Synthesis of new macrocycles with 2,2′-bipyridyl and polyamine functions

Article abstract of DOI:10.1081/SCC-120023436

A series of macrocycles with two different complexing sites of the type 3,3′-AA-2,2′-bipyridine, where AA=CONHCH₂CH ₂NHCO, CONH(CH₂)₆NHCO, CONHCH ₂CH₂NHCH₂CH₂NHCO and CONHCH ₂CH₂CH₂NHCH₂CH₂CH ₂NHCO have been synthesized by high dilution method and characterized on the basis of elemental analysis, NMR, and infrared spectral data.

Full text of DOI:10.1081/SCC-120023436

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Synthesis of New Macrocycles with 2,2′-Bipyridyl and
Polyamine Functions
a
a
a
a
B. K. Kanungo , Minati Baral , S. Bhattacharya & Y. Sahoo
a
Department of Chemistry, Sant Longowal Institute of Engineering and Technology,
Longowal, Punjab, India
Published online: 17 Aug 2006.
To cite this article: B. K. Kanungo , Minati Baral , S. Bhattacharya & Y. Sahoo (2003): Synthesis of New Macrocycles with 2,2′-
Bipyridyl and Polyamine Functions, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:18, 3159-3164
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 18, pp. 3159–3164, 2003
Synthesis of New Macrocycles with
,2 -Bipyridyl and Polyamine Functions
0
2
B. K. Kanungo,* Minati Baral, S. Bhattacharya, and Y. Sahoo
Department of Chemistry, Sant Longowal Institute of
Engineering and Technology, Longowal, Punjab, India
ABSTRACT
A series of macrocycles with two different complexing sites of the
0
0
type 3,3 -AA-2,2 -bipyridine, where AA ¼ CONHCH CH NHCO,
2
2
CONH(CH
CONHCH
2
)
6
NHCO, CONHCH
CH CH NHCH CH CH
2
CH
2 2 2
NHCH CH NHCO and
2
2
2
2
2
2
NHCO have been synthesized
by high dilution method and characterized on the basis of elemental
analysis, NMR, and infrared spectral data.
Key Words:
*
Correspondence: B. K. Kanungo, Department of Chemistry, Sant Longowal
Institute of Engineering and Technology, Longowal, Punjab, India-148 106;
E-mail: b.kanungo@vsnl.com.
3
159
DOI: 10.1081/SCC-120023436
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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3
160
Kanungo et al.
Considerable attention has been focussed on the preparation and
properties of organic compounds behaving as multidentate heterocyclic
0
chelators containing 2,2 -bipyridyl unit which can be used for the prep-
aration of several mixed-metal and multimetallic complexes. Such com-
[
1–2]
pounds have significant importance as photocatalysts,
intermolecular and intramolecular energy and electron transfer processes
reactants in
[
3–5]
building blocks for the construction of supramolecular species.
Molecular systems containing several complexing functions may display
allosteric properties, a given site of the molecule being able to affect
complexion of another coordinating fragment. Such molecules on com-
plexion could also be used to transcribe ‘digital’ behaviours in the world
[6]
[7]
of molecules. As a pioneering work, Reback et al. reproduced an
artificial heterotropic allosterism with compound (I) where acrown
ether moiety (alkali metal binding site) and a bipyridine moiety (transi-
tion metal binding site) are allosterically coupled; chelation of metals at
the bipyridyl function forces the aromatic nuclei towards coplanarity,
thereby restricting the conformational freedom of the macrocycle.
This article describes the synthesis and characterization of four
0
new organic macrocycles (II–V) containing a 2,2 -bipyridyl subunit and
polyamine fragment, capable of exhibiting allosteric effect (Fig. 1).
RESULT AND DISCUSSION
0
0
The four new 3,3 -disubstituted 2,2 -bipyridyl macrocycles of the type
0
0
3
,3 -AA-2,2 -bipy where AA ¼ CONHCH CH NHCO, CONH(CH ) -
2
2
2 6
NHCO, CONHCH CH NHCH CH NHCO and CONHCH CH -
2
2
2
2
2
2
CH NHCH CH CH NHCO were synthesized by the reaction of
2
2
2
2
O
O
O
N
n
n
n
N
N
N
N
N
O
O
O
O
O
O
N
N
N
N
N
I
II (n=1), III(n=5)
IV(n=1), V(n-=2)
Figure 1. Schematic structures of macrocycles (I–V).

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Macrocycle Functions
3161
0
0
0
3,3 -bis(chlorocarbonyl)-2,2 -bipyridine, obtained in situ from 3,3 -
dicarboxy-2,2 -bipyridine (binicotinic acid, BNA) and appropriate
0
0
amines by high dilution method. Although the synthesis of 3,3 -
0
[8]
dicarboxy-2,2 -bipyridine was reported earlier, the yield was quite
[
9]
low(30%). The method reported by Shan et al. involved many more
steps with about 43.6% yield. Here we report a modified method for the
synthesis of BNA with about 78% yield. Though the compound BNA is
partially soluble in water, good NMR spectra was obtained in D O.
2
1
The C NMR, infra red and UV absorption spectra are reported
3
1
here in addition to the earlier reported H NMR. Proton NMR is
[
similar to that reported by Shan et al. but peak for the acidic proton
9]
0
(
–COOH) at 12.95 ppm was found to be absent. The compound 3,3 -
0
bis(chlorocarbonyl)-2,2 -bipyridine (DCBNA) was obtained by reacting
BNA with thionyl choride. Characterization of this compound was not
done in detail. However, complete conversion of BNA to its acid chloride
derivative was checked from its infrared spectra where the expected
À1
broad peak ranging from 2500–3500 cm for BNA, was missing and a
À1
sharp peak at ꢀ660.7 cm due to C-Cl stretching vibration was observed.
All the compounds (II–V) are highly air sensitive and manipulations
1
were done in nitrogen atmosphere. H NMR spectraof al l compounds
in D O gave three characteristic peaks for bipyridine ring. In all the
2
compounds reported in this communication, two absorption bands
appeared at ꢀ270 (band I) and ꢀ220 (band II) nm in the UV region
ꢁ
ꢁ
[10,12]
0
for 2,2 -
attributed to n ! ꢀ and p ! p transitions respectively
bipyridine ring.
EXPERIMENTAL
All reagents and solvents were of commercial purity grade. Reaction
requiring solvents were prepared under a nitrogen atmosphere prior to
use. All reactions were performed in oven dried glassware under an atmo-
1
13
sphere of dry nitrogen. H a nd C NMR spectrawere recorded on a
00 MHz Brucker DPX 300 NMR instrument. Chemical shifts are
reported as ꢁ values in units of ppm relative to the Me Si as internal
3
4
standard. Elemental analysis were preformed through RSIC. Melting
points were obtained on a capillary melting point apparatus and are
uncorrected. Infrared spectra were obtained in solid state as KBr pallet
on aPerkin Elmer Model RX-1 FT-IR Spectrophotometer. UV–visible
spectrawere obt ai ned using aSystronics Model 119 Computer control
UV-Visible Spectrophotometer.

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162
Kanungo et al.
0
0
Preparation of 3,3 -Dicarboxy-2,2 -bipyridine
A mixture of 1,10-phenanthroline (5.0 g, 0.025 mol), sodium hydrox-
ide (2.0 g, 0.05 mol) and potassium permanganate (11.85 g, 0.075 mol)
was taken in 300 mL distilled water and refluxed for 6 h with stirring. The
brown precipitate MnO was filtered while hot. The volume of the filtrate
2
was reduced to ꢀ120 mL on a rotary evaporator. The solution was boiled
with ꢀ2 g of decolorizing charcoal and filtered. Conc. HCl was added
drop wise to the filtrate while needle shaped crystals started forming at
pHꢀ3. Addition of HCl continued till the pH of the solution reached ꢀ2.
The white crystalline solid was filtered off, washed with water, ethanol
and dried in vacuo over CaCl . The filtrate was collected and the volume
2
was reduced to half and was left undisturbed overnight while more crys-
tals separated out. This process was repeated with the filtrates till no
ꢂ
more crystals came out. Yield ¼ 78%, m.p. 260 C (decomposed); lit
ꢂ
[11]
62 C and 250–252 C (decomposed).
ꢂ
[11] 1
2
H NMR: 8.68 (dd, 2H), 8.57
dd, 2H), 7.79 (t, 2H), 6.17 (s, 2H); C NMR (D O): 169.80, 153.65,
48.360, 142.451, 128.957, 125.957; IR (in cm ): 690, 756, 1220–1260
1
3
(
2
À1
1
(
br), 1434, 1578, 1723, 2500–3500 (br); elemental analyses (%):
C ¼ 59.22, N ¼ 11.37, H ¼ 3.31.
0
0
Preparation of 3,3 -bis(Chlorocarbonyl)-2,2 -bipyridine
one point four grams (0.005 mol) of binicotinic acid was taken in a
00 mL round bottom flask and to it 1.2 g (0.01 mol) thionyl chloride was
1
added drop wise. Care was taken during addition, so that all BNA
particles should come in contact with thionyl chloride. It was then
ꢂ
heated in oil bath maintaining temperature ꢀ90 C for 1 h till all HCl
expels out. The yellow color product obtained was quite stable to air.
Yield ¼ 98%, m.p. ¼ 250 C; IR (in cm ): 660, 1730.
ꢂ
À1
Preparation of Macrocycle II
Four hundred milliliters of dichloromethane and 1.5 g of TEA were
taken in a three necked flask. To it 1.3 g of DCBNA in 150 mL of dichlo-
romethane and 1.1 mL of 1,2-diaminoethane in 50 mL of dichloromethane
were added portion-wise (3:1) through dropping funnels with continuous
stirring and refluxed in an inert condition for 4 h. Reflux was continued
for two more hours after the addition. The initial yellow colored
solution became colorless during this period. The solution was allowed

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Macrocycle Functions
3163
to cool and left for 24 h. White crystals were obtained which was filtered
off. The solution was treated with 500 mL of water three times to separate
water soluble materials. The organic layer was separated by separating
funnel and dried with anhydrous Na SO . The volume was reduced by
2
4
rotary evaporation and a very light yellow crystals were separated out
which was filtered under inert atmosphere, washed and dried in vacuo.
ꢂ
1
Yield ¼ 79%, m.p. ¼ 225 C (decomposed). H NMR (D O): 8.46 (dd,
2
1
3
H), 8.11 (dd, 2H), 7.49 (t, 2H), 6.17 (s, 2H), C NMR (D O): 36.840,
38.309; IR (in cm ): 1560 (br), 2920 (br), 3300 (w), 3500 (s); elemental
2
2
À1
1
analyses (%): C ¼ 61.89, N ¼ 20.15, H ¼ 4.64.
Preparation of Macrocycle III
A similar method was followed to prepare the compound III which
was used for the preparation of compound II. Instead of taking 1,2-
diaminoethane, 0.57 g (0.005 mol) of 1,2-diaminohexane was reacted
with 1.5 g (0.0053 mol) of DCBNA in methylene chloride in presence of
ꢂ
TEA. A white color precipitate was obtained. Yield ¼ 53%, m.p. ¼ 190 C.
1
H NMR (D O): 8.05 (dd, 2H), 7.97 (dd, 2H), 7.42 (t, 2H), 2.86 (t, 2H),
2
.48 (t, 4H), 1.25 (s, 4H); IR (in cm ): 1580 (br), 2930 (br), 3377 (s), 3540
À1
1
(
s); elemental analyses (%): C ¼ 65.91, N ¼ 16.96, H ¼ 6.32.
Preparation of Macrocycle IV
In a three necked round bottom flask 1 mL of TEA was taken with
400 mL of methylene chloride. A mixture of 1.405 g (0.005 mol) of II in
150 mL of methylene chloride and 2.5 mL of TEA and a solution of
0.515 g (0.005 mol) of diethylene triamine in 50 mL methylene chloride
were added to it in portions for about 4 h with continuous stirring and
reflux under inert condition. Reflux was continued for another 2 h after
the addition was over. A light yellow precipitate was separated out which
was filtered off under nitrogen atmosphere, washed with cold methanol
ꢂ
and diethyl ether and dried in vacuo. Yield ¼ 55%, m.p. ¼ 142 C (decom-
1
posed); H NMR (D O): 8.45 (dd, 2H), 8.12 (dd, 2H), 7.49 (t, 2H), 3.07
2
1
qr, 4H), 2.93 (qr, 4H); C NMR (D O): 155.58, 148.402, 139.032,
3
(
1
2
À1
34.70, 124.300 (CH), 45.257 (CH ), 37.960 (CH ); IR (in cm ): 1580
2
2
(
br), 3040 (br), 3500 (s); elemental analyses (%): C ¼ 61.02, N ¼ 22.38,
H ¼ 5.55.

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164
Kanungo et al.
Preparation of Macrocycle V
A similar procedure that used to prepare IV was followed to synthe-
sise V by reacting 0.976 g (0.0034 mol) of DCBNA in 100 mL of methy-
lenechloride and 2.5 mL of TEA with a solution of 0.45 g (0.0034 mol) of
dipropyltriamine in 50 mL of methylene chloride. A buff color precipitate
ꢂ
1
was obtained. Yield ¼ 57%, m.p. ¼ 150 C (decomposed); H NMR (D O):
2
8.45 (dd, 2H), 8.02 (dd, 2H), 7.44 (t, 2H), 2.93 (qnt, 8H), 1.91 (qnt, 4H);
IR (in cm ): 1570 (br), 3020 (br), 3436 (s); elemental analyses (%):
À1
C ¼ 64.34, N ¼ 18.85, H ¼ 6.02.
ACKNOWLEDGMENT
Financial support for this work by the CSIR, New Delhi (India) is
gratefully acknowledged.
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Received in the Netherlands November 17, 2002