Synthesis of new polydentate tweezers ligands of amido-amine type

Article abstract of DOI:10.1134/S1070428007020236

A series of new tweezers amido-amine ligands containing pyrrole, bipyrrole, and dipyrrolylmethane fragments were synthesized by reaction of 2-thioxothiazolidin-3-yl derivatives of α-pyrrolecarboxylic acids {5-[1-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl

Full text of DOI:10.1134/S1070428007020236

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 2, pp. 297−304. © Pleiades Publishing, Ltd. 2007.
Original Russian Text © N.V. Boev, Yu.A. Ustynyuk, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 2, pp. 303−309.
Synthesis of New Polydentate Tweezers Ligands
ofAmido-Amine Type
N. V. Boev and Yu. A. Ustynyuk
Moscow State University, Moscow, 119899 Russia
e-mail: ustynyuk@nmr.chem.msu.ru
Received March 22, 2006; revised September 08, 2006
Abstract—A series of new tweezers amido-amine ligands containing pyrrole, bipyrrole, and dipyrrolylmethane
fragments were synthesized by reaction of 2-thioxothiazolidin-3-yl derivatives of α-pyrrolecarboxylic acids {5-[1-
(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-1-methylethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-[(5-
carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)phenylmethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-(5-
carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, and 3,4-dimethyl-
pyrrole-2,5-dicarboxylic acid} with o-phenylenediamine.All compounds obtained were characterized by elemental
analysis, NMR and mass spectra.
DOI: 10.1134/S1070428007020236
Polydentate ligands containing structural fragments of
pyrrole, bipyrrole, and dipyrrolylmethane are very
interesting objects for preparation of mono- and binuclear
complexes of transition metals [1–3], and also as building
blocks for synthesis of hybrid macrocyclic Schiff bases
which we have recently shown[4–7] to be capable of
selective binding anions and thus behave as highly efficient
artificial anion receptors. Among these compounds by
now Schiff bases Ia were described that were prepared
from the corresponding diformyl derivatives of pyrrole
by anion-template method [3]. Even more promising for
building up artificial anion receptors are amides of
appropriate α-carboxylic acids since the amide CONH
groups alongside pyrrole NH groups [8, 9] are capable to
bind anions by forming with them strong hydrogen bonds.
at the third and fourth positions of the ring. Introduction
of electron-acceptor groups to the pyrrole ring
somewhat increases the stability of the α-carboxylic
acids and makes it possible to obtain their derivatives.
3,4-Dimethyl-5-ethoxycarbonylpyrrole-2-carboxylic acid
and 3,4-diphenylpyrrole-2,5-dicarboxylic acid are
sufficiently stable against decarboxylation, and within the
last decade a series of their derivatives has been
synthesized, in particular amides [9, 10]. Preliminary tests
carried out by us showed that dicarboxylic acids from
2,2'-bipyrrole and 2,2'-dipyrrolylmethane with aliphatic
substituents in positions 3, 4 were to such degree thermally
unstable and acidophobic that we failed to synthesize any
derivatives by the carboxy group. At the same time
3,4-diphenylpyrrole-2,5-dicarboxylic acid is sufficiently
stable compound [11] capable even to form acyl chloride
by reaction with thionyl chloride. Therefore to raise the
stability of initial acids we introduced in the ring a phenyl
substituent adjacent to the carboxy group.
Amide of this type containing thiophene amd pyridine
fragment Ic and Id we synthesized from the cor-
responding dicarboxylic acids or their derivatives and two
equiv of symmetric diamines [5, 7]. To carry out selective
synthesis one amino group of the diamine was sometimes
protected, and deprotection was performed in the last
stage of the process [4]. The synthesis of compound Ib
with two or more pyrrole rings is the goal of the present
investigation and is a more complex synthetic problem
owing to the known acidophobicity of α-pyrrolecarboxylic
acids and to their capability to extremely readily
decarboxylation in acid media, and also to ipso-substitution
of the carboxy group in the majority of pyrroles with alkyls
The initial ethyl 4-methyl-3-phenylpyrrole-2-carboxy-
late (II) was easily obtained by Barton–Zard reaction
[12].Applying the known semimicro synthetic procedure
[13] we carried out the reaction in THF for 16 h, and
then after purification by column chromatography we
obtained compound II in 54% yield. The modification of
the procedure for preparative synthesis (the reaction
performed in THF–2-propanol mixture) reduced the
297

BOEV, USTYNYUK
298
O
O
NH
NH
X
HN
HN
N
N
N
N
NH
N
HN
N
Y
_
Ia
Ib Id
Ph
,
,
,
X =
(b),
N
NH HN
Ph
N
NH HN
N
H
H
H
Ph
(c),
(d);
N
S
Ph
,
,
.
,
Y =
NH HN
NH HN
N
N
N
H
H
H
reaction time to 4 h, and after simple recrystallization the
pure compound II was obtained in 95% yield.
aldehyde) led to the formation in yields about 70% mono-
and bis-meso-substituted dipyrrolylmethanes III and IV.
The cross-coupling Ullmann reaction formerly adjusted
for pyrroles by Sessler [14] gave in four stages bipyr-
role V.
NC
COOEt
Ph
The choice of these three basic structures as objects
of the synthesis and further investigation was governed
by the fact that the distances between the carboxy groups
in these compounds were different and grew in the series
III < IV < V. This fact and also their various conforma-
tional lability provided a possibility to build up therefrom
macrocycles of variable rigidity with different dimensions
of inner voids.
DBU
i-PrOH/THF
COOEt
N
NO2
H
II
Ph
N
DBU
Ethyl esters III–V are stable compounds melting
without decomposition. They all were readily and
quantitatively hydrolyzed in a system THF–methanol–
water into the corresponding dicarboxylic acids VI–VIII.
Note that ester IV unlike compound III is capable to be
oxidized into the corresponding dipyrrolemethine
derivative.
N
The transformation of ester II into the corresponding
bispyrrole derivatives was performed by known proce-
dures. The known acid-catalyzed pyrrole reaction with
carbonyl compounds (in our case with acetone and benz-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007

SYNTHESIS OF NEW POLYDENTATE TWEEZERS LIGANDS
299
Me2CO
Ph
Ph
MeSO3H/CH2Cl2
HN
III
NH
Ph
COOEt
EtOOC
COOEt
N
H
Ph
PhCHO
Ph
II
Ph
MeSO3H/CH2Cl2
HN
IV
NH
COOEt
EtOOC
Ph
Ph
Ph
(COOBu-t)2O/DMAP
KI3 / Na2CO3
MeOH
CH2Cl2
I
COOEt
I
COOEt
COOEt
N
N
H
N
H
II
OBu-t
O
Ph
Ph
Ph
Ph
CF3COOH
CH2Cl2
Cu
EtOOC
COOEt
EtOOC
DMF
COOEt
N
N
H
N
N
H
t-BuO
OBu-t
O
X
O
V
.
N(CH3)2
DMAP
N
X
NaOH
_
COOEt
EtOOC
COOH
HOOC
_
THF MeOH H2O
_
_
III V
VI VIII
Ph
Ph
Ph
Ph
Ph
(IV,VII),
(III,VI),
X =
NH HN
HN
NH
Ph
Ph
(V,VIII).
N
N
H
H
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BOEV, USTYNYUK
300
S
X
O
S
O
S
X
DCC, HOBt
N
COOH
HOOC
H
N
N
_
THF
VI IX
S
S
S
_
X XIII
O
O
X
NH2
DCC
N C N
OH
HN
H2N
NH
NH2
CH2Cl2
N
HOBt
Me
N
NH2
N
_
XIV XVII
Ph
Me
NH
Me
Me
Me
Me
Ph
Ph
Ph
Ph
(VII, XI, XV),
(VI, X, XIV),
X =
HN
HN
NH
Me
Me
Me
Me
Ph
Ph
(IX, XIII, XVII).
(VIII, XII, XVI),
N
H
N
H
N
H
Dicarboxylic acids VI–VIII are more stable than their
analogs containing only alkyl groups at the pyrrole ring.
Still they slowly decompose in solution at storage and in
the solid state at heating. We attempted to synthesize
their amides through intermediate acyl chlorides which
we tried to obtain by reactions with thionyl chloride and
oxalyl chloride. The target products were obtained only
in reaction with a large excess of aliphatic diamine. The
selectivity and yield in these reactions were low, as had
been previously found for analogous compounds [15].
We failed to isolate the target diamides with o-phenyl-
enediamine both in reactions via acyl chlorides and at
a milder activation of the acids by means of dicyclo-
hexylcarbodiimide. In reactions via acyl chlorides formed
mainly oligomeric products, and with dicyclohexyl-
carbodiimide the reaction failed to proceed due to low
nucleophilicity (and, consequently, diminished reactivity)
of aromatic amines. We succeeded in preventing oligo-
merization using 2-thioxothiazolan-3-yl departing group,
less active than chlorine. This group was already success-
fully used in preparation of amides from aromatic diamines
[16].
2-Thioxothiazolan-3-yl derivatives X–XIII of pyr-
rolecarboxylic acids VI–VIII, and also of known 3,4-di-
methylpyrrole-2,5-dicarboxylic acid (IX) were obtained
by treating the acids with 1,3-thiazolane-2-thione in the
presence of dicyclohexylcarbodiimide and benzotriazol-
1-ol. They were oily substances of low stability, therefore
after separation from side products and distilling off the
solvent the compounds were without further purification
at once brought into reaction with o-phenylenedi-
amine.
Diamides XIV–XVII were obtained in reactions with
a large excess of o-phenylenediamine in dichloromethane
at room temperature for 5–7 days. They were easily
isolated from the reaction mixture by simple filtration
(compounds XVI and XVII), by recrystallization from
ethanol after evaporating the solvent (XIV), or by column
chromatography on silica gel (XV). All compounds
obtained were characterized by NMR and mass spectra
and by elemental analysis. The synthesis of unsymmetrical
polypyrrole mactocyles of amido-imine type Ib using
diamides XIV–XVII will be published in next com-
munications.
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SYNTHESIS OF NEW POLYDENTATE TWEEZERS LIGANDS
301
EXPERIMENTAL
compound II in 200 ml of methanol was added a solution
of 22 g of sodium hydrogen carbonate in 200 ml of water.
To a suspension thus obtained was added within 2 h at
50°C while stirring a solution of 23 g of iodine and 33.5 g
of potassium iodide in 150 ml of a mixture methanol–
water, 2:1 v/v. The reaction mixture was stirred for 2 h
more at this temperature, then it was poured into 1 l of
water with ice. Excess iodine was neutralized with sodium
thiosulfate till decoloration of the solution over precipitate.
The precipitate was filtered off and dried in a vacuum
desiccator over calcium chloride for 24 h. Yield 30.3 g
(95%). The reaction product was sufficiently pure to be
used in the next stage of the synthesis. mp 83°C (hexane–
ether, 3:1). 1H NMR spectrum (CDCl3), δ, ppm: 1.12 t
(3H, J 7.5 Hz), 2.09 s (3H), 4.18 q (2H, J 7.5 Hz), 7.39 m
(5H), 9.05 br (1H). 13C NMR spectrum (CDCl3), δ, ppm:
10.89, 14.16, 60.51, 119.43, 119.95, 124.58, 127.18, 127.71,
130.62, 132.27, 134.49, 161.30. Mass spectrum, m/z (Irel,
%): 355.0 (100) [M]+. Found, %: C 47.63; H 4.06; N 3.98.
C14H14INO2. Calculated, %: C 47.34; H 3.97; N 3.94.
NMR spectra were registered on a spectrometer
Bruker AVANCE-400, mass spectra were measured on
instruments Finnigan-MAT-SSQ-7000 (GC-MS) and
Bruker MALDI-TOF Reflex 3 (MALDI-TOF). Ethyl
isocyanoacetate, 1-phenyl-2-nitropropene, and 3,4-
dimethyl-1H-pyrrole-2,5-dicarboxylic acid were prepared
by known procedures [17–19]. DBU, 1,3-thiasolane-2-
thion, DCC, benzotriazol-1-ol, and o-phenylenediamine
purchased from Acros were used without additional
purification.Anhydrous THF for reactions was obtained
by distillation over sodium ketyl (stable blue color) in the
presence of a small quantity of benzophenone. Dichloro-
methane, 2-propanol, and dimethylformamide for reac-
tions were distilled over calcium hydride. The chromato-
graphy was performed using silica gel Merck Kieselgel
60, 40–60 μm.
Ethyl 4-methyl-3-phenyl-1H-pyrrole-2-carboxy-
late (II). To a solution of 8.3 g (51 mmol) of 1-phenyl-2-
nitropropene in 60 ml of mixture THF–2-propanol, 3:1 v/v,
was added 5 g (44 mmol) ethyl isocyanoacetate and then
dropwise at stirring 6 g (45 mmol) of DBU maintaining
the temperature of the reaction mixture below 15°C by
cooling with a water bath. The reaction mixture was
stirred for 3 h more at room temperature (after 1 h
a precipitate formed), then the solvent was evaporated
in a vacuum at the temperature not exceeding 50°C, to
the residue 30 ml of ether and 30 ml of water was added,
and stirring was continued till complete dissolution of
solids. The organic phase was separated, the water phase
was extracted with ether (2×30 ml). The combined
organic solutions were washed with 10% HCl (2×30 ml),
water, saturated NaCl solution, and dried with sodium
sulfate. The solvent was removed in a vacuum, the
residue was recrystallized from petroleum ether (bp 40–
70°C). Yield 9.5 g (95%), yellowish crystalline substance,
Dipyrrolylmethanes III and IV. To a solution of
40 mmol of compound II in 50 ml of anhydrous dichloro-
methane under an argon atmosphere was added at stir-
ring 25 mmol of acetone (III) or benzaldehyde (IV) and
1 ml of methanesulfonic acid, and then the reaction mix-
ture was stirred for 24 h. To the mixture 30 ml of 10%
solution of NaOH was added, and the stirring was con-
tinued for another 30 min (the color changed from dark
red to orange). On separating the organic layer the reac-
tion products were additionally extracted from the water
phase with dichloromethane (2× 20 ml), the combined or-
ganic solvents were washed with water, saturated NaCl
solution, and dried with sodium sulfate. On distilling off
the solvent the residue was ground with ethanol, filtered
off, and additionally washed with anhydrous ethanol till
the filtrate became colorless. Reaction product was col-
orless fine crystalline substance.
1
mp 63°C (oily substance according to [13]). H NMR
spectrum (CDCl3), δ, ppm: 1.13 t (3H, J 7.5 Hz), 2.01 s
(3H), 4.15 q (2H, J 7.5 Hz), 6.45 d (1H, J 1.6 Hz), 7.51–
7.22 m (5H), 9.23 br (1H). 13C NMR spectrum (CDCl3),
δ, ppm: 10.76, 14.23, 60.15, 119.82, 119.91, 124.40, 127.25,
127.91, 130.45, 132.41, 134.23, 161.23. Mass spectrum,
m/z (Irel, %): 229.1 (100) [M]+. Found, %: C 73.07;
H 6.60; N 6.08. C14H15NO2. Calculated, %: C 73.34;
H 6.59; N 6.11.
Ethyl 5-[1-(5-ethoxycarbonyl-3-methyl-4-phenyl-
1H-pyrrol-2-yl)-1-methylethyl]-4-methyl-3-phenyl-
1H-pyrrole-2-carboxylate (III). Yield 71%, mp 195°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.11 t (6H, J 7.5
Hz), 1.56 s (6H), 1.79 C (6H), 4.13 q (2H, J 7.5 Hz), 7.35
m (10H), 8.89 br (1H). 13C NMR spectrum (CDCl3), δ,
ppm: 8.23, 14.16, 32.94, 42.44, 62.92, 103.36, 116.85,
127.54, 128.81, 129.37, 132.45, 134.54, 136.37, 160.15.
Mass spectrum, m/z (Irel, %): 498.25 (100) [M] +, 483
(73) [M – CH3]+. Found, %: C 74.53; H 6.96; N 5.76.
C31H34N2O4. Calculated, %: C 74.67; H 6.87; N 5.62.
Ethyl 5-iodo-4-methyl-3-phenyl-1H-pyrrole-2-
carboxylate. This synthesis should be protected from
bright light. To a solution of 20.6 g (0.92 mmol) of
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BOEV, USTYNYUK
302
Ethyl 5-[(5-ethoxycarbonyl-3-methyl-4-phenyl-
m/z (Irel, %): 456.20 (100) [M]+.Found, %: C 73.61;
H 5.91; N 5.98. C28H28N2O4. Calculated, %: C 73.66;
H 6.18; N 6.14.
1H-pyrrol-2-yl)phenylmethyl]-4-methyl-3-phenyl-
1H-pyrrole-2-carboxylate (IV). Yield 68%, mp210°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.06 t (6H), 1.82 s
(6H), 4.07 q (4H), 5.66 s (1H), 7.32 m (15H), 8.82 br
(2H). 13C NMR spectrum (CDCl3), δ, ppm: 9.46, 13.92,
41.23, 59.94, 117.67, 117.82, 126.69, 127.20, 127.35,
127.67, 128.32, 129.20, 130.39, 131.67, 132.22, 134.68,
138.67, 161.20. Mass spectrum, m/z (Irel, %): 546.2 (100)
[M] +. Found, %: C 76.83; H 6.11; N 4.95. C35H34N2O4.
Calculated, %: C 76.90; H 6.27; N 5.12.
Acids VI–VIII. In 20 ml of THF was dissolved
10 mmol of ester III–V, and a solution of 2 g (50 mmol)
of NaOH in 10 ml of water was added. To the two-
phase system obtained methanol (about 20–30 ml) was
added at stirring till the system turned homogeneous, and
the mixture was boiled for 5 h. On cooling the organic
solvents were distilled off in a vacuum while replacing
them with warm distilled water. The crystalline precipitate
of the dicarboxylic acid sodium salt was filtered off and
washed with warm water, then it was dissolved in 70–
100 ml of methanol (at heating when necessary), filtered,
and cooled to –10°C. The cold solution was quickly
neutralized with concn. HCl till pH 1.0–1.5, the separated
dicarboxylic acid was filtered off and washed with cold
(–10°C) methanol. On drying in a vacuum the product
obtained was a pure dicarboxylic acid.
5-[1-(5-Carboxy-3-methyl-4-phenyl-1H-pyrrol-2-
yl)-1-methylethyl]-4-methyl-3-phenyl-1H-pyrrole-2-
carboxylic acid (VI). Yield 96%, mp 180°C (decomp.).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.39 s (6H),
1.76 s (6H), 7.35 m (10H), 10.47 s (2H), 11.8 br (2H).
13C NMR spectrum (DMSO-d6), δ, ppm: 8.31, 33.03,
103.43, 116.91, 127.42, 128.76, 129.37, 132.46, 134.54,
136.32, 159.55. Mass spectrum, m/z: 466 [M + Na + H]+,
488 [M + 2Na – 2H]+, 510 [M + 3Na – 3H]+, 442 [M]–.
Found, %: C 73.13; H 5.97; N 6.08. C27H26N2O4.
Calculated, %: C 73.28; H 5.92; N 6.33.
5-[(5-Carboxy-3-methyl-4-phenyl-1H-pyrrol-2-
yl)phenylmethyl]-4-methyl-3-phenyl-1H-pyrrole-2-
carboxylic acid (VII). Yield 89%, mp 180°C (decomp.).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.95 s (6H),
5.82 s (1H), 7.28 m (15H), 11.55 s (2H), 11.90 br (2H).
13C NMR spectrum (DMSO-d6), δ, ppm: 9.95, 38.48,
117.27, 118.63, 126.63, 126.82, 127.77, 128.25, 128.66,
128.73, 130.24, 130.80, 132.86, 135.71, 141.50, 162.31.
Mass spectrum, m/z: 514 [M + Na + H]+, 490 [M]+, 446
[M – CO2]+, 402 [M – 2CO2]+, 490 [M]–, 512 [M + Na –
H]–. Found, %: C 76.25; H 5.22; N 5.80. C31H26N2O4.
Calculated, %: C 75.90; H 5.34; N 5.71.
Ethyl 5-(3-methyl-4-phenyl-5-ethoxycarbonyl-
1H-pyrrol-2-yl)-4-methyl-3-phenyl-1H-pyrrole-2-
carboxylate (V) was obtained by procedure [9]. To
22 g (0.062 mol) of ethyl-5-iodo-4-methyl-3-phenylpyr-
role-2-carboxylate and 1 g of DMAP in 250 ml of
anhydrous dichloromethane was added by portions 18 g
of di-tert-butyl dicarbonate. The mixture was stirred for
3 h till the end of gas liberation. The transparent solution
obtained was passed through a bed of silica gel (80 ×
40 mm) and evaporated in a vacuum. The oily substance
obtained without further purification was dissolved in
120 ml of DMF under an argon atmosphere, and at stirring
25 g of copper powder was added. The reaction mixture
was heated to 110°C and stirred for 30 h at this tempera-
ture. Then it was cooled and filtered through a bed of
silica gel (50 × 40 mm) to remove copper compounds,
the elution with chloriform (about 300 ml) was continued
till colorless solution. The eluate was washed with 10%
solutions of HCl (3 × 100 ml) and Na2S2O3 (3 × 100 ml),
with saturated solutions of NaHCO3 (100 ml) and NaCl
(100 ml), dried with sodium sulfate, and the solvent was
removed in a vacuum. The oily residue without additional
purification was dissolved in 150 ml of dichloromethane,
and 50 ml of trifluoroacetic acid was added to the solution.
The mixture was stirred till the end of gas liberation (2–
3 h), then 100 ml of water was added. The organic phase
was separated and trice washed with 10% solution of
NaOH and with saturated NaCl solution (adding
dichloromethane in case organic substance precipitated),
then the solution was dried with sodium sulfate. On
removing the solvent in a vacuum and recrystallization
of the residue from ethanol we obtained 7.5 g of
compound V as a grayish powder. Yield 54% (overall),
5-(5-Carboxy-3-methyl-4-phenyl-1H-pyrrol-2-
yl)-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid
1
1
(VIII). Yield 93%, mp 220°C (decomp.). H NMR
mp 235°C. H NMR spectrum (CDCl3), δ, ppm: 1.12 t
spectrum (DMSO-d6), δ, ppm: 1.88 s (6H), 7.31 m (10H),
11.51 s (2H), 11.98 br (2H). 13C NMR spectrum (DMSO-
d6), δ, ppm: 10.84, 118.45, 118.89, 124.72, 126.23, 126.87,
127.39, 128.35, 130.30, 135.19, 161.73. Mass spectrum,
(6H, J 7.5 Hz), 2.09 s (6H), 4.18 q (4H, J 7.5 Hz), 7.39
m (10H), 9.05 br (2H). 13C NMR spectrum (CDCl3), δ,
ppm: 10.96, 14.28, 60.46, 119.37, 119.80, 124.63, 127.20,
127.80, 130.55, 132.33, 134.54, 161.20. Mass spectrum,
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SYNTHESIS OF NEW POLYDENTATE TWEEZERS LIGANDS
303
m/z: 400 [M]+, 356 [M – CO2]+, 400 [M]–, 355 [M – CO2
– H]–. Found, %: C 72.36; H 4.91; N 6.85. C24H20N2O4.
Calculated, %: C 71.99; H 5.03; N 7.00.
7.22–7.46 m (15H), 10.09 s (2H), 11.55 s (2H). 13C NMR
spectrum (DMSO-d6), δ, ppm: 9.81, 33.30, 116.53, 116.66,
122.47, 124.00, 124.71, 125.86, 126.45, 126.85, 127.67,
127.85, 128.27, 128.37, 128.69, 129.08, 130.68, 130.87,
131.73, 135.47, 141.70, 159.68. Mass spectrum, m/z: 693
[M + Na]+. Found, %: C 76.65; H 5.96; N 12.39.
C43H38N6O2. Calculated, %: C 76.99; H 5.71; N 12.53.
Amides XIV–XVII. A solution or suspension of
10 mmol of dicarboxylic acid in 70 ml of anhydrous THF
under argon was cooled to–5°C, and then 4.53 g
(22 mmol) of dicyclohexylcarbodiimide was added, and
after that 2.97 g (22 mmol) of benzotriazol-1-ol, and the
mixture was stirred for 30–40 min at room temperature
(when necessary the reaction mixture was heated to
complete dissolution of the acid). To a solution thus
obtained 2.62 g (22 mmol) of 1,3-thiazolane-2-thione was
added, and the mixture was stirred for 48 h. The separated
precipitate was filtered off and washed with THF. The
filtrate was evaporated to dryness in a vacuum, the
residue was dissolved in anhydrous dichloromethane, and
filtered. To the transparent solution 7.13 g (66 mmol) of
o-phenylenediamine was added, and the stirring continued
for 5–7 days. The isolation of the reaction product was
adjusted to each special case.
2-Aminophenylamide of 5-[5-(2-aminophenyl-
carboxamido)-3-methyl-4-phenyl-1H-pyrrol-2-yl]-4-
methyl-3-phenyl-1H-pyrrole-2-carboxylic acid
(XVI). The colorless precipitate was filtered off, washed
with dichloromethane, ethanol, and ether, and dried in
1
a vacuum. Yield 38%, mp 220°C (decomp.) H NMR
spectrum (DMSO-d6), δ, ppm: 1.97 s (6H), 4.70 br (4H),
6.51 d.t (2H, J1 8, J2 1.6 Hz), 6.68 d.d (2H, J1 8,
J2 1.6 Hz), 6.82 d.t (2H, J1 8, J2 1.6 Hz), 7.21 d.d (2H,
J1 8, J2 1.6 Hz), 7.32 m (2H), 7.44 m (8H), 8.09 s (2H),
11.59 s (2H). 13C NMR spectrum (DMSO-d6), δ,
ppm:11.24, 116.38, 116.78, 118.00, 123.17, 123.82, 125.30,
126.03, 127.18, 128.00, 128.61, 130.73, 135.47, 142.14,
159.55. Mass spectrum, m/z: 580 [M]+, 603 [M + Na]+.
Found, %: C 74.21; H 5.48; N 14.27. C36H32N6O2.
Calculated, %: C 74.46; H 5.55; N 14.47.
2-Aminophenylamide of 5-{1-[5-(2-aminophenyl-
carboxamido)-3-methyl-4-phenyl-1H-pyrrol-2-yl]-1-
methylethyl}-4-methyl-3-phenyl-1H-pyrrole-2-
carboxylic acid (XIV). The solvent was distilled off in
a vacuum, the residue was twice recrystallized from
ethanol. Yield 42%, light-yellow substance, mp 152°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.52 s (6H),
1.87 s (6H), 4.55 br (4H), 6.47 d.t (2H, J1 8, J2 1.6 Hz),
6.65 d.d (2H, J1 8, J2 1.6 Hz), 6.90 d.t (2H, J1 8,
J2 1.6 Hz), 7.17 d.d (2H, J1 8, J2 1.6 Hz), 7.30 m (2H),
7.42 m (8H), 8.05 s (2H), 10.57 s (2H). 13C NMR spec-
trum (DMSO-d6), δ, ppm: 10.01, 28.17, 36.58, 115.01,
115.17, 116.57, 117.01, 119.76, 124.06, 125.24, 126.00,
127.21, 128.61, 129.36, 130.86. 135.83, 137.25, 142.16,
159.46. Mass spectrum, m/z: 645 [M + Na]+. Found, %:
C 74.93; H 6.09; N 13.47. C39H38N6O2. Calculated, %:
C 75.22; H 6.15; N 13.49.
N2,N5-Bis(2-aminophenyl)amide of 3,4-dimethyl-
pyrrole-2,5-dicarboxylic acid (XVII). Yellow
precipitate was filtered off, washed with dichloromethane,
ethanol, and ether, and dried in a vacuum.Yield 34%,
1
mp 250°C (decomp.). H NMR spectrum (DMSO-d6),
δ, ppm: 2.26 s (6H), 4.93 br (4H), 6.59 d.t (2H, J1 8,
J2 1.6 Hz), 6.78 d.d (2H, J1 8, J2 1.6 Hz), 6.95 d.t (2H,
J1 8, J2 1.6 Hz), 7.26 d.d (2H, J1 8 , J2 1.6 Hz), 9.04 s
(2H), 11.63 s (2H). 13C NMR spectrum (DMSO-d6), δ,
ppm: 10.52, 116.56, 116.81, 123.76, 124.43, 126.37, 142.77,
160.04. Mass spectrum, m/z: 363 [M]+. Found, %: C 66.04;
H 5.82; N 19.09. C20H21N5O2. Calculated, %: C 66.10;
H 5.82; N 19.27.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grants
nos. 05-03-08017,06-03-81026, and 05-03-32684a).
2-Aminophenylamide of 5-{[5-(2-aminophenyl-
carboxamido)-3-methyl-4-phenyl-1H-pyrrol-2-
yl]phenylmethyl}-4-methyl-3-phenyl-1H-pyrrole-2-
carboxylic acid (XV). The solvent was distilled off in
a vacuum, the reaction product was isolated by column
chromatography on silica gel, eluent dichloromethane–
methanol, 9:1 v/v. Yield 45%, Rf 0.35–0.40, mp 150°C
The authors are especially grateful to Candidate of
Chemical Sciences RRM Reshetova and Candidate of
Chemical Sciences N.E. Borisova for valuable
suggestions and help in preparation of the article for
publication.
1
(decomp.). H NMR spectrum (DMSO-d6), δ, ppm:
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(2H, J1 8, J2 1.6 Hz), 7.20 d.d (2H, J1 8, J2 1.6 Hz),
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