Designed Monomers and Polymers

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Improved synthesis of 4-bromo-2,2'-bipyridine:

a start material for low-molecular-weight model
compounds

Daniel Ayuk Mbi Egbe , Atef Mohamed Amer & Elisabeth Klemm

To cite this article: Daniel Ayuk Mbi Egbe , Atef Mohamed Amer & Elisabeth Klemm
(2001) Improved synthesis of 4-bromo-2,2'-bipyridine: a start material for low-molecular-
weight model compounds , Designed Monomers and Polymers, 4:2, 169-175, DOI:
10.1163/156855500300203386

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Published online: 02 Apr 2012.

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Designed Monomers and Polymers, Vol. 4, No. 2, pp. 169– 175 (2001)
Ó VSP 2001.

Paper

’
Improved synthesis of 4-bromo-2,2 -bipyridine: a start
material for low-molecular-weight model compounds

DANIEL AYUK MBI EGBE, ATEF MOHAMED AMER

and ELISABETH KLEMM ¤
Institut für Organische Chemie und Makromolekulare Chemie der Friedrich-Schiller-Universität
Jena, Humboldtstrasse 10, D-07743 Jena, Germany

Abstract—An improved and simpliŽ ed synthetic method for 4-bromo-2,20 -bipyridine (5) has opened
a way to the synthesis of the model compounds 8a, b of polymer 9. 8a, b conŽ rmed the effective
conjugation segment of polymer 9 to consist of an alternation of three aryl and two ethynyl units
(Ar C C Ar C C Ar) due to the zig-zag structure of the polymer. It was found to be the
smallest conjugated unit necessary to obtain excellent  uorescence.

Keywords: 4-Bromo-2,20 -bipyridine; 1,4-diethynylbenzene; effective conjugation segment;  uores-

cence.

1. INTRODUCTION
With the goal of conŽ rming the effective conjugation segment of the zig-zag
orientated meta-conjugated polymer 9 [1], it was necessary to synthesize model
compounds 8a, b and investigate their photophysical properties. The synthesis of
8a, b requires 4-bromo-2,20 -bipyridine (5) as the starting material. However, we
encountered some difŽ culties while trying to prepare 5.

2. EXPERIMENTAL
All chemicals were purchased from Fluka. Melting points were measured on
a Büchi 530 melting apparatus. Mass spectroscopy was performed as chemical
ionization with H2 O vapour as gas on a Finnigan Mat SSQ 710. 1 H- and
13
C-NMR spectra were recorded on a Bruker AC 250. The chemical shifts, ±,

¤ To
whom correspondence should be addressed. E-mail: c5ayda@uni-jena.de or c9klel@rz.uni-
jena.de
170 D. A. M. Egbe et al.

are given in ppm related to tetramethylsilane as internal standard. The coupling

constants, J , are reported in Hz. A Nicolet Impact 400 was used for infrared
spectroscopy and KBr was the technique used. Elemental analysis was perfomed on
a CHNS-932 Automat Leco. Absorption spectra were taken in dioxane on a Perkin
Elmer UV/VIS-NIR Spectrometer Lambda 19. Emission spectra were obtained
from an LS 50 Luminescence Spectrometer (Perkin Elmer).

2.1. 2,20 -Bipyridyl-1-oxide (2)

A solution of 2,20 -bipyridine (1) (23.2 g, 148.5 mmol) and m-chloroperbenzoic acid
(30.34 g, 148.5 mmol) in 250 ml of CHCl3 was stirred at 40 ± C for 24 h. The mixture
was washed three times with 150 ml portions of 5% Na2 CO3 and the aqueous phase
was extracted three times with 100 ml portions of CHCl3 . The combined organic
phases were dried over MgSO4 and evaporated under vacuum. The residue was
chromatographed on a silica gel column, with MeOH/EtOAc (1 : 4) as the eluant.
The pure product was obtained at Rf D 0:47. Evaporation of the solvent gave
17.25 g (67%) of 2. M.p. 54 ± C (ref. [7]: 57– 58 ± C). MS: m=z D 172 (MC , 100%),
144 (45%), 78 (45%). 1 H-NMR (250 MHz, CDCl3 ): ±=ppm D 7:20– 7:31 (3H, m,
4-H, 5-H, 50 -H), 7.79 (1H, ddd, J40 ;30 D J40 ;50 D 7:8 Hz, J40 ;60 D 1:7 Hz, 40 -H),
8.13 (1H, dd, J3;4 D 7:9 Hz, J3;5 D 2:1 Hz, 3-H), 8.27 (1H, d, J6;5 D 6:4 Hz,
6-H), 8.68 (1H, d, J60 ;50 D 4:7 Hz, 60 -H), 8.85 (1H, d, J30 ;40 D 8:1 Hz, 30 -H).
13
C-NMR (62 MHz, CDCl3 ): ±=ppm D 124:2, 125.2, 125.4, 125.6, 127.8, 136.2,
140.6, 149.3, 149.6. IR (KBr): º=cm¡1 D 1251 (s, pyridyl N O). Analysis: C10 H8
N2 O (172.18). Calc.: C, 69.76; H, 4.68; N, 16.27. Found: C, 69.62; H, 4.86;
N, 15.96.

2.2. 4-Nitro-2,20 -bipyridyl 1-oxide (3)

A solution of 2,20 -bipyridyl 1-oxide (2) (10 g, 58 mmol) in concentrated sulfuric
acid (40 ml) was cooled to ¡10 ± C. Fuming sulfuric acid (65%; 8 ml) and 100%
fuming nitric acid (24 ml) were added to the solution. The mixture was heated
for 10 h under re ux. After cooling to room temperature, it was poured onto
100 g of ice and neutralized with NaOH pellets under cooling. The precipitate
was collected by Ž ltration, washed extensively with water, and recrystallized from
ethanol. Yield: 4.8 g (38%). M.p. 178– 180 ± C (ref. [6]: 181 ± C). MS: m=z D 271
(MC , 70%), 171 (50%), 143 (100%), 116 (72%), 78 (70%). 1 H-NMR (250 MHz,
CDCl3 ): ±=ppm D 7:40 (1H, ddd, J50 ;40 D 7:6 Hz, J50 ;60 D 4:8 Hz, J50 ;30 D 1:2 Hz,
50 -H), 7.84 (1H, ddd, J40 ;50 D J40 ;30 D 7:2 Hz, J40 ;60 D 1:8 Hz, 40 -H), 8.03 (1H,
dd, J5;6 D 7:2 Hz, J5;3 D 3:3 Hz, 5-H), 8.33 (1H, d, J6;5 D 7:2 Hz, 6-H), 8.76
(1H, d, J60 ;50 D 4:2 Hz, 60 -H), 8.85 (1H, d, J30 ;40 D 8:2 Hz, 30 -H), 9.13 (1H, d,
J3;5 D 3:3 Hz, 3-H). 13 C-NMR (62 MHz, CDCl3 ): ±=ppm D 118:8, 122.5, 125.1,
125.3, 136.6, 141.9, 142.4, 147.5, 148.2, 149.8. IR (KBr): º=cm¡1 D 1515 (vs, ºas
and ºs N O), 1345 (vs, aryl-N O), 1290 and 1277 (pyridyl-N O). Analysis:
 Improved synthesis of 4-bromo-2,20 -bipyridine 171

C10 H7 N3 O3 (217.18). Calc.: C, 55.30; H, 3.24; N, 19.34. Found: C, 55.55; H, 3.58;

N, 19.21.

2.3. 4-Bromo-2,20 -bipyridine (5)

4-Nitro-2,20 -bipyridyl 1-oxide (3) (1.0 g, 4.6 mmol) was dissolved in 20 ml of
glacial acetic acid. While stirring, acetyl bromide (5 ml) was added. After a
short while, a yellow precipitate was formed. Phosphorus tribromide (5 ml) was
added to the resulting suspension; this caused the precipitate to dissolve again a
few minutes later after heating at 40 ± C. The solution was heated under re ux for
1 h, whereby a new precipitate was formed which became viscous and stuck to the
bottom of the  ask. After cooling to room temperature, the solution was decanted
and the remaining sticky residue was dissolved in water. The acid solution was
neutralized to pH 9 with concentrated NaOH and extracted three times with 30 ml
portions of CHCl3 . The organic phase was dried (MgSO4 ) and evaporated under
vacuum. The resulting yellow oil crystallized upon standing. The crude product
was puriŽ ed by sublimation to yield 0.9 g (82%) of colorless crystals. M.p. 51 ± C
(ref. [3]: 51–52 ± C). MS: m=z D 236, 234 (MC , 60%), 155 (MC – Br, 100%),
128 (40%), 78 (30%). 1 H-NMR (250 MHz, CDCl3 ): ±=ppm D 7:31 (1H, ddd,
J50 ;40 D 7:5 Hz, J50 ;60 D 4:9 Hz, J50 ;30 D 1:0 Hz, 50 -H), 7.44 (1H, dd, J5;6 D 5:2 Hz,
J5;3 D 1:9 Hz, 5-H), 7.80 (1H, ddd, J40 ;30 D J40 ;50 D 7:7 Hz, J40 ;60 D 1:7 Hz, 40 -H),
8.35 (1H, d, J30 ;40 D 8:0 Hz, 30 -H), 8.45 (1H, d, J60 ;50 D 5:2 Hz, 60 -H), 8.59 (1H, d,
J3;5 D 1:8 Hz, 3-H), 8.65 (1H, d, J6;5 D 4:4 Hz, 6-H). 13 C-NMR (62 MHz, CDCl3 ):
±=ppm D 121:2 (30 -C), 124.1 (3-C), 124.3 (50 -C), 126.7 (5-C), 133.7 (4-C), 136.8
(40 -C), 149.0 (60 -C), 149.6 (6-C), 154.5 (20 -C), 157.20 (2-C). Analysis: C10 H7 N2 Br
(234.22). Calc.: C, 51.09; H, 3.00; N, 11.92; Br, 33.98. Found: C, 51.18; H, 3.26;
N, 11.99; Br, 32.77.

2.4. 1,4-[40 -(20 ,200 -Bipyridylethynyl)]benzene (8a)

4-Bromo-2,20 -bipyridine (640 mg, 2.72 mmol), 1,4-diethynylbenzene (164 mg, 1.3
mmol), Pd(PPh3 )4 (63 mg, 0.053 mmol, 2 mol%), and CuI (12 mg, 0.053 mmol, 2
mol%) were added to a degassed solution of diisopropylamine (15 ml) and toluene
(45 ml) under an Ar atmosphere. The mixture was heated at 80 ± C for 20 h. After
cooling to room temperature, it was added dropwise to 400 ml of vigorously stirred
methanol. After stirring for 1 h, the precipitate was collected by Ž ltration, dissolved
in THF (50 ml), passed through a 2 ml plug of silica gel, and then poured once more
into excess methanol. The collected solid was recrystallized in a small amount of
THF. A light yellow crystalline solid was obtained. Yield: 420 mg (74%). MS:
m=z D 435 (MC , 70%), 263 (100%). 1 H-NMR (200 MHz, CDCl3 ): ±=ppm D 7:29
(2H, br), 7.40 (2H, br), 7.55 (4H, s), 7.81 (2H, t, J D 7:66 Hz), 8.55 (8H, br). IR
(KBr): 3065 (Caryl H, w), 2227 and 2206 (disubst. C C , w) cm¡1 . Analysis:
C30 H18 N4 (434.49). Calc.: C, 82.92; H, 4.17; N, 12.89. Found: C, 82.26; H, 4.26;
N, 12.64.
172 D. A. M. Egbe et al.

2.5. 1,4-(20 ,200-bipyridine-400 -ylethynyl)-2,5-dioctadecyloxybenzene (8b) [9]

3. RESULTS AND DISCUSSION

According to the literature, the desired product 5 can be obtained in two ways: a
one-pot reaction involving re uxing 4-nitro-2,20 -bipyridyl 1-oxide (3) in a mixture
of acetyl bromide and phosphorus tribromide [2, 3], or deoxygenation of the
isolated intermediate 4-bromo-2,20 -bipyridyl 1-oxide (4) in a two-step-reaction [4].
However, when we tried the Ž rst method (one-pot reaction), we isolated large
quantities of 4-nitro-2,20 -bipyridine (6) and only small amounts of 5. With the
second method (two-step reaction), we obtained mainly unreacted starting material
3 instead of 4 in the Ž rst step. Since the acetyl bromide that we used for the
reaction was from a freshly opened bottle, we thought about the possibility that the
authors had used partially hydrolyzed acetyl bromide which contained signiŽ cant
amounts of acetic acid in their successful attempts. Therefore, we added acetyl
bromide and phosphorus tribromide to a solution of 3 in acetic acid and isolated
crude 5 in a yield of 92% (46% [2]) after work-up (Scheme 1). We believe that
protonation of the N atom in the unsubstituted ring of 3 is essential for the reaction,
because it activates the molecule for the nucleophilic substitution of the nitro group
with the bromide anion. This assumption is supported by the work of Neumann
and Vögtle [5], who prepared 2,4,6-tribromopyridine by reacting a suspension
of 2,6-dibromo-4-nitropyridine-1-oxide in glacial acetic acid with acetyl bromide
and subsequently treating the obtained crude 2,4,6-tribromopyridine-1-oxide with
phosphorus tribromide in chloroform.
We could also simplify the synthesis of 2,20 -bipyridyl 1-oxide (2) starting from
2,20 -bipyridine (1) by combining the two literature procedures. The oxidation of 1
with m-chloroperbenzoic acid [6] and subsequent work-up by column chromatog-
raphy [7] gave 2 of high purity in a 67% yield in a much simpler procedure than
either of the two methods.
Model compounds 8a, b, obtained in yields of 74% and 90% respectively, were
prepared from the Sonogashira Pd-catalyzed cross-coupling reaction of
4-bromo-2,20 -bipyridine (5) and 1,4-diethynylbenzenes (7) in a 2 : 1 ratio, under
the same reaction conditions as those described for the synthesis of polymer 9 [1, 8]
(Scheme 2).

Scheme 1.
 Improved synthesis of 4-bromo-2,20 -bipyridine 173

Figure 1 depicts the UV–visible absorption spectra of the model compounds 8a, b
and polymer 9 in dioxane. There is a clear overlap of the longest wavelength
absorption maximum of the model compound with alkoxy side-chains, 8b (¸max D
386 nm), with that of the corresponding polymer 9 (¸max D 387 nm). This is due
to the well-deŽ ned effective conjugation segment (ECS) limited to the alternation
of three arylene and two ethynylene units ( Ar C C Ar C C Ar ) of the
zig-zag orientated meta-conjugated system (Fig. 2). The absorption maximum of

Scheme 2.

Figure 1. Absorption spectra of model compounds 8a, b and polymer 9 in dioxane.

174 D. A. M. Egbe et al.

Figure 2. Effective conjugation segment (thick lines) of polymer 9 and model compounds 8 and 10.

Table 1.
Absorption maximum (¸max ), extinction coefŽ cient ("/, emission maximum (¸em ), and  uorescence
quantum yield (Á ) of the model compounds 8a, b and polymer 9 in dioxane

Compound ¸max (nm) " (l mol¡1 cm¡1 ) ¸em (nm) Á (%)

8a 327 53 000 351 (370) 100
8b 386 30 000 430 90
9 387 29 000 433 43

model compound 8a, found at ¸max D 327 nm, is blue-shifted 61 nm relative to that
of 8b; this can be attributed to the lack of alkoxy side-groups in 8a. The alkoxy
side-chains are at the origin of the hyperchromic band found at 312 nm for 8b and
316 nm for 9. The bands at 370 nm for 8a and 450 nm for 8b and 9 are assigned to
intermolecular charge-transfer processes between phenylacetylene units as donors
and bipyridine units as acceptors.
The ECS mentioned above is a prerequisite to excellent  uorescence. Compound
10 [9], whose ECS consists of two arylene units and one ethynylene unit, shows vir-
tually no  uorescence. Data from absorption and emission spectra of the new com-
 Improved synthesis of 4-bromo-2,20 -bipyridine 175

pounds are given in Table 1. Electrochemical measurements in dichloromethane

present an oxidation potential of 1.54 V vs. Ag/ AgCl and and a reduction po-
tential of ¡1.0 V vs. Ag/AgCl for 8b and 9, thus making 9 a potentially good
electron-transporting material if used in multilayer light-emitting diode (LED) de-
vices [10, 11].

Acknowledgement
We thank the Deutsche Forschungsgemeinschaft for Ž nancial support.

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