Synthesis of substituted 4,4′-dihalobiphenyls and their use for the preparation of isomeric bis(carbazolyl)biphenyls

Article abstract of DOI:10.1007/s11172-015-1104-2

Model compounds of some polychlorobiphenyl congeners, viz., 4,4′-dihalobiphenyls, were synthesized. These compounds can be successfully utilized by a chemical method for the in situ generation of arynes followed by the reaction with carbazole in order to prepare appropriate bis(carbazolyl)biphenyls as components for molecular electronics and OLED devices.

Full text of DOI:10.1007/s11172-015-1104-2

Russian Chemical Bulletin, International Edition, Vol. 64, No. 8, pp. 1978—1981, August, 2015
1978
Synthesis of substituted 4,4´ꢀdihalobiphenyls and their use
for the preparation of isomeric bis(carbazolyl)biphenyls*
I. S. Kovalev,a D. E. Pavlyuk,a V. A. Zaripov,a G. V. Zyryanov,a,b D. S. Kopchuk,a,b
V. L. Rusinov,a,b and O. N. Chupakhina,b
aUral Federal University named after the first President of Russia B. N. Yeltsin,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Eꢀmail: gvzyryanov@gmail.com
bI. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
20 ul. S. Kovalevskoi, 620219 Ekaterinburg, Russian Federation.
Eꢀmail: chupakhin@ios.uran.ru
Model compounds of some polychlorobiphenyl congeners, viz., 4,4´ꢀdihalobiphenyls, were
synthesized. These compounds can be successfully utilized by a chemical method for the in situ
generation of arynes followed by the reaction with carbazole in order to prepare appropriate
bis(carbazolyl)biphenyls as components for molecular electronics and OLED devices.
Key words: polychlorobiphenyls, 4,4´ꢀdihalobiphenyls, arynes, carbazole, bis(carbꢀ
azolyl)biphenyls.
Polychlorobiphenyls (PCB) and other halogenated
instance, we have described the reaction of halogenꢀsubꢀ
stituted benzenes with amines giving substituted anilines.14
It was established17 that the reaction proceeds through the
generation of arynes.
In the present work, we synthesized model compounds
of some PCB congeners, viz., 4,4´ꢀdihalobiphenyls, and
studied their reactions with carbazole as the Nꢀnucleoꢀ
phile.18 The expected reaction product is 4,4´ꢀbis(carbꢀ
azolyl)biphenyl, which is an important component of moꢀ
lecular electronics and OLED devices.19
The starting 4,4´ꢀdihalobiphenyls were initially synꢀ
thesized by the classical Sandmeyer reaction20 with benzꢀ
idine hydrochloride. However, target compounds 1a—c
were obtained in yields lower than 10%. A good alternative
was a modified procedure21 based on the reaction of benzꢀ
idine with isoamyl nitrite in DMSO in the presence of
paraꢀalkylbenzenesulfonic acids followed by the reaction
with anhydrous copper halides or potassium iodide. In
this case, the target 4,4´ꢀdihalobiphenyls were isolated in
yields of up to 85% (Scheme 1).
In the present study, we investigated the behavior of
copper(I) and copper(II) halides in this reaction. We found
that the use of more readily available copper(II) halides
instead of copper(I) bromide or chloride did not lead to
a considerable decrease in the yield of the target compounds.
Therefore, subsequent experiments were carried out with
copper(II) compounds.
derivatives of biphenyl are environmentally hazardous priꢀ
marily due to their high carcinogenic potential for living
organisms, extremely high toxicity, and rather long halfꢀ
life.1—4 According to the effect of the exposure of PCB and
its derivatives in humans, these compounds are assigned
to soꢀcalled xenoestrogens.5,6 The distinguishing feature
of the latter is the ability to disrupt the normal function of
the human endocrine system.7 Therefore, the developꢀ
ment of methods for the chemical utilization of PCB comꢀ
ponents is a topical problem. Chemical methods are based
mainly on the nucleophilic substitution of chlorine in PCB
components to form solid components easily utilizable by
chemical or biological methods. This is most commonly
performed by means of various Oꢀnucleophiles in the presꢀ
ence of alkali metals (for example, sodium methoxide was
used to completely convert congeners** of the Sovol techꢀ
nical mixture8), alkaline melting of PCB,2,3,9 derivatives
of ethylene glycol,2,3,10 etc. Meanwhile, in the presence of
strong bases, haloarenes can efficiently generate arynes
in situ, and the latter readily react with a wide range of
substrates to form substitution products,11—15 cycloaddiꢀ
tion products,11—15 or transformation products.11,12,16 For
* Based on the materials of the XXVI International Chugaev
Conference on Coordination Chemistry (October 6—10, 2014,
Kazan).
** Congener is a component of a PCB mixture containing multiꢀ
ple isomers at different degrees of chlorination and with differꢀ
ent arrangement of chlorine atoms in aromatic nuclei. There is
a total of 209 congeners.
In order to perform the reactions of carbazole with
arynes, the latter were generated by procedures, which we
have described earlier.14,17 As expected, the reaction of
4,4´ꢀdihalobiphenyls with potassium tertꢀbutoxide 1 and
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1978—1981, August, 2015.
1066ꢀ5285/15/6408ꢀ1978 © 2015 Springer Science+Business Media, Inc.

Synthesis of 4,4´ꢀdihalobiphenyls
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 8, August, 2015
1979
Scheme 1
Scheme 2
Hal = Cl (a), Br (b), I (c)
R = Me, nꢀC12H25
Reagents and conditions: 1) isoꢀC5H11ONO, pꢀRC6H4SO3H,
DMSO, 20 C  100 C; 2) CuHal2 (a, b), KI (c).
carbazole in toluene at 130—140 C afforded isomeric
bis(carbazolyl)biphenyls 2 in yields of up to 90%. The
reaction proceeds through the in situ generation of arynes.
The degree of conversion and regioselectivity of the subseꢀ
quent reaction of arynes with carbazole depends on the
type of the halogen atom. Thus, 4,4´ꢀbis(carbazolyl)ꢀ
biphenyl 2a was obtained in the highest yields (up to 90%)
for Hal = Cl (compound 1a). Since the carbazole moiety
can be attached at two positions of the starting aryne, the
reaction gave isomeric products, viz., 3,3´ꢀbis(carbazolꢀ
yl)biphenyl 2b (in a yield of up to 5%) and 4,3´ꢀbisꢀ
(carbazolyl)biphenyl 2c (2%).22 The similar reaction of 1b
produced compounds 2a, 2b, and 2c in 77, 8.5, and 4%
yields, respectively. The reaction of the aryne generated
from 4,4´ꢀiodobiphenyl 1c with carbazole is the least effiꢀ
cient and gave a mixture of several products, including the
target 4,4´ꢀbis(carbazolyl)biphenyl 2a (60%); bis(carbꢀ
azolyl)biphenyls 2b and 2c were obtained in trace amounts
(Scheme 2).
Hal = Cl (a), Br (b), I (c)
Reagents and conditions: ButOK, PhMe, 140 C; carbazole.
applications of the aboveꢀdescribed reactions are currentꢀ
ly underway.
Experimental
The 1H and 13C NMR spectra were recorded on a Bruker
Avanceꢀ400 spectrometer (400 and 100 MHz, respectively) with
SiMe4 as the internal standard. Gas chromatographyꢀmass
spectrometry was carried out on a SHIMADZU GCMSꢀQP2010
Ultra mass spectrometer. Massꢀspectrometric studies were perꢀ
formed on a MicrOTOFꢀQ II mass spectrometer (Bruker Dalꢀ
tonics, Bremen, Germany) using a KD Scientific syringe pump
for direct inlet (the flow rate was 180 L h–1). The melting
points are uncorrected. The starting compounds are commerꢀ
cially available.
Synthesis of 4,4´ꢀdihalobiphenyls (general procedure). Methꢀ
od A: Sandmeyer reaction. Benzidine (2.10 g, 11.4 mmol) was
dissolved with heating in 5% hydrochloric acid (300 mL). Actiꢀ
vated carbon was added to the solution heated to 80 C, and the
solution was filtered. A aqueous solution (40 mL) of sodium
nitrite (1.95 g, 28.5 mmol) was added portionwise to the benzꢀ
idine solution cooled to 0 C, the temperature of the reaction
mixture being maintained at no higher than 5 C. The solution
was allowed to stand for 15 min, and then a suspension of the
appropriate cuprous salt (30 mmol) in water (50 mL) was added.
The solution was stirred at room temperature for 30 min and
then heated to 80 C. The product was extracted with dichloroꢀ
methane (3×100 mL), and the extracts were concentrated to
dryness.
The structures of the reaction products were reliably
1
confirmed by H and 13C NMR spectroscopy and mass
spectrometry. Thus, the 1H NMR spectra show signals
for protons of the aromatic and carbazole moieties at
 7.36—8.16. The ESI mass spectra of compounds 2 have
a molecular ion peak.
In summary, in the present work we synthesized model
compounds of some polychlorobiphenyl congeners in orꢀ
der to study the reactivity of these compounds in the deꢀ
hydrohalogenation with in situ generated arynes. It was
shown that these model compounds, which are compoꢀ
nents of anthropogenic wastes, can be in principle used for
the synthesis of isomeric bis(carbazolyl)biphenyls, which
are practically valuable as components of molecular elecꢀ
tronics and OLED devices. Investigations of further

1980
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 8, August, 2015
Kovalev et al.
Method B. Isoamyl nitrite (30 mmol) and DMF (20 mL)
were placed in a 100 mL Erlenmeyer flask. Benzidine (1.99 g,
10.8 mmol) and paraꢀtoluenesulfonic acid (4.13, 24 mmol) were
separately dissolved in DMF (20 mL). The solutions of benzꢀ
idine and paraꢀtoluenesulfonic acid were added with stirring to
the solution of isoamyl nitrite. The reaction mixture was stirred
at room temperature for 10 min. Freshly calcinated copper(II)
chloride (3.22 g, 24 mmol) was added into the flask. The reacꢀ
tion mixture was heated to 100 C and allowed to stand for 1 h.
Then the mixture was cooled to room temperature and diluted
with water to 500 mL. The precipitate was filtered off and washed
with water.
126.1, 126.0, 125.9, 125.6, 123.4, 120.3, 120.2 120.0, 109.7.
ESIꢀMS, m/z (Irel (%)): 485.20 [M + H]+ (100).
This study was financially supported by the Ministry of
Education and Science of the Russian Federation (State
Contract 8430), the Council on Grants at the President of
the Russian Federation (Program for State Support of
Leading Scientific Schools of the Russian Federation and
Young Scientists, Grant MKꢀ3079.2015.3), and the Govꢀ
ernment of the Russian Federation (Program 211, agreeꢀ
ment No. 02.A03.21.0006).
Method C. The experiment was performed by the method B
in DMSO using paraꢀdodecylbenzenesulfonic acid.
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Synthesis of 4,4´ꢀdihalobiphenyls
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Received December 22, 2014;
in revised form April 7, 2015