New Approaches to the Synthesis of 2,2′: 6′,2″-Terpyridine and Some of Its Derivatives

Article abstract of DOI:10.1134/S1070428018030089

A new two-step procedure has been developed for the synthesis of 2,2′: 6′,2″-terpyridine and 4′-methylsulfanyl-2,2′: 6′,2″-terpyridine in more than 70% yield on the basis of Potts’ condensation. Efficient methods have been proposed for purification of all condensation products.

Full text of DOI:10.1134/S1070428018030089

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 3, pp. 419–425. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © V.V. Zamalyutin, V.A. Bezdenezhnykh, A.I. Nichugovskiy, V.R. Flid, 2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54,
No. 3, pp. 414–420.
Dedicated to Full Member of the Russian Academy of Sciences
I.P. Beletskaya on her jubilee
New Approaches to the Synthesis of 2,2′:6′,2″-Terpyridine
and Some of Its Derivatives
V. V. Zamalyutin,* V. A. Bezdenezhnykh, A. I. Nichugovskiy, and V. R. Flid
Lomonosov Institute of Fine Chemical Technologies Moscow Technological University,
pr. Vernadskogo 86, Moscow, 119571 Russia
*
e-mail: zamalyutin@mail.ru
Received December 14, 2017
Abstract—A new two-step procedure has been developed for the synthesis of 2,2′:6′,2″-terpyridine and
′-methylsulfanyl-2,2′:6′,2″-terpyridine in more than 70% yield on the basis of Potts’ condensation. Efficient
4
methods have been proposed for purification of all condensation products.
DOI: 10.1134/S1070428018030089
Nitrogen-containing heterocyclic compounds based
on 2,2′ :6′,2″-terpyridine (TerPy) have long been
known [1]. In recent time, interest in such compounds
has increased considerably due to broad spectrum of
their applications in various fields of science and
technology [2–12]. New monolayer electrochromic
materials have been designed on the basis of TerPy [2];
ruthenium(II) complexes with TerPy form supramolec-
ular metallopolymers possessing magnetic and con-
ducting properties [3]; platinum 2,2′:6′,2″-terpyridine
metallopolymer electrodes have been proposed as
an economically efficient substitute for bulk platinum
catalysts in the reduction of oxygen and conversion of
hydrogen [4, 5]. Nitrogen-containing ligands are used
in catalytic cross-coupling reactions [6]. The complex
TerPy–CoCl efficiently catalyzes Suzuki–Miyaura
2
cross-coupling [7]. Ruthenium(II) and platinum(II)
complexes with TerPy and its derivatives showed
antitumor activity [8] and luminescence properties [9];
they can be used as photosensitizers [10] and prom-
ising catalysts for the oxidation of water [11, 12] and
solar energy generation [13]; nickel(II) complexes with
TerPy are selective photocatalysts for the conversion
of carbon dioxide dissolved in water [14].
Scheme 1.
O
Alk
Ar
CHO
Alk
Ar
N
Base
Me
+
N
O
Alk
Alk
Ar
Alk
Alk
N
O
Me, base
N
AcONH , AcOH, ∆
O
4
O
Alk
N
N
N
N
Ar
Alk
4
19

4
20
ZAMALYUTIN et al.
Scheme 2.
SMe
N
Me
N
Ni(PPh )Cl2
MeMgBr
3
N
N
N
N
CHO
SeO2
MePPh Br, BuLi
3
N
N
N
CH2
N
N
Me
Me
Me
Me
N
Li
OMe
N
N
+
MeOCH Cl
t-BuOK
2
N
N
Nevertheless, 2,2′:6′,2″-terpyridine remains a dif-
2,2′:6′,2″-terpyridine, and the subsequent desulfuriza-
tion or replacement of the methylsulfanyl group gave
2,2′ :6′,2″-terpyridine or its derivatives in 30–50%
yield (Scheme 2) [19, 24, 25].
ficultly accessible reagent. Methods for the synthesis
of TerPy are fairly complex, and the yields are gen-
erally low (no more than 30–40%), which was noted in
publications on optimization of the synthetic proce-
dures [15–27]. The most widely used methods of
synthesis of 4′-aryl-substituted 2,2′:6′,2″-terpyridine
derivatives are those based on the Kröhnke condensa-
tion [15–21], which implies aldolization/crotonization
of 2-acetylpyridine with an aromatic aldehyde,
Michael addition of the second 2-acetylpyridine mole-
cule to the condensation product, and formation of the
,2′:6′,2″-terpyridine fragment (Scheme 1). However,
despite the possibility of one-step synthesis, the yield
of the condensation product is generally equal to 30–
0% due to subsequent isolation and multistep
purification [15–19].
Jameson and Guise [26] obtained 2,2′:6′,2″-ter-
pyridine in 47% yield by two-step synthesis based on
the Potts condensation. In the first step, the authors
used a solution of N,N-dimethylformamide dimethyl
acetal (DMFDMA) in toluene instead of more acces-
sible carbon disulfide. Treatment of 2-acetylpyridine
with that solution gave 86% of yellow crystalline
enaminone. The reaction was accompanied by libera-
tion of methanol which was gradually distilled off
from the reaction mixture. In the second step, potas-
sium enolate in THF was added, and the mixture was
refluxed with addition of ammonium acetate and
glacial acetic acid. The final product was formed in
an overall yield of 47% and was isolated as dark
crystals, which indicated the presence of impurities
2
5
An attractive laboratory procedure for the synthesis
of 2,2′:6′,2″-terpyridine and its 4′-substituted deriva-
tives is based on the Potts condensation [22–25] which
utilizes accessible reagents and solvent. The two-
step Potts condensation afforded 4′-methylsulfanyl-
[22, 24] (Scheme 3).
The synthesis of various 2,2′:6′,2″-terpyridines via
Stille cross-coupling can be regarded as the most
Scheme 3.
(
1) t-BuOK,
Me
N
O
Me NCH(OMe)
(2) NH OAc, HOAc
N
N
2
2
4
Me
NMe2
N
N
N
O
O
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 3 2018

NEW APPROACHES TO THE SYNTHESIS OF 2,2′:6′,2″-TERPYRIDINE
421
Scheme 4.
Pd(PPh3)4
Br
N
N
+
N
N
SnMe3
Br
N
Br
N
N
N
N
N
N
Cl
Cl
Pd(PPh3)4
N
Me Sn
N
N
3
+
N
N
N
N
N
Br
Br
N
Cl
Pd(PPh3)4
N
+
N
N
SnBu3
N
Cl
general approach to such systems [19, 27, 28]. The use
of trialkylstannylpyridines makes it possible to obtain
various products by introducing functional groups into
almost any position, and the overall yields exceed the
average values [19, 27, 28] (Scheme 4).
tion of several stable intermediate products which can
be isolated from the reaction mixture (Scheme 5).
2,2′:6′,2″-Terpyridine was obtained in [22] in three
steps. In the first step, the key intermediate, 3,3-bis-
(methylsulfanyl)-1-(pyridin-2-yl)prop-2-en-1-one (2)
was isolated in 61% yield as yellow crystalline solid
Despite obvious advantages of this method (yield
up to 70%) and thoroughly studied mechanism of the
Stille reaction [29], the experimental procedure is
complicated due to specific conditions necessary for
handling with organotin compounds, their high
toxicity, low accessibility of the reagents, and the use
of fairly expensive solvents and palladium-based
catalysts [25–29].
[22–26]. Compound 2 can be used to synthesize both
4
4
′-(methylsulfanyl)-2,2′:6′,2″-terpyridine (4) and its
- or 6-methyl derivatives [24]. Sodium hydride
(
a 50% suspension with dimethyl sulfoxide) [23] can
be used as a base instead of potassium tert-butoxide to
generate nucleophilic species (enolate ion). The second
step in the synthesis of 4′-(methylsulfanyl)-2,2′:6′,2″-
terpyridine (4) involves formation of several solid
intermediates 3; therefore, vigorous stirring is espe-
cially necessary in this step. Heating with ammonium
acetate in glacial acetic acid afforded 74% of 4. In the
third step, compound 4 was treated with an alkaline
solution of sodium tetrahydridoborate in the presence
of nickel(II) salt, and the target 2,2′:6′,2″-terpyridine
(5) was isolated in 60% yield. Thus, the overall yield
of 5 in three steps was about ~30%. Furthermore,
Thus, we can state that there are no procedures
ensuring the synthesis and purification of 2,2′:6′,2″-
terpyridine with an overall yield higher than 70% and
utilizing readily accessible reagents and solvents.
Taking into account fairly high cost [30] and low
accessibility of 2,2′:6′,2″-terpyridine, development of
such procedures would favor more detailed study of
its properties and considerable extension of its applica-
tion scope.
1
analysis of the H NMR spectra of the compounds
obtained in [22] clearly indicated the presence of
unidentified impurities in the products.
Herein, we report a new two-step procedure for the
synthesis of chemically pure 2,2′:6′,2″-terpyridine and
the corresponding intermediate products on the basis
of the Potts method [22–24]. The yield in each step
was higher than 70%. The synthesis involves forma-
The two-step procedure developed by us on the
basis of the Potts approach allowed us to achieve
an overall yield of chemically pure 2,2′:6′,2″-terpyri-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 3 2018

4
22
ZAMALYUTIN et al.
Scheme 5.
t-BuOK, CS , THF
MeI
2
–
S K+
Me
SMe
SMe
N
N
N
–
S K+
O
O
O
1
2
SMe
t-BuOK,
Me
N
NH OAc, AcOH, ∆
O
4
N
N
N
N
–
+
O
SMe O K
N
3
4
4
'
3
'
5'
6'
NaBH , [Ni(H O) ]Cl
EtOH, ∆
4
2
6
2
3
6
2'
2
2"
N
4
5
6"
N
N
3"
5
"
4"
5
dine of higher than 70% without preliminary isolation
of compound 2 (Scheme 6). This result was attained
due to the use of chemically pure reagents and
thoroughly dried solvent.
acetic acid promoted cyclization of 3 with formation of
a lustrous gray porous material containing compound
4. By extraction we isolated terpyridine 4 as a bright
yellow powder in 75% yield.
The yields of condensation products 2, 4, and 5
strongly depended on the purity of tetrahydrofuran
used as solvent. The presence of even traces water led
to low yields. The solvent was prepared in several
steps. It was initially checked for the presence of
peroxides and was then dried and distilled.
In the final step, compound 4 was treated with
an alkaline solution of 30 equiv of sodium tetrahy-
dridoborate in the presence of 10 equiv of nickel(II)
salt, and the reaction mixture was passed through
a layer of silica gel (Silicagel 60). The overall yield of
2,2′:6′,2″-terpyridine in two step was 71% calculated
on the initial 2-acetylpyridine.
To isolate chemically pure intermediate 2, the dark
material obtained according to Potts [22] (Scheme 5)
was purified by column chromatography using
an eluent preliminarily selected on the basis of the
TLC data. Yellow compound 2 was thus isolated in
Successive treatment of 2-acetylpyridine with
a suspension of 2.2 equiv of potassium tert-butoxide in
THF and carbon disulfide gave orange intermediate
dipotassium 3-oxo-3-(pyridin-2-yl)prop-1-ene-1,1-bis-
(
1
thiolate) (1) (see Scheme 5) which was alkylated with
equiv of methyl iodide to afford bright yellow com-
6
0% yield. The purity of compounds 2, 4, and 5 was
pound 2. Addition to the reaction mixture of the same
1
confirmed by H NMR spectra, elemental analyses,
and comparing their melting points with the reported
data.
amounts of t-BuOK and CS favored formation of
2
a red heterogeneous mixture of intermediate 3-(meth-
ylsulfanyl)-1,5-di(pyridin-2-yl)pent-2-ene-1,5-dione
and its potassium salt 3. Treatment of that mixture with
In summary, we have developed a new two-step
1
0 equiv of ammonium acetate and 23 equiv of glacial
method of synthesis of chemically pure 2,2′:6′,2″-ter-
Scheme 6.
SMe
(
(
(
(
1) t-BuOK, CS , THF
2) MeI
2
3) t-BuOK, CS , THF
NaBH
, [Ni(H O) ]Cl
4 2 6 2
2
4) NH OAc, HOAc, ∆
EtOH, ∆
4
N
Me
N
N
N
N
N
O
N
4
5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 3 2018

NEW APPROACHES TO THE SYNTHESIS OF 2,2′:6′,2″-TERPYRIDINE
423
pyridine and 4′-(methylsulfanyl)-2,2′:6′,2″-terpyridine
without isolation of 3,3-bis(methylsulfanyl)-1-(pyri-
din-2-yl)prop-2-en-1-one on the basis of the Potts con-
densation; the developed procedure ensures more than
for purification of THF. It was then dried using reagent
grade metallic sodium and benzophenone.
The elemental analyses were obtained on a Flash
EA 1112 ThermoQuest CHNS analyzer (Italy) with
a thermal conductivity detector (accuracy 0.2–0.3%).
The melting points of compounds 2, 4, and 5 were
measured in capillaries [31].
7
0% overall yield of the target product. Efficient
methods for purification of all condensation products
have been proposed. To achieve high yields, the
experimental setup should be purged with dry nitrogen
and protected from contact with the atmosphere. The
yields of the condensation product strongly depend on
the purity of the solvent (THF) and initial reactants.
1
13
The H and C NMR spectra were recorded on
a Bruker Avance DPX 300 spectrometer using the
residual proton (CHCl , δ 7.26 ppm) and carbon
3
signals of the solvent as reference.
EXPERIMENTAL
All reagents were purchased from Acros Organics
(
(
Belgium): 2-acetylpyridine (98%, USA), t-BuOK
All operations with the solvent and hygroscopic
substances were carried out in a 6BP1-OS dry box
charged with reagent grade P O . The setup for the
≥98%, USA), CS (≥99.9% for spectroscopy, UK),
2
methyl iodide (99%, stabilized by copper, UK),
NH OAc (reagent grade, Germany), glacial acetic acid
2
5
4
Potts condensation should be isolated from the atmo-
sphere. During the synthesis it was purged with dry
nitrogen which was vented through a hydraulic seal
containing concentrated sulfuric acid. Ultrapure nitro-
gen, grade 5.5 (technical specification 20.11.11.140-
HOAc (99.8%), NaBH (94.6%), [Ni(H O) ]Cl
4
2
6
2
(
reagent grade).
4
′-(Methylsulfanyl)-2,2′:6′,2″-terpyridine (4).
A 250-mL three-necked flask was charged with a solu-
tion of 4.14 g (0.0370 mol) of potassium tert-butoxide
in 100 mL of anhydrous THF, and 1.88 mL
0
09-45905715-2017, NII KM), was dried by passing
through a gas-washing bottle charged with concen-
trated sulfuric acid and through a Tishchenko bottle
charged with granular potassium hydroxide. In all
syntheses, the reaction mixtures were efficiently stirred
with an anchor type mechanical stirrer equipped with
a cylindrical ground joint lubricated with a silicone
grease.
(
0.0167 mol) of 2-acetylpyridine was added dropwise
over a period of 15 min. A light yellow solid separated
from the solution. Carbon disulfide, 1.01 mL
(
0.0167 mol), was then added over a period of 35 min
to obtain an orange viscous mixture, and 2.09 mL
0.0335 mol) of methyl iodide was added over a period
(
of 1 h. The resulting brown mixture was stirred for 7 h,
a solution of 4.14 g (0.0370 mol) of t-BuOK in 80 mL
of anhydrous THF and 1.88 mL (0.0167 mol) of
2
0
Refractive indices of the solvents (n ) were
D
–
5
measured with an accuracy of 5× 10 using an IRF-
54B2M laboratory refractometer. Thin-layer chroma-
4
2
-acetylpyridine were added, and the mixture was
tography was performed according to standard proce-
dure [31] on 1×5-cm aluminum plates coated with
unmodified Silicagel 60 containing Silica gel F254
green fluorescent indicator (Merck, Germany); prelim-
inarily distilled chloroform of chemically pure grade
stirred for 12 h. To the red suspension thus formed we
added 12.89 g (0.167 mol) of ammonium acetate and
2
2.36 mL (0.3906 mol) of glacial acetic acid, and THF
was distilled off over a period of 2 h. After cooling to
room temperature, the dark mixture was poured onto
(
Komponent-Reaktiv, Russia) was used as eluent; spots
were visualized under UV light. Silica gel (grain size
3–200 μm, pore diameter 60 Å; Sigma-Aldrich, USA)
5
1
0 g of ice, distilled water was added to a volume of
00 mL, and the mixture was left to stand for 2 h. The
6
gray solid was filtered off and dried in a vacuum
desiccator under reduced pressure (20°C, 0.1 mm) for
12 h. The dry gray material was Soxhlet extracted with
150 mL of hexane for 48 h. After cooling to room
temperature, 3.50 g (75%) of light yellow powder
separated from the extract, mp 117–119°C (118–119°C
was used for column chromatography [31].
The solvents used were tetrahydrofuran (≥99.98%,
Ashland, Switzerland), ethanol (95%, RFK), hexane
(
chemically pure), and chloroform-d (98% of deute-
rium, for NMR, Acros Organics, Belgium). The hy-
draulic seal and gas-washing bottle were charged with
concentrated sulfuric acid of chemically pure grade
1
[22]). H NMR spectrum (300 MHz), δ, ppm: 2.67 s
(3H, CH ), 7.35 d.d.d (2H, 6-H, 6″-H, J = 7.5, 4.8,
3
(
Khimmed, Russia). Reagent grade copper(I) chloride
1.2 Hz), 7.87 t.d (2H, 4′-H, 4″-H, J = 7.8, 1.8 Hz),
8.35 s (2H, 3′-H, 5′-H), 8.62 d.t (2H, 3-H, 3″-H, J =
and analytical grade potassium hydroxide were used
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 3 2018

4
24
ZAMALYUTIN et al.
8
0
1
1
.0, 1.0 Hz), 8.71 d.d.d (2H, 5-H, 5″-H, J = 4.8, 1.8,
7.78 d.d.d (1H, 3-H, J = 7.9, 0.9 Hz), 8.25 d.d.d
(1H, 6-H, J = 4.8, 1.8, 0.9 Hz). C NMR spectrum
1
3
13
.9 Hz). C NMR spectrum (75 MHz), δ , ppm:
C
4.05, 117.08, 121.57, 123.96, 137.16, 148.78, 152.68,
54.54, 155.63. Found, %: C 68.50; H 4.60; N 14.95.
(75 MHz), δ
, ppm: 14.07, 117.10, 121.58, 123.97,
C
137.18, 148.79, 152.70, 154.56, 155.65. Found, %:
C H N S. Calculated, %: C 68.79; H 4.69; N 15.04.
C 53.21; H 4.70; N 6.20. C10
C 53.30; H 4.92; N 6.22.
H11NOS . Calculated, %:
2
1
6
13
3
2
,2′ : 6′,2″-Terpyridine (5). A 500-mL three-
necked flask was charged with 120 mL of ethanol,
.0 g (0.0072 mol) of compound 4, and 17.12 g
0.072 mol) of finely powdered [Ni(H O) ]Cl . The
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 17-03-00463).
2
(
2
6
2
resulting green suspension was cooled to 0°C for 1 h in
an ice bath, and a solution of 8.16 g (0.216 mol) of
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 3 2018

NEW SYNTHETIC APPROACHES TO 2,2′:6′,2″-TERPYRIDINE
425
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