Synthesis and fluorescence of pyrazolines substituted with pyrimidine and ferrocene subunits

Article abstract of DOI:10.1515/hc-2015-0129

1,3,5-Trisubstituted 2-pyrazolines were synthesized by the reaction of chalcones with hydrazine in hot ethanol. Their structures were elucidated by ¹H NMR, ¹³C NMR, IR, MS and elemental analysis. The fluorescence spectra were measure

Full text of DOI:10.1515/hc-2015-0129

Heterocycl. Commun. 2016; aop
Manman Liu and Jian Zhang*
Synthesis and fluorescence of pyrazolines
substituted with pyrimidine and ferrocene
subunits
DOI 10.1515/hc-2015-0129
and fluorescence of novel ethyl 2-(3-ferrocenyl)-5-aryl-4,
-dihydropyrazol-1-yl)-6-methyl-5-phenylpyrimidine-4-
carboxylates 6a-h (Scheme 1).
Received June 1, 2015; accepted August 7, 2015
5
Abstract: 1,3,5-Trisubstituted 2-pyrazolines were synthe-
sized by the reaction of chalcones with hydrazine in hot
1
13
ethanol. Their structures were elucidated by H NMR, C
NMR, IR, MS and elemental analysis. The fluorescence Results and discussion
spectra were measured in different organic solvents. The
emission wavelength is blue shifted with the increase in Starting compounds 1-5 were prepared by using literature
solvent polarity.
procedures [35]. The desired pyrazoline derivatives 6a-h
were obtained by the reaction of ferrocenyl chalcones 5
with pyrimidin-2-ylhydrazine 4 under reflux conditions in
Keywords: ferrocene; fluorescence; pyrazoline; pyrimi-
dine; synthesis.
51–82% yields. The structures of products 6a-h were char-
acterized by spectroscopic methods and elemental analysis.
The fluorescence spectra of compounds 6a-h were
recorded in chloroform, tetrahydrofuran and dichlo-
Introduction
-5
romethane (1ꢀ×ꢀ10 ꢁ) at room temperature at the excita-
Pyrazoline derivatives have attracted increasing attention tion wavelength of 371 nm. The emission wavelengths
due to their pharmaceutical properties such as antimi- are from 422 nm to 434 nm. The spectra are shown in
crobial [1–3], antiamoebic [4, 5], antinociceptive [6], anti- Figures 1–3. It can be concluded that different aromatic
cancer [7] and antidepressant [8] activities. In addition, groups at C5 of the central 4,5-dihydropyrazole moiety
because of their excellent fluorescence [9, 10], they have have little influence on the emission wavelengths.
been widely used as fluorescent brightening agents, fluo-
rescence chemosensors, hole-transport materials in elec-
trophotography, as components of OLEDs and as novel
Experimental
All chemicals were of reagent grade, purchased from commercial
sources and used without further purification. Melting points were
fluorescent materials [11–21].
Substituted pyrimidines [22–26] are central subunits
of interesting pharmacological agents, such as calcium
channel modulators, α1 a-adrenergic receptor antago- recorded on electrothermal digital melting point apparatus and were
nists, mitotic kinesin inhibitors and hepatitis B virus rep- uncorrected. Aromatic aldehydes, ethyl acetoacetate, phosphorus
oxychloride and hydrazine were purchased from the Alladin Chemical
lication inhibitors [27–31]. Ferrocene has been used for the
preparation of small bioactive molecules due to its good
Company and were used without further purification. All solvents were
1
13
dried using standard methods before use. H NMR (400 MHz) and
C
biocompatibility [32–34]. Recently, ferrocene containing
multichannel chemosensors with electrochemical proper-
NMR (100 MHz) spectra were recorded in CDCl on a Bruker AVANCE
3
III 400 instrument. IR spectra were recorded with an FTIR 1730 spec-
ties have received considerable attention. In light of these trometer. Fluorescence spectra were obtained on a Sanyo 970CRT
spectrofluorometer with the excitation wavelength of 371 nm. Starting
materials 1-5 were prepared by using literature procedures [36–39].
data,wewouldliketoreportthesynthesis,characterization
*
Corresponding author: Jian Zhang, College of Chemistry and
Synthesis of compounds 6a-h
materials, South-Central University for Nationalities,
Wuhan 430074, P. R. China, e-mail: jianzhangye@gmail.com
Manman Liu: College of Chemistry and materials, South-Central
University for Nationalities, Wuhan 430074, P. R. China
To a mixture of ferrocenyl chalcone 5a-h (0.01 mol) and pyrimi-
dine hydrazine 4 (0.012 mol) in ethanol (30 mL) was added sodium
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ꢀꢀꢀꢀꢁꢀM. Liu and J. Zhang: Synthesis and fluorescence of substituted pyrazolines
O
O
O
H N
HNO3
b
2
AlCl3
EtO
NH
CHO
O
EtO
a
H N
2
N
H
O
1
O
O
O
POCl3
c
NH NH
2
2
EtO
N
EtO
N
EtO
N
d
N
O
N
Cl
N
NHNH2
H
2
3
4
O
OEt
N
N
O
N
N
Ar
Ar
NaOH
e
4
Fe
Fe
5a-5h
6a-6h
Cl
Br
Me
OMe
Ar = a:
b:
c:
S
d:
e: Ph
f:
g:
h:
O
Cl
Scheme 1ꢀReagents, conditions and yields: (a) AlCl , EtOH, reflux 3 h, 78–83%; (b) HNO (50–60%), ice-bath 1 h, 68–79%; (c) POCl , EtOH,
3
3
3
reflux, 3 h, 69–85%; (d) NH NH , EtOH, reflux 4 h, 77–85%; (e) acetic acid, Ar-CHO, EtOH, reflux 8–12 h, 75–80%.
2
2
6
6
6
6
6
6
6
e
a
b
c
d
f
900
800
6
6
6
6c
6d
6f
e
a
b
3
3
3
2
2
2
2
2
1
1
1
1
1
400
200
000
800
600
400
200
000
800
600
400
200
000
7
00
600
g
6g
6
5
4
00
00
6h
h
300
200
100
0
8
6
4
2
00
00
00
00
0
-100
3
50
400
450
500
550
600
-
200
Wavelength/nm
350
400
450
500
550
600
Wavelength/nm
Figure 2ꢀFluorescence emission spectra of 6a-h in THF.
Figure 1ꢀFluorescence emission spectra of compounds 6a-h in
CHCl .
3
Ethylꢀ2-(3-ferrocenyl-5-(2-chlorophenyl)-4,5-dihydropyrazol-
1
-yl)-4-methyl-6-phenylpyrimidine-5-carboxylateꢀ(6a)ꢂThis
hydroxide (0.005 mol) at room temperature, and the resulting mix- compound was obtained as pale yellow powder in 81% yield; mp
ture was stirred at reflux for 10 h. Then the mixture was cooled to 250–251°C; H NMR: δ 7.48 (d, J ꢀ=ꢀ 6.8 Hz, 1H, aromatic), 7.35 (d, J ꢀ=ꢀ
1
room temperature, poured into ice water and neutralized with hydro- 7.4 Hz, 4H, aromatic), 7.25 (d, J ꢀ=ꢀ 11.2 Hz, 3H, aromatic), 6.16 (dd,
chloric acid. The resultant precipitate was filtrated, washed with J ꢀ=ꢀ 11.9, 4.5 Hz, 1H, pyrazoline), 4.91 (s, 1H, ortho-C H ), 4.61 (s, 1H,
5
4
water and crystallized from ethanol to afford compound 6a-h.
ortho-C H ), 4.42 (d, J ꢀ=ꢀ 9.7 Hz, 2H, meta-C H ), 4.13 (s, 5H, C H ), 4.08
5 4 5 4 5 5
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M. Liu and J. Zhang: Synthesis and fluorescence of substituted pyrazolinesꢂꢁꢀꢀꢀꢂ3
Ethylꢀ2-(3-ferrocenyl-5-(4-bromophenyl)-4,5-dihydropyrazol-
3
2
2
1
1
000
500
000
500
000
6e
1
-yl)-4-methyl-6-phenylpyrimidineꢀ-5-carboxylate(6d)ꢂThis
6
6
6
6
a
b
c
d
compound was obtained as pale yellow powder in 86% yield; mp
1
198–199°C; H NMR: δ 7.48 (d, J ꢀ=ꢀ 8.2 Hz, 2H, aromatic), 7.39 (d, J ꢀ=ꢀ 4.9
Hz, 1H, aromatic), 7.33 (d, J ꢀ=ꢀ 5.8 Hz, 3H, aromatic), 7.24 (d, J ꢀ=ꢀ 9.5 Hz,
6f
3
H, aromatic), 5.69 (dd, J ꢀ=ꢀ 12.5, 2.9 Hz, 1H, pyrazoline), 4.87 (s, 1H,
6
6
g
h
ortho-C H ), 4.59 (s, 1H, ortho-C H ), 4.41 (d, J ꢀ=ꢀ 10.1 Hz, 2H, meta-
5
4
5
4
C H ), 4.12 (s, 5H, C H ), 4.06 (m, 2H, methylene), 3.75 (dd, J ꢀ=ꢀ 16.9,
5
4
5
5
1
2
2.1 Hz, 1H, pyrazoline), 3.09 (dd, J ꢀ=ꢀ 17.4, 4.4 Hz, 1H, pyrazoline),
1
3
.56 (s, 3H, methyl), 0.96 (t, J ꢀ=ꢀ 7.2 Hz, 3H, methyl); C NMR: δ 168.8,
1
1
67.6, 165.4, 156.9, 155.4, 146.1, 138.9, 129.5, 128.4, 128.1, 126.6, 124.4,
24.3, 116.4, 76.0, 70.3, 70.0, 69.4, 68.1, 67.5, 61.1, 57.1, 43.8, 23.3, 13.1;
5
00
0
IR: 2926(CH, aliphatic), 1712(Cꢀ=ꢀO), 1545(Cꢀ=ꢀN), 1513(Cꢀ=ꢀN), 1466(Cꢀ=ꢀN)
-1
+
cm ; MS: m/z 649.1(M +1). Anal. Calcd for C H BrFeN O : C, 61.04; H,
4
33
29
4
2
.50; N, 8.63. Found: C, C, 60.91; H, 4.35; N, 8.41.
350
400
450
500
550
600
Wavelength/nm
Ethylꢀ2-(3-ferrocenyl-5-phenyl-4,5-dihydropyrazol-1-yl)-4-
Figure 3ꢀFluorescence emission spectra of compounds 6a-h in
CH Cl .
methyl-6-phenylpyrimidine-5-carboxylate (6e)ꢂThis compound
1
2
2
was obtained as pale yellow powder in 83% yield; mp 195–196°C; H
NMR: δ 7.38 (d, J ꢀ=ꢀ 4.3 Hz, 5H, aromatic), 7.36–7.29 (m, 5H, aromatic),
5
.77 (dd, J ꢀ=ꢀ 11.9, 4.8 Hz, 1H, pyrazoline), 4.92 (s, 1H, ortho-C H ), 4.60
5 4
(
s, 1H, ortho-C H ), 4.42 (d, J ꢀ=ꢀ 11.2 Hz, 2H, meta-C H ), 4.14 (s, 5H,
5
4
5
4
(
(
m, 2H, methylene), 3.83 (dd, J ꢀ=ꢀ 16.9, 11.4 Hz, 1H, pyrazoline), 3.05
dd, J ꢀ=ꢀ 17.9, 4.2 Hz, 1H, pyrazoline), 2.59 (s, 3H, methyl), 1.01 (t, J ꢀ=ꢀ 7.1
C H ), 4.12–4.03 (m, 2H, methylene), 3.77 (dd, J ꢀ=ꢀ 17.1, 11.9 Hz, 1H,
pyrazoline), 3.16 (dd, J ꢀ=ꢀ 17.0, 4.3 Hz, 1H, pyrazoline), 2.59 (s, 3H,
5
5
1
3
Hz, 3H, methyl); C NMR: δ 168.8, 167.7, 165.27, 156.7, 155.4, 155.3, 142.4,
38.8, 131.8, 129.6, 128.3, 127.7, 121.1, 116.2, 75.8, 75.8, 70.4, 70.2, 69.3,
8.0, 67.6, 61.1, 43.7, 23.4, 13.6; IR: 2982(CH, aliphatic), 1704(Cꢀ=ꢀO),
1
3
methyl), 0.98 (t, J ꢀ=ꢀ 7.2 Hz, 3H, methyl); C NMR: δ 168.9, 167.7, 165.6,
56.8, 155.5, 143.3, 138.8, 129.5, 128.7, 128.3, 128.0, 127.4, 125.9, 115.9,
1
1
6
7
6.1, 70.3, 70.0, 69.3, 68.1, 67.6, 61.6, 61.1, 43.9, 23.4, 13.6; IR: 2975(CH,
-
1
+
1
544(Cꢀ=ꢀN), 1510(Cꢀ=ꢀN), 1466(Cꢀ=ꢀN) cm ; MS: m/z 605.1(M +1). Anal.
-1
aliphatic), 1700(Cꢀ=ꢀO), 1545(Cꢀ=ꢀN), 1515(Cꢀ=ꢀN), 1466(Cꢀ=ꢀN) cm ; MS:
Calcd for C H ClFeN O : C, 65.52; H, 4.83; N, 9.26. Found: C, 65.37;
33
29
4
2
+
m/z 571.1(M +1). Anal. Calcd for C H FeN O : C, 69.48; H, 5.30; N,
33
30
4
2
H, 4.64; N, 9.06.
9
.82. Found: C, 69.22; H, 5.15; N, 9.64.
Ethylꢀ2-(3-ferrocenyl-5-(4-chlorophenyl)-4,5-dihydropyrazol-
-yl)-4-methyl-6-phenylpyrimidine-5-carboxylateꢀ(6b)ꢂThis
Ethyl 2-(3-ferrocenyl-5-(4-methylphenyl)-4,5-dihydropyrazol-1-yl)-
1
4
-methyl-6-phenylpyrimidine -5-carboxylate (6f)ꢂThis compound
compound was obtained as pale yellow powder in 75% yield; mp
1
1
was obtained as pale yellow powder in 81% yield; mp 195–196°C; H
2
18–219°C; H NMR: δ 7.42 (s, 2H, aromatic), 7.38–7.32 (m, 6H, aro-
NMR: δ 7.37 (s, 3H, aromatic), 7.28 (d, J ꢀ=ꢀ 5.4 Hz, 2H, aromatic), 7.18
matic), 7.31 (s, 1H, aromatic), 5.73 (dd, J ꢀ=ꢀ 12.6, 4.4 Hz, 1H, pyrazoline),
(
d, J ꢀ=ꢀ 8.1 Hz, 2H, aromatic), 5.74 (dd, J ꢀ=ꢀ 12.4, 4.6 Hz, 1H, pyrazoline),
4
.90 (s, 1H, ortho-C H ), 4.63 (s, 1H, ortho-C H ), 4.44 (d, J ꢀ=ꢀ 10.1 Hz,
5
4
5
4
4
.91 (s, 1H, ortho-C H ), 4.60 (s, 1H, ortho-C H ), 4.42 (d, J ꢀ=ꢀ 11.2 Hz, 2H,
2
H, meta-C H ), 4.15 (s, 5H, C H ), 4.12 – 4.05 (m, 2H, methylene),
5
4
5
4
5
4
5
5
meta-C H ), 4.15 (s, 5H, C H ), 4.11–4.04 (m, 2H, methylene), 3.75 (dd, J ꢀ=ꢀ
3
.77 (dd, J ꢀ=ꢀ 17.9, 11.9 Hz, 1H, pyrazoline), 3.11 (dd, J ꢀ=ꢀ 17.5, 3.7 Hz, 1H,
5
4
5
5
1
3
17.2, 12.2 Hz, 1H, pyrazoline), 3.14 (dd, J ꢀ=ꢀ 17.2, 3.8 Hz, 1H, pyrazoline),
pyrazoline), 2.58 (s, 3H, methyl), 0.99 (t, J ꢀ=ꢀ 7.1 Hz, 3H, methyl);
C
2
.59 (s, 3H, methyl), 2.36 (s, 3H, methyl), 0.99 (t, J ꢀ=ꢀ 7.0 Hz, 3H, methyl);
NMR: δ 168.8, 167.5, 165.3, 156.8, 155.4, 142.1, 138.6, 130.3, 129.6, 128.9,
13
C NMR: δ 169.9, 167.6, 165.2, 156.8, 155.5, 140.3, 138.9, 137.0, 129.4, 129.3,
1
28.3, 128.1, 127.4, 121.3, 75.9, 70.3, 70.2, 69.3, 68.0, 67.7, 61.2, 57.2, 43.9,
3.4, 13.6; IR: 2977(CH, aliphatic), 1708(Cꢀ=ꢀO), 1547(Cꢀ=ꢀN), 1511(Cꢀ=ꢀN),
1
28.4, 128.0, 125.9, 115.8, 76.2, 70.3, 70.00, 69.3, 68.0, 67.6, 61.4, 61.1, 43.9,
2
-1
-1
23.4, 21.1, 13.6; IR: 1703(Cꢀ=ꢀO), 1583(Cꢀ=ꢀN), 1512(Cꢀ=ꢀN), 1469(Cꢀ=ꢀN) cm ;
1
465(Cꢀ=ꢀN) cm ; MS: m/z 605.1(M+1). Anal. Calcd for C H ClFeN O :
33 29 4 2
MS: m/z 585.1(M+1). Anal. Calcd for C H FeN O : C, 69.87; H, 5.52; N,
9
C, 65.52; H, 4.83; N, 9.26. Found: C, 65.45; H, 4.76; N, 9.13.
34 32
4
2
.59. Found: C, 69.65; H, 5.31; N, 9.37.
Ethylꢀ2-(3-ferrocenyl-5-(thiophene-2-yl)-4,5-dihydropyrazol-
1
-yl)-4-methyl-6-phenylpyrimidine-5-carboxylateꢀ(6c)ꢂThis Ethyl 2-(3-ferrocenyl-5-(4-methoxyphenyl)-4,5-dihydropyrazol-
compound was obtained as pale yellow powder in 71% yield; mp199– 1-yl)-4-methyl-6-phenylpyrimidine-5-carboxylateꢀ(6g)ꢂThis
1
2
00°C. H NMR: δ 7.49 (d, J ꢀ=ꢀ 6.9 Hz, 5H, aromatic), 7.29–7.18 (m, 1H, compound was obtained as pale yellow powder in 79% yield; mp
1
aromatic), 7.10 (d, J ꢀ=ꢀ 2.9 Hz,1H, aromatic), 7.08 – 6.91 (m, 1H, aro- 185–186°C; H NMR: δ 7.38 (s, 4H, aromatic), 7.28 (s, 4H, aromatic),
matic), 6.10 (dd, J ꢀ=ꢀ 11.4, 3.9 Hz, 1H, pyrazoline), 4.96 (s, 1H, ortho- 5.73 (dd, J ꢀ=ꢀ 10.4, 4.3 Hz, 1H, pyrazoline), 4.91 (s, 1H, ortho-C H ), 4.61
5
4
C H ), 4.59 (s, 1H, ortho-C H ), 4.45 (t, J ꢀ=ꢀ 18.4 Hz, 2H, meta-C H ), (s, 1H, ortho-C H ), 4.42 (d, J ꢀ=ꢀ 10.2 Hz, 2H, meta-C H ), 4.15 (s, 5H,
5
4
5
4
5
4
5
4
5
4
4
.12 (s, 5H, C H ), 4.10 (m, 2H, methylene), 3.74 (dd, J ꢀ=ꢀ 17.1, 11.6 Hz, C H ), 4.12–4.02 (m, 2H, methylene), 3.82 (s, 3H, methoxy), 3.73 (dd,
5 5
5 5
1
H, pyrazoline), 3.32 (dd, J ꢀ=ꢀ 17.1, 4.0 Hz, 1H, pyrazoline), 2.61 (s, 3H, J ꢀ=ꢀ 12.0, 3.4 Hz, 1H, pyrazoline), 3.14 (dd, J ꢀ=ꢀ 16.0, 4.2 Hz, 1H, pyrazo-
1
3
13
methyl), 1.00 (t, J ꢀ=ꢀ 7.1 Hz, 3H, methyl); C NMR: δ 168.9, 167.7, 165.3, line), 2.59 (s, 3H, methyl), 0.98 (t, J ꢀ=ꢀ 5.8 Hz, 3H, methyl); C NMR: δ
56.9, 155.6, 146.0, 138.7, 129.6, 128.4, 128.1, 126.6, 124.5, 124.4, 116.2, 168.9, 167.3, 166.4, 156.7, 154.8, 141.4, 140.0, 138.0, 128.3, 128.4, 128.2,
1
7
5.7, 70.4, 70.1, 69.4, 68.1, 67.5, 61.2, 57.1, 43.9, 23.4, 13.6; IR: 2987(CH, 127.9, 125.0, 116.9, 76.3, 70.6, 70.0, 69.4, 68.3, 67.4, 62.1, 61.1, 55.8, 43.0,
-1
-1
aliphatic), 1702(Cꢀ=ꢀO), 1580(Cꢀ=ꢀN), 1503(Cꢀ=ꢀN), 1469(Cꢀ=ꢀN) cm ; MS: 23.4, 13.6; IR: 1713(Cꢀ=ꢀO), 1584(Cꢀ=ꢀN), 1512(Cꢀ=ꢀN), 1467(Cꢀ=ꢀN) cm ; MS:
+
m/z 577.1(M +1). Anal. Calcd for C H FeN O S: C, 64.59; H, 4.90; N, m/z 601.1(M+1). Anal. Calcd for C H FeN O : C, 68.01; H, 5.37; N, 9.33.
3
1
28
4
2
34 32
4
3
9.72. Found: C, 65.32; H, 4.72; N, 9.54.
Found: C, 67.88; H, 5.16; N, 9.14.
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ꢀꢀꢀꢀꢁꢀM. Liu and J. Zhang: Synthesis and fluorescence of substituted pyrazolines
Ehylꢀ2-(3-ferrocenyl-5-furan-2-yl-4,5-dihydropyrazol-1-yl)-4-
methyl-6-phenylpyrimidine-5-carboxylate (6h)ꢂThis compound
was obtained as pale yellow powder in 79% yield; mp 105–106°C;
[6] Kaplancikli, Z. A.; Turan-Zitouni, G.; Ozdemir, A, Can, O. D.;
Chevallet, P. Synthesis and antinociceptive activities of some
pyrazoline derivatives. Eur. J.Med. Chem. 2009, 44, 2606–2610.
[7] Shaharyar, M.; Abdullah, M. M.; Bakht, M. A.; Majeed, J.
Pyrazoline bearing benzimidazoles: search for anticancer
agent. Eur. J. Med. Chem. 2010, 45, 114–119.
[8] Gökhan-Kelekçi, N.; Koyunog, S.; Yabanog, S.; Yelekçi, K;
Özgen, Ö.; Uçar, K.; Erol, G.; Kendi, E.; Yesilada, A. Prepara-
tion of both enantiomers of ethyl 4,4,4-trifluoro-3-hydroxy
butanoate by enantionselective microbial reduction. Bioorg.
Med. Chem. 2009, 17, 675–689.
[9] Yang, B.; Li, Y.; Xu, C. X. The progress of organic flurescent
materials. Chem. Res. Appl. 2003, 15, 11–16.
1
H NMR: δ 7.54 (s, 2H, aromatic), 7.41 (d, J ꢀ=ꢀ 19.1 Hz, 3H, aromatic),
7
.28 (s, 1H, aromatic), 5.91 (dd, J ꢀ=ꢀ 11.2, 3.4 Hz, 1H, pyrazoline), 5.01
(
s, 1H, ortho-C H ), 4.55 (s, 1H, ortho-C H ), 4.43 (d, J ꢀ=ꢀ 13.1 Hz, 2H,
5
4
5
4
meta-C H ), 4.23 (s, 5H, C H ), 4.15–4.01 (m, 2H, methylene), 3.60 (dd,
J ꢀ=ꢀ 17.4, 11.3 Hz, 1H, pyrazoline), 3.42 (dd, J ꢀ=ꢀ 17.9, 5.1 Hz, 1H, pyrazo-
line), 2.61 (s, 3H, methyl), 0.99 (t, J ꢀ=ꢀ 4.7 Hz, 3H, methyl); C NMR:
δ 168.7, 167.0, 165.4, 157.9, 156.1, 146.2, 139.1, 129.6, 128.5, 128.0, 126.2,
5
4
5
5
1
3
1
1
25.3, 124.4, 117.1, 76.2, 70.7, 70.2, 69.6, 68.9, 67.6, 62.1, 56.9, 44.1, 23.6,
-1
3.7;IR: 1715(Cꢀ=ꢀO), 1630(Cꢀ=ꢀN), 1511(Cꢀ=ꢀN), 1468(Cꢀ=ꢀN) cm ; MS: m/z
5
61.1(M+1). Anal. Calcd for C H FeN O : C, 66.44; H, 5.04; N, 10.00.
31 28 4 3
Found: C, 66.21; H, 4.87; N, 9.86.
[10] Lu, Z. H.; Jing, Q.; Zhu, W. G.; Xie, M. G.; Hou, Y. B.; Chen, X. H.;
Wang, Z. J.; Zou, D. C.; Tsutu, T. Efficient blue emission from
pyrazoline organic light emitting diodes. Synth. Mehods. 2000,
1
11, 425–427.
[
11] Young, R. H.; Fitzgerald, J. J. Dipole moments of hole-transporting
Conclusions
materials and their influence on hole mobility in molecularly
doped polymers. J. Phys. Chem. 1995, 99, 4230–4240.
We have designed and synthesized a series of novel pyra- [12] Sano, T.; Fujii, T.; Nishio, Y.; Hamada, Y.; Shibata, K.; Kuroki, K.
zoline chromophores containing pyrimidine and ferrocene
moieties which show a blue emission. This fluorescence
is blue shifted with the increase of solvent polarity. The
synthetic strategy is straightforward, benefits from high
yield and facile purification without tedious silica gel
chromatography.
Pyrazoline dimers for hole transport materials in organic
electroluminescent devices. Jpn. J. Appl. Phys. 1995, 34,
3
124–3127.
[
[
[
[
13] Barbera, J.; Koen, C.; Raquel, G.; Stephan, H.; Andre, P.;
Jose, L. S. Versatile optical materials: fluorescence, non-linear
optical and mesogenic properties of selected 2-pyrazoline
derivatives. J. Mater. Chem. 1998, 8, 1725–1730.
14] Gao, Z. Q.; Lee, C. S.; Bello, I.; Lee S. T.; Wu, S. K.; Yan, Z. L.
Organic single- and doublelayer electroluminescent devices
based on substituted phthalocyanines. Synth. Methods 1999,
Acknowledgments: The authors express their thanks to
the Nature Science Foundation of Hubei Province of China
1
05, 141–149.
(
No. 2012FFB07410) for financial support during this
15] Zhang, X. H.; Lai, W. Y.; Gao, Z.Q.; Wong, T. C.; Lee, C.S.;
Kwong, H. L. Photoluminescence and electroluminescence of
pyrazoline monomers and dimers. Chem. Phys. Lett. 2000,
investigation.
3
20, 77–80.
16] Gao, X. C.; Cao, H.; Zhang, L. Q.; Zhang, B. W.; Cao, Y.;
Huang, C. H. Properties of a new pyrazoline derivative and its
application in electroluminescence. J. Mater. Chem. 1999, 9,
1077–1080.
References
[
1] Manna, K.; Agrawal, Y. K. Microwave assisted synthesis of new
indophenazine 1,3,5-trisubstituted pyrazoline derivatives of
benzofuran and their antimicrobial activity. Bioorg. Med. Chem.
[17] Xiao, D. B.; Xi, L.; Yang, W. S.; Fu, H. B.; Shuai, Z. G.; Fang, Y.
Size-tunable emission from 1,3-diphenyl-5-(2-anthryl)-
2-pyrazoline nanoparticles. J. Am. Chem. Soc. 2003, 125,
6740–6745.
[18] Sun, Y. F.; Cui, Y. P. The synthesis, structure and spectroscopic
properties of novel of novel oxazolone-, pyrazolone- and
pyrazoline-containing heterocycle chromophores. Dyes Pig-
ments 2009, 81, 27–34.
2
009, 19, 2688–2692.
[2] Abdel-Wahab, B. F.; Abdel-Aziz, H. A.; Ahmed, E. M. Synthesis
and antimicrobial evaluation of 1-(benzofuran-2-yl)-4-nitro-
3
-arylbutan-1-ones and 3-(benzofuran-2-yl)-4,5-dihydro-5-aryl-1-
4-(aryl)-1,3-thiazol-2-yl]-1H-pyrazoles. Eur. J. Med. Chem. 2009,
4, 2632–2635.
[
4
[
[
[
3] El-Sayed, W. A.; Nassar, I. F.; Abdel-Rahman, A. A.-H. C-Furyl
glycosides, II: synthesis and antimicrobial evaluation of C-furyl
glycosides bearing pyrazolines,isoxazolines, and 5,6-dihydro-
pyrimidine-2(1H)-thiones. Monatsh. Chem. 2009, 140, 365–370.
4] Abid, M.; Bhat, A. R.; Athar, F.; Azam, A. Synthesis, spectral
studies and antiamoebic activity of new 1-N-substituted
[19] Bai, G.; Li, J. F.; Li, D. X.; Dong, C.; Han, X. Y.; Lin, P. H. Synthesis
and spectrum characteristic of four new organic fluorescent
dyes of pyrazoline compounds. Dyes Pigments 2007, 75, 93–98.
[20] Shi, H. B.; Ji, S. J.; Bian, B. Studies on transition metal ions
recognition properties of 1-(2-benzothiazole)-3-(2-thiophene)-
2-pyrazoline derivatives. Dyes Pigments 2007, 73, 394–396.
[21] Bing, B.; Ji, S. J.; Shi, H. B. Synthesis and fluorescent property
of some novel bis-chromophore compounds containing pyra-
zoline and naphthalimide groups. Dyes Pigments 2008, 76,
348–352.
thiocarbamoyl-3-phenyl-2-pyrazolines. Eur. J. Med. Chem. 2009,
44, 417–425.
5] Budakoti, A.; Bhat, A. R.; Azam, A. Synthesis of new 2-
(
5-substituted-3-phenyl-2-pyrazolinyl)-1, 3-thiazolino[5,4-b]
quinoxaline derivatives and evaluation of their antiamoebic
[22] Kappe, C. O. 100 years of the Biginelli dihydropyrimidine
synthesis. Tetrahedron 1993, 49, 6937–6963.
activity. Eur. J. Med. Chem. 2009, 44, 1317–1325.
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M. Liu and J. Zhang: Synthesis and fluorescence of substituted pyrazolinesꢂꢁꢀꢀꢀꢂ5
[
23] Kappe, C. O. Recent advances in the Biginelli dihydropyrimi-
[31] Singh, K.; Arora, D.; Falkowski, D. An Efficacious Protocol
for 4-Substituted 3, 4-Dihydropyrimidinones: Synthesis and
Calcium Channel Binding Studies. Eur. J. Med. Chem, 2009, 19,
3258–3264.
[32] Staveren, D. V.; Metzler-Nolte, N. Bioorganometallic chemistry
of ferrocene. Chem. Rev. 2004, 104, 5931–5985.
[33] Roux, C.; Biot, C. Ferrocene-based antimalarials Future. Med.
Chem. 2012, 4, 783–797.
[34] Ganesh, V.; Sudhir, V.; Kundu, T. S. Chandrasekaran 10 years of
click chemistry: synthesis and applications of ferrocene-derived
triazoles Chemistry. Asian J. Chem. 2011, 6, 2670–2694.
[35] Pavia, D. L. Introduction to Spectroscopy; Brooks & Cole:
New York, 2009.
[36] Puchala, A.; Belaj, F.; Bergman, J. On the reaction of
3,4-dihydropyrimidones with nitric acid. Preparation and X-ray
structure analysis of a stable nitrolic acid. J. Heterocycl. Chem.
2001, 38, 1345–1352.
dine synthesis. Acc. Chem. Res. 2000, 33, 879–888.
24] Dallinger, D.; Stadler, A.; Kappe, C. O. Solid-and solution-
phase synthesis of bioactive dihydropyrimidines. Pure Appl.
Chem. 2004, 76: 1017–1024.
[
[
[
25] Gong, L. Z.; Chen, X. H.; Xu, X. Y. Asymmetric organocatalytic
biginelli reactions: a new approach to quickly access optically
active 3,4-Dihydropyrimidin-2-(1H)-ones. Chem. Eur. J. 2007,
13, 8920–8926.
26] Kolosov, M. A.; Orlov, V. D.; Beloborodov, D. A. Achemical pla-
cebo: NaCl as an effective, cheapest, non-acidic and greener
catalyst for Biginelli-type 3, 4-d ihydropyrimidin-2 (1H)-ones
(
-thiones) synthesis. Mol. Divers. 2009, 13, 5–25.
[
[
[
[
27] Kappe, C. O. Biologically active dihydropyrimidones of the
Biginelli-type – a literature survey. Eur. J. Med. Chem. 2000, 35,
1
043–1052.
28] Deres, K.; Schröder, C. H.; Paessens, A. Inhibition of hepatitis
B virus replication by drug-induced depletion of nucleocap-
sids. Science 2003, 299, 893–896.
29] Lengar, A.; Kappe, C. O. Tunable carbon-carbon and carbon-
sulfur cross-coupling of boronic acids with 3, 4-dihydropyrimi-
dine-2-thiones. Org. Lett. 2004, 6, 771–774.
30] Singh, K.; Arora, D.; Poremsky, E. 1-Alkylated 3, 4-dihydropy-
rimidine-2-ones: Convenient one-pot selective synthesis and
evaluation of their calcium channel blocking activity. Eur. J.
Med. Chem. 2009, 44, 1997–2001.
[37] Singh K.; Wan B. Facile transformation of Biginelli pyrimidin-
2-(1H)-ones to pyrimidines. In vitro evaluation as inhibitors
of Mycobacterium tuberculosis and modulators of cytostatic
activity. Eur. J. Med. Chem, 2011, 46, 2290–2294.
[38] Shibata K.; Katsuyama I.; Matsui M. and Muramatsu H. Synthe-
sis of ferrocenyl-substituted 3-cyano-2-methylpyridines. Bull.
Chem.Soc. Jpn. 1990, 63, 3710–3712.
[39] Wu, X.; Wilairat, P.; Go, M. L. Antimalarial activity of ferrocenyl
chalcones. Bioorg. Med. Chem. Lett. 2002, 12, 2299–2302.
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