The synthesis of new pyrrolo[1,2-a]perimidin-10-one dyes via two convenient routes and its characterizations

Article abstract of DOI:10.1016/j.dyepig.2012.04.016

Efficient synthesis of pyrrolo[1,2-a]perimidin-10-ones (4, 8) are accomplished via two new convenient methods in moderate yields. The first method is the reaction of oxalyl chloride with heterocyclic ketene aminals (HKAs) containing perimidine moiety (3),

Full text of DOI:10.1016/j.dyepig.2012.04.016

Dyes and Pigments 95 (2012) 421e426
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The synthesis of new pyrrolo[1,2-a]perimidin-10-one dyes via two convenient
routes and its characterizations
a
a
,
a
b
_
_
*
Irfan Koca , S¸ evket Hakan Üngören , Ibrahim E. Kıbrız , Filiz Yılmaz
a Department of Chemistry, Faculty of Arts and Sciences, Bozok University, 66200 Yozgat, Turkey
b Department of Chemistry, Faculty of Sciences, Anadolu University, 26470 Eskis¸ehir, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Efficient synthesis of pyrrolo[1,2-a]perimidin-10-ones (4, 8) are accomplished via two new convenient
methods in moderate yields. The first method is the reaction of oxalyl chloride with heterocyclic ketene
aminals (HKAs) containing perimidine moiety (3), and the second is the reaction of 1,8-
naphthalenediamine (1) with 2-alkoxycarbonylmethylene substituted furan-3-ones (7). The visible
absorption spectrums of 4 and 8 were dominated by the characteristic perimidines bands in the region
381e439 nm. While compounds 4b-d show thermal stability up to 250 ꢀC, compounds 8 are stable up to
216e235 ꢀC. The structures of all products were confirmed by IR, 1H and 13C NMR spectroscopic methods,
in case of 8b also by XRD analysis.
Received 27 December 2011
Accepted 30 April 2012
Available online 21 May 2012
Keywords:
Pyrrolo[1,2-a]perimidin-10-one
1H-perimidine
Heterocyclic ketene aminals
Naphthalene-1,8-diamine
Furan-3-one
Ó 2012 Elsevier Ltd. All rights reserved.
Pyrrole dyes
1. Introduction
In this work, we aimed to prepare new pyrrolo[1,2-a]perimidin-
10-ones and their spectroscopic characterization via two conve-
The importance of substituted pyrroles in organic chemistry is
well-known. Pyrrol-2-ylidenes are especially interesting structures,
and this unit is found in many vital natural compounds (vitamin
B12, prodigiosins), natural colorants (porphyrins, chlorophylls) and
synthetic colorants (BODIPY dyes).
nient methods. The first method is the reaction of oxalyl chloride
with heterocyclic ketene aminals (HKAs) containing perimidine
moiety, and the second is the reaction of
alkoxycarbonylmethylene substituted furan-3-ones.
1
with 2-
Pyrrolo[1,2-a]perimidin-10-one framework is an integral part of
the structure of some patented dyes and pigments recommended
for a wide range of industrial plastics [1e5]. They exhibit shades of
colour from red to orange. Pyrroloperimidine-containing polymers
have contributed to the remarkable growth of interest in coloring
materials, luminescent sensors, organic light emitting diodes and
other optoelectronic devices [4,6,7]. Consequently, pyrrolo[1,2-a]
perimidines are interesting compounds from the viewpoint of both
their reactions and applications.
Several methods have been reported for construction of the
pyrrolo[1,2-a]perimidine skeleton. All the methods are based on
naphthalene-1,8-diamine (1) chemistry [2,4,7e15]. These proceed
in moderate yields by refluxing at high temperatures, mostly in the
presence of various catalysts.
2. Experimental
Solvents and all other chemical reagents were purchased from
Merck, Sigma, Aldrich and Fluka. Solvents were dried by refluxing
with the appropriate drying agents and distilled before use. The
reactions were followed by TLC (Silica gel, aluminium sheets 60
F254, Merck). Melting points were uncorrected and recorded on
Electrothermal 9200 digital melting point apparatus. Microanal-
yses were performed on a Leco-932 CHNS-O Elemental Analyser. A
Jasco 460 or Shimadzu 8400 FT-IR Spectrophotometer were used
for IR spectra (4000-400 cmꢁ1). The 1H and 13C NMR spectra were
measured with Bruker Avance III 400 MHz spectrometers and the
chemical shifts were recorded in ppm units. Thermal data were
obtained by using a Setaram Labsys TG-DSC/DTA thermobalance in
N2 atmosphere. Single crystal diffraction measurements were per-
formed on Bruker AXS APEX diffractometer [16]. Diffraction data
were collected over the full sphere and were corrected for
absorption. The crystal structure was solved by direct methods and
refined by using SHELXS-97 and SHELXL-97 crystallographic
* Corresponding author. Tel./fax: þ90 354 2421022.
E-mail addresses: shakan.ungoren@bozok.edu.tr, hungoren@yahoo.com,
hungoren@erciyes.edu.tr (S¸ .H. Üngören).
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2012.04.016

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I. Koca et al. / Dyes and Pigments 95 (2012) 421e426
software packages [17,18]. 2,3-Furandiones (5) were synthesized
according to published methods for the synthesis of 7a,b [19,20].
removal of the solvent, the residue was treated with cold methanol
(20 ml, 0e5 ꢀC) and crystallized from methanol to give pure 7.
2.2.1. Methyl (2Z)-[4-(3,4-dimethoxybenzoyl)-5-(3,4-
2.1. General procedure for the synthesis of compound 4
dimethoxyphenyl)-3-oxofuran-2(3H)-ilidene]acetate (7c)
Data for 7c: Orange crystals, yield: 0.363 g, 80%; mp 172 ꢀC. FT-IR
(KBr): nmax: 1722, 1697, 1668 (C]O), 1634 cmꢁ1 (C]C); 1H NMR
(CDCl3): 7.75e6.80 (m, 6H, AreH), 6.18 (s, 1H, C]CH), 3.95, 3.93,
3.91, 3.89, 3.78 (5 ꢂ s, 15H, OCH3); 13C NMR (CDCl3): 188.49 (C]O,
aroyl), 184.21 (C3]O), 176.81 (C]O, ester), 163.98, 154.51, 151.32,
149.43, 149.09, 129.83, 125.73, 124.39, 118.96, 114.97, 111.48, 111.10,
110.67, 110.17, 100.16 (C]C), 56.20, 56.15, 56.07, 55.88, 55.27
(OCH3). Anal. Calcd. For C24H22O9: C, 63.43; H, 4.88; Found: C,
63.21; H, 4.72%.
Solutions of 3a-d (1 mmol) and oxalyl chloride (0.127 g, 1 mmol)
in CH3CN (60 ml) were stirred for 1 h at 50 ꢀC. after removal of the
solvent, the residue was crystallized from corresponding solvent to
give pure 4.
2.1.1. 8-Acetyl-9-hydroxy-10H-pyrrolo[1,2-a]perimidin-10-one (4a)
Data for 4a: Recrystallized from DMF, orange crystals, yield
0.248 g, 89%; m.p: 312 ꢀC. FT-IR (KBr): nmax: 3306 (OH), 1765 (C]O,
lactam), 1703 (C]O, acetyl), 1645, 1622 cmꢁ1 (C]N and C]C); 1H
NMR (DMSO-d6): 12.23 (s (br), 1H, OH was D2O exchangeable),
8.34e7.50 (m, 6H, AreH), 2.42 ppm (COCH3); 13C NMR (DMSO-d6):
192.08 (C]O, acetyl), 173.30 (C]CeOH), 160.03 (C]O, lactam),
152.08, 137.19, 133.59, 128.42, 128.18, 124.37, 123.99, 117.21, 115.82,
113.66, 110.19, (C]C), 28.65 ppm (CH3). Anal. Calcd. For
C16H10N2O3: C, 69.06; H, 3.62; N, 10.07 Found: C, 69.23; H, 3.54; N,
10.23%.
2.2.2. Ethyl (2Z)-[4-(3,4-dimethoxybenzoyl)-5-(3,4-
dimethoxyphenyl)-3-oxofuran-2(3H)-ilidene]acetate (7d)
Data for 7d: Orange crystals, yield: 0.356 g, 76%; mp 150 ꢀC. FT-
IR (KBr): nmax: 1718, 1695, 1670 (C]O), 1638 cmꢁ1 (C]C); 1H NMR
(CDCl3): 7.70e6.82 (m, 6H, AreH), 6.16 (s, 1H, C]CH), 4.35 (q, 2H,
J ¼ 7.1 Hz, OCH2), 3.95, 3.92, 3.89, 3.73 (4 ꢂ s, 12H, OCH3), 1.40 ppm
(t, 3H, J ¼ 7.1 Hz, CH3); 13C NMR (CDCl3): 188.54 (C]O, aroyl),
184.26 (C3]O), 176.79 (C]O, ester), 163.58, 154.47, 151.13, 149.41,
149.09, 129.88, 125.71, 124.36, 119.04, 115.01, 111.44, 111.08, 110.69,
110.17, 100.73 (C]C), 61.31 (OCH2), 56.20, 56.15, 56.07, 55.90
(OCH3), 14.24 ppm (CH3). Anal. Calcd. For C25H24O9: C, 64.10; H,
4.88; Found: C, 64.37; H, 4.98%.
2.1.2. 8-Benzoyl-9-hydroxy-10H-pyrrolo[1,2-a]perimidin-10-one
(4b)
Data for 4b: Recrystallized from diethylether-hexane(1:1), red
crystals, yield 0.289 g, 85%; m.p: 215 ꢀC. FT-IR (KBr): nmax: 3308
(OH), 1720 (C]O, lactam), 1673 (C]O, benzoyl), 1646, 1631 cmꢁ1
(C]N and C]C); 1H NMR (DMSO-d6): 12.63 (s (br), 1H),
8.29e7.40 ppm (m, 11H, AreH); 13C NMR (DMSO-d6): 188.01 (C]O,
benzoyl), 161.41 (C]CeOH), 159.78 (C]O, lactam), 148.66, 138.73,
136.29, 135.97, 135.46, 133.81, 131.05, 130.51, 129.75, 128.90, 128.56,
127.91, 124.69, 123.51, 117.46, 109.90 ppm (C]C). Anal. Calcd. For
C21H12N2O3: C, 74.11; H, 3.55; N, 8.23 Found: C, 73.94; H, 3.75; N,
8.49%.
2.3. General procedure for the synthesis of compound 8
Solutions of furan-3-ones 7 (1 mmol) and naphthalene-1,8-
diamine (1 mmol) in methanol (60 ml) were refluxed for
30 min the resulting solid was collected and recrystallized from
n-butanol.
2.3.1. Methyl (2Z)-[9-hydroxy-8-(4-methoxybenzoyl)-7a-(4-
methoxyphenyl)-7,7a-dihydro-10H-pyrrolo[1,2-a]perimidin-10-
iliden]acetate (8a)
2.1.3. 9-Hydroxy-8-(4-methoxybenzoyl)-10H-pyrrolo[1,2-a]
perimidin-10-one (4c)
Data for 4c: Recrystallized from diethylether-hexane(1:1), red
crystals, yield 0.318 g, 86%; m.p: 198 ꢀC. FT-IR (KBr): nmax: 3303
(OH), 1729 (C]O, lactam), 1655 (C]O, aroyl), 1638, 1628 cmꢁ1 (C]
N and C]C); 1H NMR (CDCl3): 13.10 (s, br, 1H), 8.55e6.94 ppm (m,
10H, AreH); 3.92 (s, 3H, OCH3); 13C NMR (CDCl3): 188.08, 185.18
(C]O), 165.17 (C]CeOH), 159.34 (C]O, lactam), 153.85, 147.50,
138.60, 136.82, 133.61, 132.56, 132.41, 131.53, 130.42, 128.57, 127.95,
125.59, 123.61, 117.46, 114.36, 110.75 (C]C), 55.68, 55.45 ppm
(OCH3). Anal. Calcd. For C22H14N2O4: C, 71.35; H, 3.81; N, 7.56
Found: C, 71.14; H, 3.54; N, 7.67%.
Data for 8a: Red crystals, yield: 0.412 g, 77%; mp 185 ꢀC. FT-IR
(KBr): nmax
: 3441 (OH, br.), 3387 (NH), 1670, 1638 (C]O),
1631 cmꢁ1 (C]N); 1H NMR (DMSO-d6): 14.54 (s,1H, OH), 7.88e6.63
(m, 14H, AreH), 5.94 (s, 1H, C]CH), 3.82, 3.72, 3.53 (s, 9H, OCH3);
13C NMR (DMSO-d6): 189.17 (C]O),173.99 (C]O, ester),159.11 (C]
CeOH), 163.65, 156.21, 154.84, 139.85, 134.29, 131.80, 131.45, 131.14,
131.03, 128.55, 128.50, 126.09, 125.27, 119.70, 117.26, 117.14, 116.35,
114.00, 113.90, 109.76 (C]C), 84.85 (C]CHCOOMe), 81.63
(NHeCeN), 55.97, 55.26, 53.22 (OCH3). Anal. Calcd. For
C32H26N2O6: C, 71.90; H, 4.90; N, 5.24 Found: C, 71.76; H, 4.59; N,
5.02%.
2.1.4. 8-(3,4-Dimethoxybenzoyl)-9-hydroxy-10H-pyrrolo[1,2-a]
perimidin-10-one (4d)
2.3.2. Ethyl (2Z)-[9-hydroxy-8-(4-methoxybenzoyl)-7a-(4-
methoxyphenyl)-7,7a-dihydro-10H-pyrrolo[1,2-a]perimidin-10-
iliden]acetate (8b)
Data for 4d: Recrystallized from diethylether-hexane(1:1), red
crystals, yield 0.320 g, 80%; m.p: 255 ꢀC. FT-IR (KBr): nmax: 3303
(OH), 1672, 1653, 1641 cmꢁ1 (C]O, C]N); 1H NMR (DMSO-d6):
13.84, 12.40 (s, 1H, OH); 7.75e6.66 (m, 9H, AreH); 4.65 (s, 1H, CH);
3.88, 3.84 ppm (s, 6H, OCH3); 13C NMR (DMSO-d6): 190.80, 170.89
(C]O), 163.50 (C]CeOH), 157.53 (C]O, lactam), 149.26, 134.79,
133.02, 129.23, 124.15, 122.89, 111.61, 110.70, 108.33, 105.65 (C]C),
56.38, 56.15 ppm (OCH3). Anal. Calcd. For C23H16N2O5: C, 69.00; H,
4.03; N, 7.00 Found: C, 68.85; H, 3.84; N, 7.18%.
Data for 8b: Red crystals, yield: 0.400 g, 73%; mp 196 ꢀC. FT-IR
(KBr): nmax
: 3435 (br, OH), 3389 (NH), 1665, 1638 (C]O),
1630 cmꢁ1 (C]C); 1H NMR (DMSO-d6): 14.62 (s, 1H, OH), 7.78e6.63
(m, 14H, AreH), 5.91 (s, 1H, C]CH), 4.17 (q, 2H, J ¼ 7.0 Hz, OCH2),
3.87, 3.54 (s, 6H, OCH3), 1.22 ppm (t, 3H, J ¼ 7.0 Hz, CH3); 13C NMR
(DMSO-d6): 189.17 (C]O), 173.61 (C]O, ester), 159.11 (C]CeOH),
163.64, 156.29, 154.94, 139.85, 134.29, 131.79, 131.50, 131.18,
131.07, 128.51, 126.11, 125.25, 119.67, 117.30, 117,12, 116.35, 113.99,
113.90, 109.72, (C]C), 85.16 (C]CHCOOMe), 81.63 (NHeCeN),
62.12 (OCH2), 55.97, 55.28 (OCH3), 14.49 ppm (CH3). Anal. Calcd.
For C33H28N2O6: C, 72.25; H, 5.14; N, 5.11 Found: C, 72.38; H, 5.34;
N, 5.40%.
2.2. General procedure for the synthesis of compound 7
Solutions of 2,3-dihydrofuran- 2,3-diones 5 (1 mmol) and 6
(1 mmol) in dry benzene (60 ml) were refluxed for 30 min after

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423
Scheme 1. The first method of the synthesis of pyrrolo[1,2-a]perimidin-10-ones.
2.3.3. Methyl (2Z)-[8-(3,4-dimethoxybenzoyl)-7a-(3,4-
3. Results and discussion
dimethoxyphenyl)-9-hydroxy-7,7a-dihydro-10H-pyrrolo[1,2-a]
perimidin-10-iliden]acetate (8c)
3.1. Synthesis of pyrrolo[1,2-a]perimidin-10-ones
Data for 8c: Red crystals, yield: 0.470 g, 79%; mp 195 ꢀC. FT-IR
(KBr): nmax
:
3448 (br, OH), 3385 (NH), 1670, 1655 (C]O),
According to literatures, enaminones undergo cyclo-
condensations with OxCl2 to provide the corresponding pyrroles
[21e23]. This method was considered as a general procedure for
a new type of pyrrolo[1,2-a]perimidin-10-one dyes. Firstly, HKAs
1618 cmꢁ1 (C]C); 1H NMR (DMSO-d6):14.45 (s, 1H, OH), 7.78e6.62
(m, 12H, AreH), 5.92 (s, 1H, C]CH), 3.83, 3.78, 3.72, 3.59, 3.53 ppm
(s, 15H, OCH3);13C NMR (DMSO-d6): 189.25 (C]O), 173.97 (C]O,
ester), 156.44 (C]CeOH), 154.56, 153.71, 148.78, 148.74, 148.61,
140.01, 134.30, 131.80, 131.24, 130.79, 128.52, 126.14, 125.26, 124.84,
119.93, 119.61, 117.36, 117.17, 116.39, 111.76, 111.40, 111.16, 111.04,
109.63 (C]C), 84.90 (C]CHCOOMe), 81.80 (NHeCeN), 56.20,
56.09, 56.02, 55.58, 53.19 ppm (OCH3). Anal. Calcd. For C34H30N2O8:
C, 68.68; H, 5.09; N, 4.71 Found: C, 68.39; H, 5.15; N, 4.88%.
were prepared from 1 and corresponding b-keto esters 2 in xylene
[24]. Simply heating an MeCN solution of HKAs and OxCl2 led to the
formation 8-acyl-9-hydroxy substituted pyrrolo[1,2-a]perimidin-
10-ones in good yields (80e89%) as outlined in Scheme 1.
Alkyl (2E)-[4-aroyl-5-aryl-3-oxofuran-2(3H)-ylidene]acetates
(7a-d) were prepared for the synthesis of the planned perimidine
ring-system as the second-type of starting material. While 7a,b
were known compounds [25,26], 7c,d were newly synthesized.
Subsequently, compounds 7a-d were smoothly reacted with 1 in
boiling methanol to give pyrrolo[1,2-a]perimidin-10-ylidenes 8a-
d in good yields (72e79%), (Scheme 2). On completion of the
reaction, the orange-red crude products 8 precipitated in highly
pure state.
2.3.4. Ethyl (2Z)-[8-(3,4-dimethoxybenzoyl)-7a-(3,4-
dimethoxyphenyl)-9-hydroxy-7,7a-dihydro-10H-pyrrolo[1,2-a]
perimidin-10-iliden]acetate (8d)
Data for 8d: Red crystals, yield: 0.438 g, 72%; mp 183 ꢀC. FT-IR
(KBr): nmax
: 3443 (br, OH), 3376 (NH), 1671, 1636 (C]O),
1621 cmꢁ1 (C]C); 1H NMR (DMSO-d6): 14.55 (s, 1H, OH), 7.78e6.63
(m, 12H, AreH), 5.89 (s, 1H, C]CH), 4.18 (q, 2H, J ¼ 7.1 Hz, OCH2),
3.83, 3.78, 3.58, 3.53 (s,12H, OCH3), 1.22 ppm (t, 3H, J ¼ 7.1 Hz, CH3);
13C NMR (DMSO-d6): 189.25 (C]O), 173.59 (C]O, ester), 156.52
(C]CeOH), 154.67, 153.68, 148.76, 148.61, 140.02, 134.30, 131.83,
130.81, 128.53, 126.16, 125.24, 124.58, 119.94, 119.57, 117.41, 116.39,
111.73, 111.38, 111.04, 109.60 (C]C), 85.20 (C]CHCOOMe), 81.79
(NHeCeN), 62.08 (OCH2), 56.20, 56.09, 56.02, 55.58 (OCH3),
14.50 ppm (CH3). Anal. Calcd. For C35H32N2O8: C, 69.07; H, 5.30; N,
4.60 Found: C, 68.85; H, 5.05; N, 4.71%.
3.2. Spectral characterizations of pyrrolo[1,2-a]perimidin-10-ones
In the 13C NMR spectra of 4, lactam carbonyl carbons were
clearly observed in the range of
d 157.5e160.0 ppm. Both Cesignals
attached to enoleOH of 4 and 8 appeared in the range of
d
156.5e159.1 ppm.
In the 1H NMR spectra, there were no signals of 8a-d related to
tautomeric equilibrium. However, 1H NMR signals of compound 4
Scheme 2. The preparation of furan-3-ones (7a-d) and their reactions with napthalene-1,8- diamine.

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I. Koca et al. / Dyes and Pigments 95 (2012) 421e426
Scheme 3. The possible tautomeric forms of 4 in CDCl3.
of compounds 4a,b were observed at
d 12.23 and 13.10 ppm,
respectively. On the other hand, compound 4c is in equilibrium
with approximately 20% of the corresponding ketoeamine form
and 80% enoleimine form in CDCl3. OH proton signals of
enoleimine form of 4c shows two distinct resonances at d 8.43 and
8.45 ppm as two singlets. This observation is revealed that there are
two different intramolecular hydrogen bondings between the OeH
proton of enoleimine form and two different C]O groups. More-
over, in the 1H NMR spectra of 4c, there was no signal from
a methine proton belonging to the ketoeimine tautomer in CDCl3
solution. But, 4d showed a signal at
d 4.65 ppm from methine
proton belonging to the ketoeimine tautomer in DMSO-d6 solution.
In addition, NH signal of 4d belonging to ketoeamine tautomer was
detected at
The 1H NMR spectrum of 8a showed the OeH proton at
and an olefinic proton signal at 5.94 ppm. The three methoxy
protons appeared as sharp singlets at
3.82, 3.72, 3.53 ppm 1H
d 13.56 ppm.
d
14.54,
d
d
NMR data of the other compounds (8b-d) agree with the proposed
molecular structure.
The IR spectra of 4a-d clearly showed absorption bands in the
ranges of 1765e1720 cmꢁ1 (C]O, lactam), 1703e1655 cmꢁ1 (C]O,
acyl) and 1646e1638 cmꢁ1 (C]N). The OeH vibrations were
Fig. 1. UVevis spectra of compounds 4 in DMF.
observed as broad bands in the range of 3306e3303 cmꢁ1
.
were showed evidence of all the possible tautomeric form in
solution (Scheme 3).
According to the published report, the origin of the
longewavelength absorption band of perimidines is the
According to the 1H NMR data; compounds 4a,b exist mainly in
the ketoeamine form in DMSO-d6. NH signals of ketoeamine forms
Fig. 3. Thermogravimetric analyses curve in N2 atmosphere of pyrrolo[1,2-a]peri-
Fig. 2. UVevis spectra of compounds 8 in DMF.
midin-10-ones.

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I. Koca et al. / Dyes and Pigments 95 (2012) 421e426
425
Fig. 4. Molecular structure of 8b.
peelectron transfer from the naphthalene ring to the heteroring.
3.3. X-Ray crystallography
This band that is responsible for the colour of the perimidines is
observed about 400 nm [10].
Unambiguous evidence for the structure of 8 with the atom
labeling was obtained by using X-ray analysis (Fig. 4). The X-Ray
crystallographic analysis show that 8b crystallizes in triclinic
system and space group P-1. Compound 8b was crystallized from
CH2Cl2-cyclohexane (1:1) for single crystal studies. So, the structure
consists of the two 8b molecules and one CH2Cl2 as a solvent. The
inter atomic bond lengths and angles are almost similar in the two
molecules. The bond distances are typical single bond character in
Pyrrolidine-3-ol ring. The dihedral angle between pyrrolidine plane
[Cg1: N(1)eC(1)eC(2)eC(3)eC(4)] and perimidine plane in mole-
cule 1 is 37.2ꢀ. This value is 44.8ꢀ in molecule 2. The pyrrolidine-3-
ol ring and methoxy benzene are nearly perpendicular with an
angle of 81.2ꢀ. The loss of planarity of the perimidine ring is worth
mentioning. The C(1) atom lies below the plane of perimidine ring
in molecule of 8b [27].
The UVeVis absorption spectra of 4a-c and 8a-d in DMF at
a concentration of 1.000 ꢂ 10ꢁ5 are showed in Figs. 1 and 2,
respectively. In the visible region, the molar absorption coefficients
and absorption maxima of compounds 4a-c were observed in the
range 1.400 ꢂ 104 to 2.330 ꢂ 104 dm3 molꢁ1 cmꢁ1 (415e439 nm).
Similarly, the visible absorption spectrums of 8a-d were domi-
nated by the characteristic perimidines bands in the region
381e383 nm. The molar absorption coefficients were calculated in
the range of 2.170 ꢂ 104 to 2.360 ꢂ 104 dm3 molꢁ1 cmꢁ1. There was
no significant difference between them.
While compounds 4b-d show thermal stability up to 250 ꢀC,
compounds 8 are stable up to 216e235 ꢀC as seen in Fig. 3. The
curves obtained from thermogravimetric analyses have character-
istic one-step decomposition region up to 500 ꢀC.
Fig. 5. Perspective view of N2eH2$$$O3i and N4eH4$$$O9ii interactions. Some hydrogen atoms have been omitted for clarity. (i) ꢁx þ 2, ꢁy þ 1, ꢁz þ 1; (ii) ꢁx þ 1, ꢁy, ꢁz þ 2.

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[8] Cado F, Bazureau JP, Hamelin J. Synthesis of 2-oxo-delta(2)-pyrrolino-[1,2-a]-
There are strong and nearly linear intramolecular hydrogen
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We have developed two novel and convenient routes for the
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Acknowledgment
The authors are indebted to Anadolu University and the
Medicinal Plants and Medicine Research Centre of Anadolu
University, Eskisehir, Turkey, for the use of the X-ray diffractometer.
This study was financially supported by The Scientific and Tech-
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[27] Crystallographic data for the structural analysis of 8b has been deposited at
the Cambridge Crystallographic Data Centre as deposition No. CCDC
830382. Copies of the data can be obtained, free of charge, on applicant to
the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cam-
bridge, CB2 1EZ UK (fax: þ44 (1223) 336033); email: deposit@ccdc@cam.
ac.uk.