Reactivity of C-H bonds of polychlorobenzenes for palladium-catalysed direct arylations with aryl bromides

Article abstract of DOI:10.1039/c3cy00757j

The reactivity of polychlorobenzenes vs. polyfluorobenzenes for palladium-catalysed direct arylation was studied. The PdCl(C₃H ₅)(dppb)/KOAc system was found to promote the direct arylation of some polychlorobenzenes with aryl bromid

Full text of DOI:10.1039/c3cy00757j

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Reactivity of C–H bonds of polychlorobenzenes
for palladium-catalysed direct arylations with
aryl bromides
Cite this: Catal. Sci. Technol., 2014,
4, 352
*
Liqin Zhao, Tao Yan, Christian Bruneau and Henri Doucet
The reactivity of polychlorobenzenes vs. polyfluorobenzenes for palladium-catalysed direct arylation was
studied. The PdCl(C3H5)(dppb)/KOAc system was found to promote the direct arylation of some
polychlorobenzenes with aryl bromides. However, the reactivity of polychlorobenzenes was found to be
lower than that of polyfluorobenzenes. The best yields were obtained from the coupling of 1,2,4,5-
tetrachlorobenzene or 1,3,5-trichlorobenzene with electron-deficient aryl bromides. The C3 arylation of
2,5-dichlorothiophene was also found to proceed nicely.
Received 2nd October 2013,
Accepted 5th November 2013
DOI: 10.1039/c3cy00757j
www.rsc.org/catalysis
co-workers described that the carboxylic acid group in
2,4-dichlorobenzoic acid allows for direct arylation at C6
Introduction
Among benzene derivatives, several (poly)chlorobenzene
derivatives display important biological properties. For exam-
ple, lamotrigine is an anticonvulsant used in the treatment of
epilepsy, hexachlorophene is a disinfectant used in soaps,
ambigol A also has antimicrobial activity, dicloxacillin is an
antibiotic, clobuzarit is an antirheumatic, and tanomastat is a
protease inhibitor (Fig. 1). Therefore, the discovery of general
simple routes for access to a variety of (poly)chlorobenzene
derivatives has potential in medicinal chemistry.
The direct coupling of arenes with aryl halides via C–H
bond activation/functionalisation provides a cost-effective and
environmentally attractive procedure for the preparation of
biaryls.1,2 Such couplings are very attractive compared to
classical palladium-catalysed reactions such as Stille, Suzuki
or Negishi couplings as they do not require the preliminary
synthesis of organometallic derivatives.3 Moreover, the major
by-product is HX (X = I, Br or Cl) associated to a base instead
of a metallic salt using more classical coupling procedures.
The reactivity of arenes such as polyfluorobenzenes for the
palladium-catalysed direct arylation has been largely studied
in recent years.4–6 On the other hand, the influence of chloro
substituents on benzenes for such couplings has attracted
much less attention.7–9 The palladium-catalyzed 2-arylation
of 4-chlorobenzamide or 6-arylation of 3,4-dichlorobenzamide
using aryl iodides as the coupling partners has been recently
reported by Wang and co-workers (Fig. 2, top).8b They demon-
strated that the amide group directs the arylation at the less
hindered ortho-position of the amide. Similarly, Larrosa and
(Fig. 2, bottom).8c
The Gibbs free energies of activation for direct arylation via
the concerted metalation deprotonation (CMD)10 pathway of
several polychloro- and polyfluorobenzenes have been calculated
by Gorelsky (Fig. 3).10c A lower reactivity of pentachlorobenzene
compared to pentafluorobenzene could be expected as the
energies of activation (ΔG298 K) for the cleavage of C–H bonds
are 27.2 and 21.9, respectively. Similarly, 1,3,5-trichlorobenzene
was expected to be less reactive than 1,3,5-trifluorobenzene
(energies: 28.5 vs. 24.5); and for 1,3-dichlorobenzene, the most
reactive C–H should be at the C2 position. However, as these
calculated reactivities have not yet been confirmed by experi-
ments, the outcome of the reaction of polychlorobenzenes with
aryl halides in the presence of palladium-catalysts was quite
unpredictable and needed to be investigated.
Here, we wish to report on (i) the influence of chloro-
substituents on benzene on the reactivity and regioselectivity
of the palladium-catalysed direct arylation with aryl halides;
(ii) the scope of the reaction using a set of aryl bromides.
Results and discussion
Commercially
available
pentachlorobenzene
and
4-bromobenzonitrile were employed as the test substrates
(Scheme 1, Table 1). We initially examined the influence of
the nature of the base on the yield of this reaction using DMA
as the solvent and 2 mol% of PdCl(C3H5)(dppb) as the cata-
lyst, as such conditions were previously found operative for
some direct arylations of (hetero)aromatics.2b In all cases, par-
tial conversion of 4-bromobenzonitrile was observed. In the
presence of NaOAc, KOAc or K2CO3 as bases, very similar
yields of 1 were obtained, whereas CsOAc was less effective
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes
“Organométalliques Matériaux et Catalyse”, Campus de Beaulieu, 35042 Rennes,
France. E-mail: henri.doucet@univ-rennes1.fr; Fax: +33 (0)2 23 23 69 39;
Tel: +33 (0)2 23 23 63 84
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Scheme 1 Influence of the reaction conditions for the palladium-catalysed
direct arylation of pentachlorobenzene with 4-bromobenzonitrile.
Table 1 Influence of the reaction conditions for the palladium-catalysed
direct arylation of pentachlorobenzene with 4-bromobenzonitrile
(Scheme 1)a
Yield in
1 (%)
Entry Ratio ArBr : C6HCl5 Catalyst (mol%)
Base
Fig. 1 Examples of bioactive (poly)chlorobenzenes.
1
2
3
4
5
6
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.5
1 : 3
PdCl(C3H5)(dppb) (2) NaOAc 23
PdCl(C3H5)(dppb) (2) KOAc
PdCl(C3H5)(dppb) (2) CsOAc
24
8
PdCl(C3H5)(dppb) (2) K2CO3 21
PdCl(C3H5)(dppb) (2) KOAc
Pd(OAc)2 (2) KOAc
25
25
1 : 1.5
a
Conditions: base (4 equiv.), DMA, 20 h, 150 °C.
Scheme 2 Direct arylations of pentachlorobenzene with aryl bromides.
Fig. 2 Reported Pd-catalysed direct arylations of mono- and
di-chlorobenzenes.8b,c
The influence of two other bromobenzene substituents on
the reactivity for the coupling with pentachlorobenzene was then
examined (Scheme 2). In the presence of the electron-deficient
aryl bromides, 4-bromonitrobenzene or 4-bromobenzaldehyde,
the products 2 and 3 were obtained in 44% and 46% yields,
respectively, when PdCl(C3H5)(dppb) was employed as the cat-
alyst. The use of Pd(OAc)2 catalyst gave 3 in a lower yield.
Again, in all cases, only a partial conversion of the aryl bro-
mide and pentachlorobenzene was observed.
The reactivity of 1,2,4,5-tetrachlorobenzene was found to be
slightly higher than that of pentachlorobenzene (Scheme 3). For
these couplings, in order to avoid the formation of 1,4-diarylated
tetrachlorobenzenes, 3 equiv. of 1,2,4,5-tetrachlorobenzene
was employed. In the presence of aryl bromides substituted at
C4 by nitrile, nitro or formyl substituents, the desired mono-
arylation products 4–6 were obtained in 47–66% yields, and
no significant amount of diarylation products was formed.
From 3-bromobenzonitrile, a similar yield of 58% for 7 was
obtained. We also found that the coupling of 3-bromopyridine
or 5-bromopyrimidine proceeded quite nicely to give 8 and 9
in 64% and 60% yields, respectively.
Fig. 3 Gibbs free energies of activation (ΔG298 K) of the cleavage of
C–H bonds for different polyhaloarenes in the CMD process using
the [Pd(C6H5)(PMe3)(OAc)] catalyst.10c
(Table 1, entries 1–4). The ratio of the reactants also appeared
to have a minor influence on the yield. Another catalyst pre-
cursor was also employed. However, the use of phosphine-free
Pd(OAc)2 led to 1 in similar yield (Table 1, entry 6).
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Scheme
5
Direct arylation of 1,3,5-trichlorobenzene with various
aryl bromides.
Scheme 3 Direct arylation of 1,2,4,5-tetrachlorobenzene with various
aryl bromides.
In order to gain more insight on the reactivity of chloro-
vs. fluoro-substituted benzenes, we compared the reactivity of
tetrachloro- and tetrafluorobenzenes. An equimolar mixture
of 1,2,4,5-tetrachlorobenzene and 1,2,4,5-tetrafluorobenzene
reacted with 4-bromobenzonitrile gave a mixture of products
4 and 10 in a 1 : 3 ratio (Scheme 4). Moreover, some forma-
tion of the diarylation product of 1,2,4,5-tetrafluorobenzene
was also detected using GC/MS analysis, whereas no diarylation
of 1,2,4,5-tetrachlorobenzene was observed. This result con-
firms that 1,2,4,5-tetrachlorobenzene is less reactive than
1,2,4,5-tetrafluorobenzene for Pd-catalysed direct arylation.
Gorelsky had calculated a Gibbs free energy of activation for
direct arylation of 1,3,5-trichlorobenzene of 28.5 (Fig. 3).10c
Under similar conditions, the desired arylation products 11–14
were obtained in higher yields with 1,3,5-trichlorobenzene than
with pentachlorobenzene (Scheme 5). Very similar yields were
obtained from cyano-, nitro- or formyl-substituted bromobenzenes.
1,2,3-Trichlorobenzene reacted with 4-bromobenzonitrile,
4-bromonitrobenzene or 4-bromobenzaldehyde to give 15 and
16 in poor yields (Scheme 6). However, the reaction was
regioselective in favour of the formation of the 4-arylated
products. Better yields were obtained for the coupling with
3-bromoquinoline and 5-bromopyrimidine, as the desired products
17 and 18 were obtained in 40% and 48% yields, respectively.
Scheme
aryl bromides.
6 Direct arylation of 1,2,3-trichlorobenzene with various
Unexpectedly, quite good yields were obtained for
the coupling of 1,4-dichlorobenzene with aryl bromides.
From 4-bromobenzonitrile, 19 was obtained in 48% yield
(Scheme 7). Both 3-trifluoromethylbromobenzene and
3,5-bis(trifluoromethyl)bromobenzene also gave the expected
products 22 and 23 in quite good yields. The best yield was
obtained in the presence of 3-bromoquinoline to give 24 in
55% yield.
According to Gorelsky, for 1,3-dichlorobenzene, carbon 2
should be more reactive than carbon 4 (energies: 28.9 vs. 30.9)
(Fig. 3).10c Our first attempt of coupling 1,3-dichlorobenzene
with 4-bromobenzonitrile using PdCl(C3H5)(dppb) as catalyst
and KOAc as base in DMA led to
regioisomers according to GC/MS analysis. Surprisingly,
a mixture of two
Scheme
4 Competitive experiment for palladium-catalysed direct
arylation using an equimolar mixture of 1,2,4,5-tetrachlorobenzene
and 1,2,4,5-tetrafluorobenzene.
Scheme
aryl bromides.
7 Direct arylation of 1,4-dichlorobenzene with various
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Scheme
8
Direct
arylation
of
1,3-dichlorobenzene
with
4-bromobenzonitrile.
Scheme 10 Attempts of direct arylation of 4-substituted chloroben-
zenes with 4-bromobenzonitrile.
Table 2 Influence of the reaction conditions for the palladium-catalysed
direct arylation of 1,3-dichlorobenzene with 4-bromobenzonitrile
(Scheme 8)a
Entry Catalyst (mol%)
Solvent Conv. (%) Yield in 25 (%)
1
2
3
4
5
6
PdCl(C3H5)(dppb) (2) DMA
PdCl(C3H5)(dppb) (2) DMF
PdCl(C3H5)(dppb) (2) NMP
57
64
56
47
69
54
34
25
26
—
33
—
Pd(OAc)2 (2)
DMA
Scheme 11 Direct arylation of 2,5-dichlorothiophene with various
aryl bromides.
Pd(OAc)2 (2)/dppe (2) DMA
Pd(OAc)2 (2)/dppb (2) DMA
a
Conditions: 4-bromobenzonitrile (1 equiv.), 1,3-dichlorobenzene
(3 equiv.), KOAc (4 equiv.), 20 h, 150 °C, conv. of 4-bromobenzonitrile;
in all cases, 25 was obtained in 66% regioselectivity.
the major product of the reaction was the C4-arylated
1,3-dichlorobenzene 25 with a selectivity of 66% (Scheme 8,
Table 2). Arylation at the less reactive C4 position might be
due to the steric hindrance of the chloro substituents. The
influence of several reaction conditions has been studied, but
in all cases, the same regioselectivity was obtained. However,
the reactions performed in DMF or NMP led to lower yields of
25 due to the formation of side-products, whereas Pd(OAc)2
gave a lower conversion.
Scheme 12 Direct arylation of 2,5-dichlorothiophene with various
The reaction of an equimolar mixture of 1,3-dichloroben-
zene and 1,3-difluorobenzene using the same reaction condi-
tions gave a mixture of the 2-arylated 1,3-difluorobenzene
26 and the 4-arylated 1,3-dichlorobenzene 25 in a 4 : 1 ratio
(Scheme 9). Again, the fluorobenzene derivative is more reac-
tive than the chlorobenzene derivative. Moreover, the
regioselectivities of these two reactions were different, with
the less sterically demanding fluoro substituents making the
calculated arylation at C2 possible (Fig. 3).
aryl bromides.
The reactivity of three 4-substituted chlorobenzenes with
4-bromobenzonitrile as coupling partner using similar reaction
conditions was also examined (Scheme 10). However, the pres-
ence of electron-withdrawing or electron-donating substituents
on chlorobenzene led to unreacted aryl bromide, and no for-
mation of the target products 27–29 was detected.
Finally, we examined the reactivity of 2,5-dichlorothiophene
for direct arylation (Schemes 11 and 12). The influence of a
few reaction conditions has been examined. The best yield in
30 was obtained using 1 mol% PdCl(C3H5)(dppb) as catalyst
in DMF and KOAc as base. However, quite similar results were
obtained in DMA or using 2 mol% Pd(OAc)2/dppb as catalyst
(Table 3).
The reaction tolerates a variety of substituents on the aryl
bromide such as acetyl, formyl, nitrile or nitro (Scheme 12).
The best yields were obtained from the reactions with
2-bromobenzonitrile and 4-bromoisoquinoline. With these
reactants, the desired products 36 and 38 were obtained in
81 and 78% yields, respectively. On the other hand, from
4-bromoacetophenone, 31 was only produced in 48% yield
due to the formation of unidentified side-products.
Scheme
9 Competitive experiment for palladium-catalysed direct
arylation using an equimolar mixture of 1,3-dichlorobenzene and 1,3-
difluorobenzene.
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Table 3 Influence of the reaction conditions for the palladium-catalysed direct arylation of 2,5-dichlorothiophene with 4-bromobenzonitrile
(Scheme 11)a
Entry
Catalyst (mol%)
Base
Solvent
Conv. (%)
Yield in 30 (%)
1
2
3
4
5
6
7
PdCl(C3H5)(dppb) (1)
PdCl(C3H5)(dppb) (2)
PdCl(C3H5)(dppb) (1)
PdCl(C3H5)(dppb) (1)
PdCl(C3H5)(dppb) (1)
PdCl(C3H5)(dppb) (0.5)
Pd(OAc)2 (2)/dppb (2)
KOAc
KOAc
CsOAc
KOAc
KOAc
KOAc
KOAc
DMA
DMA
DMA
NMP
DMF
DMF
DMF
70
78
30
60
87
44
88
56
60
—
50
63
—
62
a
Conditions: 4-bromobenzonitrile (1 equiv.), 2,5-dichlorothiophene (2 equiv.), base (4 equiv.), 20 h, 150 °C, conv. of 4-bromobenzonitrile.
under argon affords the coupling product after evaporation
of the solvent and purification on silica gel.
In summary, we report herein the first examples of palladium-
Conclusions
catalysed direct ortho-arylations of polychlorobenzene deriva-
2′,3′,4′,5′,6′-Pentachlorobiphenyl-4-carbonitrile (1)
From 4-bromobenzonitrile (0.182 g, mmol) and
pentachlorobenzene (0.375 g, 1.5 mmol), 1 was obtained in
25% (0.088 g) yield.
tives with aryl bromides using chloro-substituent as
a
directing group. The reactivity of polychlorobenzenes was
found to be lower than that of the corresponding
polyfluorobenzene derivatives as calculated by Gorelsky. The
influence of the number and positions of chloro-substituents
on benzene on their reactivity was studied. The steric proper-
ties of chloro-substituents likely partially modify the reactiv-
ity of this family of compounds. Although moderate yields
were obtained in several cases, this method gives access to
functionalised polychlorobiphenyls in only one step.
1
1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 8.0 Hz, 2H), 7.27
(d, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ 141.3,
138.4, 134.2, 132.6, 132.4, 132.2, 130.0, 118.2, 113.0. Elemen-
tal analysis: calcd (%) for C13H4Cl5N (351.44): C 44.43, H 1.15;
found: C 44.50, H 1.22.
2,3,4,5,6-Pentachloro-4′-nitrobiphenyl (2)12
Experimental
General remarks
From 4-bromonitrobenzene (0.202 g,
1
mmol) and
pentachlorobenzene (0.375 g, 1.5 mmol), 2 was obtained in
44% (0.163 g) yield.
All reactions were performed in Schlenk tubes under argon.
DMA analytical grade was not distilled before use. Potassium
acetate 99+ was used. Commercial aryl halide derivatives
were used without purification. 1H (300 and 400 MHz) and
13C (75 and 100 MHz) spectra were recorded in CDCl3 solu-
tions. Chemical shifts are reported in ppm relative to CDCl3
(1H: 7.26 and 13C: 77.0). Flash chromatography was performed
on silica gel (230–400 mesh).
1H NMR (400 MHz, CDCl3): δ 8.39 (d, J = 8.9 Hz, 2H),
7.43 (d, J = 8.9 Hz, 2H).
2′,3′,4′,5′,6′-Pentachlorobiphenyl-4-carbaldehyde (3)
From 4-bromobenzaldehyde (0.185 g,
pentachlorobenzene (0.375 g, 1.5 mmol), 3 was obtained
in 46% (0.163 g) yield.
1
mmol) and
1H NMR (400 MHz, CDCl3): δ 10.12 (s, 1H), 8.04 (d, J =
8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ 191.5, 142.8, 139.1, 136.4, 133.9, 132.3, 132.2, 130.0,
129.8. Elemental analysis: calcd (%) for C13H5Cl5O (354.44):
C 44.05, H 1.42; found: C 44.14, H 1.60.
Preparation of the PdCl(C3H5)(dppb) catalyst11
An oven-dried 40 mL Schlenk tube equipped with a magnetic
stirring bar under argon atmosphere was charged with
[Pd(C3H5)Cl]2 (182 mg, 0.5 mmol) and dppb (426 mg, 1 mmol).
10 mL of anhydrous dichloromethane was added, and then
the solution was stirred at room temperature for twenty
minutes. The solvent was removed in vacuum. The yellow
powder was used without purification. 31P NMR (81 MHz,
CDCl3) δ = 19.3 (s).
2′,3′,5′,6′-Tetrachlorobiphenyl-4-carbonitrile (4)
From 4-bromobenzonitrile (0.182 g, 1 mmol) and 1,2,4,5-
tetrachlorobenzene (0.647 g, 3 mmol), 4 was obtained in 61%
(0.193 g) yield.
1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.0 Hz, 2H), 7.62
(s, 1H), 7.27 (d, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3):
δ 141.6, 140.7, 132.5, 132.4, 131.4, 130.9, 130.0, 118.3, 112.8.
Elemental analysis: calcd (%) for C13H5Cl4N (317.00): C 49.26,
H 1.59; found: C 49.40, H 1.49.
General procedure for the synthesis of compounds 1–31
As a typical experiment, the reaction of the aryl bromide
(1 mmol), polychlorobenzene derivative (1.5 or 3 mmol) and
KOAc (0.392 g, 4 mmol) at 150 °C during 20 h in DMA (4 mL)
in the presence of PdCl(C3H5)(dppb) (12.2 mg, 0.02 mmol)
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2,3,5,6-Tetrachloro-4′-nitrobiphenyl (5)
1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.1 Hz, 2H), 7.39
(s, 2H), 7.30 (d, J = 8.1 Hz, 2H). 13C NMR (100 MHz, CDCl3):
δ 140.5, 136.3, 135.0, 134.9, 132.2, 130.6, 128.3, 118.5, 112.5.
Elemental analysis: calcd (%) for C13H6Cl3N (282.55): C 55.26,
H 2.14; found: C 55.11, H 2.07.
From 4-bromonitrobenzene (0.202 g, 1 mmol) and 1,2,4,5-
tetrachlorobenzene (0.647 g, 3 mmol), 5 was obtained in 47%
(0.158 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.29 (d, J = 8.9 Hz, 2H), 7.64
(s, 1H), 7.43 (d, J = 8.9 Hz, 2H). 13C NMR (100 MHz, CDCl3):
δ 148.0, 143.4, 140.4, 132.5, 131.4, 131.0, 130.3, 124.0. Ele-
mental analysis: calcd (%) for C12H5Cl4NO2 (336.98): C 42.77,
H 1.50; found: C 42.64, H 1.38.
2,4,6-Trichloro-4′-nitrobiphenyl (12)
From 4-bromonitrobenzene (0.202 g, 1 mmol) and 1,3,5-
trichlorobenzene (0.544 g, 3 mmol), 12 was obtained in 55%
(0.166 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.25 (d, J = 8.7 Hz, 2H), 7.39
(s, 2H), 7.36 (d, J = 8.7 Hz, 2H). 13C NMR (100 MHz, CDCl3):
δ 146.8, 141.3, 135.0, 134.1, 133.9, 129.9, 127.4, 122.7. Ele-
mental analysis: calcd (%) for C12H6Cl3NO2 (302.54): C 47.64,
H 2.00; found: C 47.80, H 1.88.
2′,3′,5′,6′-Tetrachlorobiphenyl-4-carbaldehyde (6)
From 4-bromobenzaldehyde (0.185 g, 1 mmol) and 1,2,4,5-
tetrachlorobenzene (0.647 g, 3 mmol), 6 was obtained in 66%
(0.211 g) yield.
1H NMR (400 MHz, CDCl3): δ 10.03 (s, 1H), 7.94 (d, J =
8.4 Hz, 2H), 7.61 (s, 1H), 7.32 (d, J = 8.4 Hz, 2H). 13C NMR
(100 MHz, CDCl3): δ 191.6, 143.0, 141.3, 136.3, 132.3, 131.5,
130.7, 130.0, 129.9. Elemental analysis: calcd (%) for
C13H6Cl4O (320.00): C 48.79, H 1.89; found: C 48.62, H 2.04.
2′,4′,6′-Trichlorobiphenyl-4-carbaldehyde (13)
From 4-bromobenzaldehyde (0.185 g, 1 mmol) and 1,3,5-
trichlorobenzene (0.544 g, 3 mmol), 13 was obtained in 63%
(0.180 g) yield.
1H NMR (400 MHz, CDCl3): δ 10.02 (s, 1H), 7.93 (d, J =
8.1 Hz, 2H), 7.39 (s, 2H), 7.35 (d, J = 8.1 Hz, 2H). 13C NMR
(100 MHz, CDCl3): δ 191.7, 142.0, 136.9, 136.1, 135.0, 134.7,
130.5, 129.7, 128.3. Elemental analysis: calcd (%) for
C13H7Cl3O (285.55): C 54.68, H 2.47; found: C 54.49, H 2.67.
2′,3′,5′,6′-Tetrachlorobiphenyl-3-carbonitrile (7)
From 3-bromobenzonitrile (0.182 g, 1 mmol) and 1,2,4,5-
tetrachlorobenzene (0.647 g, 3 mmol), 7 was obtained in 58%
(0.184 g) yield.
1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 7.8 Hz, 1H), 7.63
(s, 1H), 7.55 (t, J = 7.8 Hz, 1H), 7.46 (s, 1H), 7.39 (d, J =
7.8 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 141.2, 138.3,
133.6, 132.7, 132.4, 132.3, 131.8, 130.9, 129.6, 118.2, 113.2.
Elemental analysis: calcd (%) for C13H5Cl4N (317.00): C 49.26,
H 1.59; found: C 49.21, H 1.64.
2,4,6-Trichloro-3′-nitrobiphenyl (14)
From 3-bromonitrobenzene (0.202 g, 1 mmol) and 1,3,5-
trichlorobenzene (0.544 g, 3 mmol), 14 was obtained in 62%
(0.187 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.24 (d, J = 8.7 Hz, 1H), 8.08
(s, 1H), 7.59 (t, J = 8.0 Hz, 1H), 7.51 (d, J = 8.7 Hz, 1H), 7.41
(s, 2H). 13C NMR (100 MHz, CDCl3): δ 148.3, 137.3, 135.9,
135.7, 135.3, 135.2, 129.5, 128.4, 125.0, 123.5. Elemental anal-
ysis: calcd (%) for C12H6Cl3NO2 (302.54): C 47.64, H 2.00;
found: C 47.61, H 1.97.
3-(2,3,5,6-Tetrachlorophenyl)-pyridine (8)
From 3-bromopyridine (0.158 g,
1 mmol) and 1,2,4,5-
tetrachlorobenzene (0.647 g, 3 mmol), 8 was obtained in 64%
(0.187 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.68 (bs, 1H), 8.47 (bs, 1H),
7.64 (s, 1H), 7.61 (d, J = 7.8 Hz, 1H), 7.47 (s, 1H). 13C NMR
(100 MHz, CDCl3): δ 148.5, 148.4, 138.5, 138.1, 132.5, 132.2,
131.2. Elemental analysis: calcd (%) for C11H5Cl4N (292.97):
C 45.10, H 1.72; found: C 45.27, H 1.89.
2′,3′,4′-Trichlorobiphenyl-4-carbonitrile (15)
From 4-bromobenzonitrile (0.182 g, 1 mmol) and 1,2,3-
trichlorobenzene (0.544 g, 3 mmol), 15 was obtained in 35%
(0.099 g) yield.
1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 8.0 Hz, 2H), 7.43
(d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.3 Hz, 1H), 7.09 (d, J = 8.3 Hz,
1H). 13C NMR (100 MHz, CDCl3): δ 143.1, 139.1, 134.4, 132.8,
132.6, 132.1, 130.1, 128.8, 128.5, 118.4, 112.2. Elemental anal-
ysis: calcd (%) for C13H6Cl3N (282.55): C 55.26, H 2.14; found:
C 55.08, H 2.22.
5-(2,3,5,6-Tetrachlorophenyl)-pyrimidine (9)
From 5-bromopyrimidine (0.159 g, 1 mmol) and 1,2,4,5-
tetrachlorobenzene (0.647 g, 3 mmol), 9 was obtained in 60%
(0.176 g) yield.
1H NMR (400 MHz, CDCl3): δ 9.24 (s, 1H), 8.61 (s, 2H),
7.67 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 158.5, 157.0, 135.7,
132.7, 132.2, 131.7, 131.6. Elemental analysis: calcd (%) for
C10H4Cl4N2 (293.96): C 40.86, H 1.37; found: C 40.77, H 1.27.
2,3,4-Trichloro-4′-nitrobiphenyl (16)
From 4-bromonitrobenzene (0.202 g, 1 mmol) and 1,2,3-
trichlorobenzene (0.544 g, 3 mmol), 16 was obtained in 21%
(0.063 g) yield.
2′,4′,6′-Trichlorobiphenyl-4-carbonitrile (11)
From 4-bromobenzonitrile (0.182 g, 1 mmol) and 1,3,5-
trichlorobenzene (0.544 g, 3 mmol), 11 was obtained in 63%
(0.178 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.25 (d, J = 8.9 Hz, 2H), 7.50
(d, J = 8.9 Hz, 2H), 7.43 (d, J = 8.3 Hz, 1H), 7.12 (d, J = 8.3 Hz, 1H).
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13C NMR (100 MHz, CDCl3): δ 147.7, 144.9, 138.8, 134.6,
132.9, 132.6, 130.3, 128.8, 128.5, 123.6. Elemental analysis:
calcd (%) for C12H6Cl3NO2 (302.54): C 47.64, H 2.00; found:
C 47.49, H 1.89.
analysis: calcd (%) for C13H8Cl2O (251.11): C 62.18, H 3.21;
found: C 62.10, H 3.08.
2,5-Dichloro-3′-trifluoromethylbiphenyl (22)
From 3-trifluoromethylbromobenzene (0.225 g, 1 mmol) and
1,4-dichlorobenzene (0.441 g, 3 mmol), 22 was obtained in
54% (0.157 g) yield.
3-(2,3,4-Trichlorophenyl)-quinoline (17)
From 3-bromoquinoline (0.208 g,
1 mmol) and 1,2,3-
1H NMR (400 MHz, CDCl3): δ 7.61 (s, 1H), 7.60 (d, J = 8.0 Hz,
1H), 7.54 (d, J = 7.8 Hz, 1H), 7.50 (t, J = 7.8 Hz, 1H), 7.36 (d, J =
9.0 Hz, 1H), 7.28 (d, J = 2.4 Hz, 1H), 7.25 (dd, J = 9.0, 2.4 Hz,
1H). 13C NMR (100 MHz, CDCl3): δ 140.4, 138.8, 132.9, 132.7,
133.2, 131.0, 130.8 (q, J = 32.0 Hz), 129.2, 128.7, 128.5, 126.1
(q, J = 3.9 Hz), 124.9 (q, J = 3.7 Hz), 124.0 (q, J = 271.9 Hz).
Elemental analysis: calcd (%) for C13H7Cl2F3 (291.10): C 53.64,
H 2.42; found: C 53.82, H 2.28.
trichlorobenzene (0.544 g, 3 mmol), 17 was obtained in 40%
(0.123 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.89 (s, 1H), 8.15–8.10
(m, 2H), 7.82 (d, J = 8.1 Hz, 1H), 7.73 (t, J = 8.0 Hz, 1H), 7.56
(t, J = 8.0 Hz, 1H), 7.45 (d, J = 8.3 Hz, 1H), 7.21 (d, J = 8.3 Hz,
1H). 13C NMR (100 MHz, CDCl3): δ 150.2, 146.9, 137.4, 136.5,
134.3, 133.3, 132.8, 131.7, 130.5, 129.4, 129.0, 128.6, 128.1,
127.5, 127.4. Elemental analysis: calcd (%) for C15H8Cl3N
(308.59): C 58.38, H 2.61; found: C 58.28, H 2.57.
2,5-Dichloro-3′,5′-bis-trifluoromethylbiphenyl (23)
From 1-bromo-3,5-bis(trifluoromethyl)benzene (0.293 g, 1 mmol)
and 1,4-dichlorobenzene (0.441 g, 3 mmol), 23 was obtained
in 52% (0.187 g) yield.
5-(2,3,4-Trichlorophenyl)-pyrimidine (18)
From 5-bromopyrimidine (0.159 g, 1 mmol) and 1,2,3-
trichlorobenzene (0.544 g, 3 mmol), 18 was obtained in 48%
(0.124 g) yield.
1H NMR (400 MHz, CDCl3): δ 7.86 (s, 1H), 7.82 (s, 2H),
7.39 (d, J = 9.0 Hz, 1H), 7.32–7.25 (m, 2H). 13C NMR (100 MHz,
CDCl3): δ 140.0, 138.8, 133.2, 131.7 (q, J = 33.0 Hz), 131.4,
130.9, 130.7, 130.0, 129.6 (m), 123.1 (q, J = 271.5 Hz), 122.0 (q,
J = 3.8 Hz). Elemental analysis: calcd (%) for C14H6Cl2F6
(359.09): C 46.83, H 1.68; found: C 46.74, H 1.79.
1H NMR (400 MHz, CDCl3): δ 9.21 (s, 1H), 8.76 (s, 2H),
7.47 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H). 13C NMR
(100 MHz, CDCl3): δ 158.1, 156.7, 135.2, 133.9, 133.2, 128.9,
128.8. Elemental analysis: calcd (%) for C10H5Cl3N2 (259.52):
C 46.28, H 1.94; found: C 46.41, H 2.01.
3-(2,5-Dichlorophenyl)-quinoline (24)
2′,5′-Dichlorobiphenyl-4-carbonitrile (19)
From 3-bromoquinoline (0.208 g,
dichlorobenzene (0.441 g, 3 mmol), 24 was obtained in 55%
(0.151 g) yield.
1 mmol) and 1,4-
From 4-bromobenzonitrile (0.182 g,
dichlorobenzene (0.441 g, 3 mmol), 19 was obtained in
48% (0.119 g) yield.
1 mmol) and 1,4-
1H NMR (400 MHz, CDCl3): δ 8.94 (s, 1H), 8.20 (s, 1H),
8.16 (d, J = 8.1 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.74 (t, J =
7.9 Hz, 1H), 7.57 (t, J = 7.9 Hz, 1H), 7.41 (d, J = 9.0 Hz, 1H),
7.38 (d, J = 2.4 Hz, 1H), 7.29 (dd, J = 9.0, 2.4 Hz, 1H).
13C NMR (100 MHz, CDCl3): δ 149.4, 145.7, 137.8, 137.6,
133.2, 131.5, 131.4, 131.3, 131.2, 131.0, 129.8, 128.2, 128.1,
127.8, 127.6. Elemental analysis: calcd (%) for C15H9Cl2N
(274.14): C 65.72, H 3.31; found: C 65.67, H 3.17.
1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 8.0 Hz, 2H), 7.46
(d, J = 8.0 Hz, 2H), 7.36 (d, J = 9.0 Hz, 1H), 7.28–7.23 (m, 2H).
13C NMR (100 MHz, CDCl3): δ 142.6, 140.0, 133.0, 132.0,
131.4, 130.8, 130.6, 130.1, 129.6, 118.5, 112.1. Elemental anal-
ysis: calcd (%) for C13H7Cl2N (248.11): C 62.93, H 2.84; found:
C 62.74, H 2.71.
2,5-Dichloro-4′-nitrobiphenyl (20)13
2′,4′-Dichlorobiphenyl-4-carbonitrile (25)
From 4-bromonitrobenzene (0.202 g, 1 mmol) and 1,4-
dichlorobenzene (0.441 g, 3 mmol), 20 was obtained in
40% (0.107 g) yield.
From 4-bromobenzonitrile (0.182 g,
dichlorobenzene (0.441 g, 3 mmol), 25 was obtained in 34%
(0.084 g) yield.
1 mmol) and 1,3-
1H NMR (400 MHz, CDCl3): δ 8.24 (d, J = 8.3 Hz, 2H), 7.53
(d, J = 8.3 Hz, 2H), 7.38 (d, J = 9.0 Hz, 1H), 7.30–7.23 (m, 2H).
1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 8.0 Hz, 2H), 7.46
(d, J = 8.0 Hz, 2H), 7.45 (d, J = 1.9 Hz, 1H), 7.28 (dd, J = 8.3,
1.9 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H). 13C NMR (100 MHz,
CDCl3): δ 142.8, 137.2, 135.0, 133.0, 132.0, 131.7, 130.2, 130.1,
127.5, 118.6, 111.9. Elemental analysis: calcd (%) for
C13H7Cl2N (248.11): C 62.93, H 2.84; found: C 63.07, H 3.04.
2′,5′-Dichlorobiphenyl-4-carbaldehyde (21)
From 4-bromobenzaldehyde (0.185 g, 1 mmol) and 1,4-
dichlorobenzene (0.441 g, 3 mmol), 21 was obtained in
38% (0.095 g) yield.
1H NMR (400 MHz, CDCl3): δ 10.02 (s, 1H), 7.90 (d, J =
8.0 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 9.0 Hz, 1H),
7.28 (d, J = 2.4 Hz, 1H), 7.25 (dd, J = 9.0, 2.4 Hz, 1H).
13C NMR (100 MHz, CDCl3): δ 191.8, 144.1, 140.7, 135.8,
132.9, 131.3, 130.9, 130.7, 130.1, 129.6, 129.3. Elemental
4-(2,5-Dichlorothiophen-3-yl)-benzonitrile (30)
From 4-bromobenzonitrile (0.182 g,
1 mmol) and 2,5-
dichlorothiophene (0.306 g, 2 mmol), 30 was obtained in
63% (0.160 g) yield.
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1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.0 Hz, 2H), 7.63
(d, J = 8.0 Hz, 2H), 6.91 (s, 1H). 13C NMR (100 MHz, CDCl3):
δ 137.7, 136.2, 132.4, 129.0, 127.4, 126.8, 123.6, 118.5, 111.7.
Elemental analysis: calcd (%) for C11H5Cl2NS (254.14): C 51.99,
H 1.98; found: C 52.12, H 2.14.
134.8, 134.2, 129.6, 127.5, 126.8, 123.5, 123.3, 122.8. Elemental
analysis: calcd (%) for C10H5Cl2NO2S (274.12): C 43.81, H 1.84;
found: C 43.67, H 1.70.
2-(2,5-Dichlorothiophen-3-yl)-benzonitrile (36)
From 2-bromobenzonitrile (0.182 g,
dichlorothiophene (0.306 g, 2 mmol), 36 was obtained in
81% (0.205 g) yield.
1 mmol) and 2,5-
1-[4-(2,5-Dichlorothiophen-3-yl)-phenyl]-ethanone (31)
From 4-bromoacetophenone (0.199 g, 1 mmol) and 2,5-
dichlorothiophene (0.306 g, 2 mmol), 31 was obtained in
48% (0.130 g) yield.
1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 8.0 Hz, 1H), 7.67
(t, J = 7.6 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.49 (t, J = 7.6 Hz,
1H), 6.94 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 136.8, 134.9,
133.4, 132.7, 130.7, 128.7, 127.2, 127.1, 125.0, 117.6, 112.5.
Elemental analysis: calcd (%) for C11H5Cl2NS (254.14): C 51.99,
H 1.98; found: C 52.07, H 1.84.
1H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 8.0 Hz, 2H), 7.62
(d, J = 8.0 Hz, 2H), 6.94 (s, 1H), 2.63 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ 197.4, 137.8, 137.0, 136.3, 128.6, 128.5,
127.1, 127.0, 123.0, 26.6. Elemental analysis: calcd (%) for
C12H8Cl2OS (271.16): C 53.15, H 2.97; found: C 53.29, H 3.09.
2,5-Dichloro-3-(2-nitrophenyl)-thiophene (37)
2,5-Dichloro-3-(4-nitrophenyl)-thiophene (32)
From 2-bromonitrobenzene (0.202 g, 1 mmol) and 2,5-
dichlorothiophene (0.306 g, 2 mmol), 37 was obtained in
67% (0.183 g) yield.
From 4-bromonitrobenzene (0.202 g, 1 mmol) and 2,5-
dichlorothiophene (0.306 g, 2 mmol), 32 was obtained in
70% (0.192 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.04 (d, J = 8.0 Hz, 1H), 7.67
(t, J = 7.6 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.42 (t, J = 7.6 Hz,
1H), 6.77 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 148.8, 134.1,
132.9, 132.3, 129.5, 128.2, 127.0, 126.8, 124.7, 123.9. Elemen-
tal analysis: calcd (%) for C10H5Cl2NO2S (274.12): C 43.81,
H 1.84; found: C 44.03, H 1.97.
1H NMR (400 MHz, CDCl3): δ 8.29 (d, J = 8.5 Hz, 2H), 7.69
(d, J = 8.5 Hz, 2H), 6.95 (s, 1H). 13C NMR (100 MHz, CDCl3):
δ 147.2, 139.5, 135.8, 129.2, 127.6, 126.8, 123.9, 123.8.
Elemental analysis: calcd (%) for C10H5Cl2NO2S (274.12):
C 43.81, H 1.84; found: C 43.98, H 1.89.
4-(2,5-Dichlorothiophen-3-yl)-benzaldehyde (33)
4-(2,5-Dichlorothiophen-3-yl)-isoquinoline (38)
From 4-bromobenzaldehyde (0.185 g, 1 mmol) and 2,5-
dichlorothiophene (0.306 g, 2 mmol), 33 was obtained in
64% (0.164 g) yield.
From 4-bromoisoquinoline (0.208 g,
dichlorothiophene (0.306 g, 2 mmol), 38 was obtained in
78% (0.218 g) yield.
1 mmol) and 2,5-
1H NMR (400 MHz, CDCl3): δ 10.05 (s, 1H), 7.94 (d, J =
8.0 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H), 6.95 (s, 1H). 13C NMR
(100 MHz, CDCl3): δ 191.6, 139.1, 136.8, 135.5, 129.9, 128.9,
127.2, 127.0, 123.3. Elemental analysis: calcd (%) for
C11H6Cl2OS (257.14): C 51.38, H 2.35; found: C 51.09, H 2.20.
1H NMR (400 MHz, CDCl3): δ 9.29 (s, 1H), 8.49 (s, 1H),
8.05 (d, J = 8.0 Hz, 1H), 7.75–7.60 (m, 3H), 6.90 (s, 1H). 13C
NMR (100 MHz, CDCl3): δ 153.0, 143.8, 134.1, 134.0, 130.9,
128.4, 128.1, 127.5, 127.0, 125.1, 124.9, 124.4. Elemental anal-
ysis: calcd (%) for C13H7Cl2NS (280.17): C 55.73, H 2.52;
found: C 55.49, H 2.31.
3-(2,5-Dichlorothiophen-3-yl)-benzonitrile (34)
Acknowledgements
From 3-bromobenzonitrile (0.182 g,
dichlorothiophene (0.306 g, 2 mmol), 34 was obtained in
66% (0.168 g) yield.
1 mmol) and 2,5-
We are grateful to the “Chinese Scholarship Council” for a
grant to Z. L. and to the “Fondation Rennes 1” for a master
grant to T. Y. We thank CNRS and “Rennes Metropole” for
providing financial support.
1H NMR (400 MHz, CDCl3): δ 7.81 (s, 1H), 7.75 (d, J =
8.0 Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H),
6.90 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 135.7, 134.5,
132.6, 131.8, 131.4, 129.5, 127.4, 126.8, 123.2, 118.4, 112.9.
Elemental analysis: calcd (%) for C11H5Cl2NS (254.14): C 51.99,
H 1.98; found: C 52.20, H 2.17.
Notes and references
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From 3-bromonitrobenzene (0.202 g, 1 mmol) and 2,5-
dichlorothiophene (0.306 g, 2 mmol), 35 was obtained in
60% (0.164 g) yield.
1H NMR (400 MHz, CDCl3): δ 8.39 (s, 1H), 8.22 (d, J =
8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.62 (t, J = 7.6 Hz, 1H),
6.96 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 148.4, 135.6,
This journal is © The Royal Society of Chemistry 2014
Catal. Sci. Technol., 2014, 4, 352–360 | 359

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Paper
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360 | Catal. Sci. Technol., 2014, 4, 352–360
This journal is © The Royal Society of Chemistry 2014