenyl [44]. A 15 mL screw-top
glass tube was loaded with 4 mL of 96% ethanol,
226 mg (1 mmol) of 1-bromo-2,4-dichlorobenzene,
172 mg (1.1 mmol) of 4-chlorophenylboronic acid, and
207 mg (1.5 mmol) of anhydrous K2CO3. The tube was
put in an oil bath heated to 78°C. The reaction mixture
was stirred during 3 min, and then 0.7 mg (0.0012 mmol)
of acyclic diaminocarbene complex of palladium 7 in
3,4,4'-Trichlorobiphenyl [46] was prepared similarly
from 410 mg (1.5 mmol) of 1-iodo-3,4-dichloro-
benzene and 258 mg (1.65 mmol) of 4-chloro-
phenylboronic acid. Crude product yield 359 mg
1
(92.9%), mp 88–89°C (methanol). H NMR spectrum,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 8 2017

REGULARITIES OF Pd/C-CATALYZED REDUCTION
1661
δ, ppm: 7.39 d.d (1H, H6, J = 8.4, 2.1 Hz), 7.44 and
7.49 (4H, AA'XX' system, J = 8.6 Hz), 7.52 (1H, H5,
J = 8.4 Hz), 7.65 d (1H, H2, J = 2.1 Hz). 13C NMR spec-
trum, δС, ppm: 126.18 (C6), 128.20 (C3',5'), 128.81 (C4),
129.20 (C2',6'), 130.81 (C5), 131.84 (C4), 133.03 (C3),
134.35 (C4'), 137.21 (C1'), 139.98 (C1).
The experiments were performed using the equipment
of Resource Centers of St. Petersburg State University:
“Magnetic Resonance Methods” and “Education
Resource Center for Chemistry field.”
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ACKNOWLEDGMENTS
This study was financially supported by St.
Petersburg State University (grant no. 12.37.214.2016).
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