Synthesis and fluorescent property of pyrazoline derivatives

Article abstract of DOI:10.1002/cjoc.201100642

A series of fluorinated pyrazoline derivatives were synthesized by the reaction of fluorinated chalcone with hydrazine ArNHNH₂ (Ar=4-BrC₆F₄, 4-ClC₆H₄, C ₆H₅, 4-CH₃C

Full text of DOI:10.1002/cjoc.201100642

FULL PAPER
DOI: 10.1002/cjoc.201100642
Synthesis and Fluorescent Property of Pyrazoline Derivatives†
Lu, Beiqionga(陆蓓琼)
Zhang, Jianming*,a b(章建民)
Wang, Mingjiana(王明剑)
Zhou, Yuanhaia(邹元海)
Chen, Xiaoleia(陈晓蕾)
a Department of Chemistry, School of Science, Shanghai University, No. 99, Shangda Road, Shanghai 200444,
China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sci-
ences, 354 Fenglin Lu, Shanghai 200032, China
A series of fluorinated pyrazoline derivatives were synthesized by the reaction of fluorinated chalcone with hy-
drazine ArNHNH2 (Ar＝4-BrC6F4, 4-ClC6H4, C6H5, 4-CH3C6H4 and 4-CH3OC6H4). The structures of all these
compounds were fully supported by their spectroscopic data and one of products was further confirmed by X-ray
single crystal diffraction analysis. The capability of fluorinated triaryl-2-pyrazolines to detect metal cations was in-
＋
＋
＋
＋
＋
vestigated, by monitoring changes in their fluorescence spectra in the presence of Cd2 , Co2 , Cu2 , Mn2 , Ni2
＋
and Zn2
.
Keywords fluorinated chalcone, hydrazine, pyrazoline, fluorescent probes
Introduction
phenyl)prop-2-en-1-one 3f. It was found that ethanol
may actively participate in the reaction. All the chal-
cones 3 were easily reacted with aryl hydrazine in etha-
nol catalyzed by 0.2 equiv. HCl (37%) affording the
target compounds 5 in moderated yields (Scheme 1 and
Table 1).
Fluorescent probes are powerful tools in cell biology
for the non-invasive measurement of intracellular ion
concentrations.[1] They have found widespread dapplica-
tions, e.g., to gauge intracellular calcium concentra-
tions,[2] to visualize labile zinc[3-5] and iron pools,[6] or
as pH sensors.[7] Pyrazoline derivatives are five-mem-
bered, nitrogen-containing heterocyclic compounds
which have high hole-transport efficiency, excellent
blue emission and high quantum yield (Φf≈0.6—
0.8).[8,9] Thus, pyrazoline derivatives have been used as
fluorescent materials[10] and fluorescent p-robes.[11-13]
Previously Song and Zhu[14,15] have prepared 1-fluoro-
phenyl-5-hydroxy-5-trifluoromethyl-2-pyrazoline by the
reaction of ArfNHNH2 with trifluoromethyl-1,3-dike-
tones or β-alkoxyvinyltrifluoromethyl ketone.
Scheme 1 Synthesis of triaryl-2-pyrazolines 5
O
a
Me2N
CHO
H3C
Ar1
+
1
2
Ar2
O
N
N
Ar1
Ar1
b
Me2N
Me2N
3
5
Herein we synthesized a series of fluorinated pyra-
Condition and reagents: (a) NaOH, EtOH, room temp.; (b) Ar2NHNH2
zoline derivatives and presented their fluorescence
(4), HCl (37%), EtOH, reflux.
＋
characteristics and capability to detect Cu2 .
All the new products were fully characterized by IR,
1H NMR, 19F NMR, MS and HRMS. The compound 5f
was further determined by X-ray single crystal diffrac-
tion analysis, its molecular structure and the packing
map were shown in Figure 1 (CCDC 825257).
Results and Discussion
The synthetic routes to target compounds triaryl-2-
pyrazolines 5 are shown in Scheme 1. The fluorinated
chalcones 3 were prepared by Claisen-Schmidt conden-
sation of an acetophenone with an aldehyde in the pres-
ence of NaOH.[16] Pentafluoroace tophenone 2 reacted
with aldehyde 1 to afford the product (E)-3-(4-(dime-
thylamino)phenyl)-1-(4-ethyoxyl-2,3,5,6-tetrafluoro-
UV-vis absorption and fluorescence spectra
The UV-vis absorption properties of compounds 5 (1
×10－6 mol/L) in ethanol were presented in Figure 2.
Compounds 5b, 5d, 5g and 5h) exhibited two prominent
*
E-mail: jmzhang@shu.edu.cn ; Tel.: ＋86 21 66133801; Fax: ＋86 21 66133801
Received November 30, 2011; accepted February 12, 2012; published online June 1, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201100642 or from the author.
Dedicated to Professor Jun Zhou on the occasion of his 80th birthday.
†
Chin. J. Chem. 2012, 30, 1345—1350
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Lu et al.
FULL PAPER
Table 1 Preparation of fluorinated pyrazoline derivatives 5
Reactant
Ar1
Entry
Product Yield/% m.p./℃
3
4
Ar2
1
2
2-FC6H4
3-FC6H4
4-BrC6F4
4-BrC6F4
4-BrC6F4
4-BrC6F4
4-BrC6F4
4-BrC6F4
4-BrC6F4
4-BrC6F4
4-ClC6H4
C6H5
5a
5b
5c
5d
5e
5f
50
60
62
63
47
45
68
41
61
64
53
47
189—190
144
3
2,4-F2C6H3
3,4-F2C6H3
2,5-F2C6H3
4-EtOC6F4
4-NO2C6H4
4-CH3C6H4
2-FC6H4
141—142
130—131
157—158
147
4
5
6
7
5g
5h
5i
194
8
178—180
143—145
154
Figure 2 UV-vis absorption spectra of compounds 5 (b, d, g, h)
in ethanol (1×10－6 mol/L).
9
10
11
12
2-FC6H4
5j
2-FC6H4
4-CH3C6H4
5k
5l
145—146
148
2-FC6H4 4-CH3OC6H4
Figure 3 UV-vis absorption spectra of compounds 5b, 5i, 5j,
5k and 5l in ethanol (1×10－6 mol/L).
backbone.[10] The peak centered at 330—334 nm was
related with Ar1 group, and 5g displayed a 60 nm
red-shift compared with 5b, 5d and 5g, which indicated
that an electron-withdrawing substituent such as nitro
group could lead to a red-shift phenomenon.
(a)
In Figure 3 compounds 5i, 5j, 5k and 5l exhibited
three prominent absorption peaks from 256 to 263 nm,
304 to 315 nm and 362 to 372 nm. But 5b was an ex-
ception, it had two peaks and the maximum peak at 332
nm was blue-shifted by 30 nm, meanwhile the peak at
261 nm was lower than others, which indicated that
aromatic π-π* transition of the conjugated structure
could be broken when Ar2 group was 4-BrC6F4.
The fluorescence emission spectra of 5 in ethanol (1
×10－ mol/L) were shown in Figure 4, the emission
6
peaks varied from 406 to 506 nm. The emission wave-
lengths of 5b, 5i, 5j, 5k and 5l were 406, 452, 463, 476
and 506 nm, respectively, which demonstrated that Ar2
group with an electron-donating substituent such as
methoxyl group could lead to a red-shift phenomenon of
emission spectra. The fluorescence intensities of 5b, 5d,
5g and 5h were decreased when Ar2 group was
4-BrC6F4, we deduced that the heavy atom effect may
quench the fluorescence intensity. On the other hand,
the fluorescence intensity could be reduced for Ar2 with
(b)
(c)
Figure 1 The molecular structure (a) and the packing map (b, c)
of compound 5f.
absorption peaks from 256 to 268 nm and from 330 to
334 nm. The peak centered at 261 nm was attributed to
the localized aromatic π-π* transition of the conjugated
1346
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Chin. J. Chem. 2012, 30, 1345—1350

Synthesis and Fluorescent Property of Pyrazoline Derivatives
4
an electron-donating substituent. So it was concluded
that both Ar1 and Ar2 groups had very strong influence
on the fluorescence emission and UV-vis absorption
spectra of compounds 5.
5b to Cu2 was studied. A titration of 5b (3×10－
＋
mol/L) with CuCl2•2H2O in water-ethanol (1∶7, V/V)
revealed a linear increase of the fluorescence intensity
＋
with increasing Cu2 ions concentration (Figure 6).
This dependence has been studied in the 0—2.4×10－
3
＋
mol/L concentration range of Cu2 ions. It was obvious
＋
that the initial addition of the Cu2 ions (6×10－
4
mol/L) to the 5b solution led to an increase of the fluo-
＋
rescent intensity. Upon further addition of Cu2 ions
into the 5b solution, the fluorescent intensity increased
up to 1.5×10－3 mol/L. After this concentration, change
in fluorescence intensity was negligible. Therefore, it
can be inferred that an effective electron transfer from
＋
＋
pyrazoline to the Cu2 ions occured when Cu2 ions
coordinated with the nitrogen atom of pyrazoline.
Figure 4 Fluorescence emission spectra of compounds 5 in
ethanol (1×10－6 mol/L).
Influence of metal cations on the fluorescence inten-
sity
The abilities of compounds 5 to detect metal cations
have been tested in water-ethanol (1∶7, V/V) by moni-
toring the changes in their fluorescence intensity in the
absence and presence of various metal cations. Since
5b's characteristic can represent most of compounds 5,
so we took 5b as a ligand for example. Experiments
have been performed in the presence of different metal
Figure 6 Fluorescence spectra of 5b (3×10－4 mol/L) in a mix-
ture of water-ethanol (1∶7, V/V) solution at pH＝7 in the pres-
＋
ence of different concentration of Cu2 (0—2.4×10－3 mol/L).
＋
＋
＋
＋
＋
＋
cations: Cu2 , Cd2 , Zn2 , Co2 , Mn2 and Ni2 . Fig-
ure 5 showed under the identical condition, 5b exhibited
no response to the addition of 5 equiv. of metal cations
The inset shows the dependence of the fluorescence intensity on
＋
the concentration of Cu2
.
＋
＋
＋
＋
＋
such as Cd2 , Zn2 , Co2 , Mn2 and Ni2 . But the
＋
fluorescence intensity of 5b was enhanced when Cu2
Conclusions
ions were added to the solution.[13]
A series of fluorinated pyrazoline derivatives were
synthesized and their UV-vis absorption and fluores-
cence emission spectra in ethanol were investigated. We
found that both Ar1 and Ar2 groups can control the
UV-vis absorption and fluorescence emission wave-
length of pyrazoline derivatives. When Ar2 group was
4-BrC6F4, the fluorescence intensity of 5 was quenched,
which may be due to the heavy atom effect. The abili-
ties of compounds 5 to detect metal cations have been
＋
tested, five cations are limited, and Cu2 showed rela-
tively selectivity.
Experimental
General description of the experimental techniques
Melting points were measured and not corrected.
TLC was performed on precoated silica gel F-254 plates
(0.25 nm; E. Merck), and products and starting materi-
als were detected by viewing under UV light. Column
chromatography was performed on silica gel (200—300
mesh). Infrared spectra were recorded on an AVA-
Figure 5 Effect of the metal cations at concentration (1.5×
10－ mol/L) on the fluorescence of 5b in water-ethanol (1∶7,
3
V/V) at pH＝7 (5b 3×10－4 mol/L, λex＝371 nm, λem＝418 nm).
Furthermore, the selective fluorimetric response of
Chin. J. Chem. 2012, 30, 1345—1350
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www.cjc.wiley-vch.de
1347

Lu et al.
FULL PAPER
TAR370 FT spectrophotometer (Perkin Elmer, USA).
NMR spectra were determined with DRX500 MHz
spectometer (Bruker, Germany), using solutions in
deuterated dimethylsulfoxide and deuterated chloroform
with Me4Si and CFCl3 as the internal and external stan-
dards for 1H and 19F NMR, respectively. Low resolution
mass spectra or high resolution mass spectra were ob-
tained on Finnigan MAT-8430 instrument using the
electron impact ionization technique (70 eV).
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(2,4-diflu-
orophenyl)-5-(4-(dimethylamino)phenyl)-2-pyrazoline
(5c): Yellow solid, m.p. 141—142 ℃; H NMR (500
1
MHz, DMSO-d6) δ: 2.79 (s, 6H, 2×NCH3), 3.26 (dd,
J＝7, 16.5 Hz, 1H, CH2 pyrazoline), 3.84 (dd, J＝12,
16.5 Hz, 1H, CH2 pyrazoline), 5.39 (dd, J＝7, 12 Hz,
1H, CH pyrazoline), 6.57 (d, J＝9 Hz, 2H, Ar-H), 7.02
(d, J＝9 Hz, 2H, Ar-H), 7.14—7.18 (m, 1H, Ar-H), 7.32
—7.37 (m, 1H, Ar-H), 7.81—7.86 (m, 1H, Ar-H); 19F
NMR (470 MHz, DMSO-d6) δ: －108.00—－108.07
(m, 1F), －108.68—－108.74 (m, 1F), －135.60—
－135.68 (m, 2F), －146.75—－146.81 (m, 2F); FTIR
(KBr) ν: 3443, 2892, 1614, 1525, 1487, 1424, 1363,
Typical experimental procedure
The fluorinated chalcones 3 (Yield 44%—80%),
prepared according to literature,[16] were served as our
staring materials for further synthetic studies. Hydrazine
(1.1 mmol), fluorinated chalcones 3 (1 mmol), and 37%
HCl (0.2 mmol) in ethanol was refluxed for 8—10 h
under nitrogen atmosphere. The mixture was allowed to
cool to room temperature and the precipitates were fil-
tered to afford the crude product, which can be purified
by flash chromatography using ethyl acetate/petroleum
ether (1∶20, V/V) as the eluant for the compounds 5.
－
1
1166, 1098, 960, 855, 812 cm ; EI-MS (70 eV) m/z
(%): 527.2 ([M]＋, 64), 285.2 ([M－C6BrF4N]＋, 48),
147.2 ([C10H13N]＋, 100); HRMS cacld for C23H16Br-
F6N3: 527.0431, found 527.0432.
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(3,4-diflu-
orophenyl)-5-(4-(dimethylamino)phenyl)-2-pyrazoline
(5d): Grey solid, m.p. 130—131℃; 1H NMR (500 MHz,
DMSO-d6) δ: 2.79 (s, 6H, 2×NCH3), 3.27 (dd, J＝7,
17.5 Hz, 1H, CH2 pyrazoline), 3.76 (dd, J＝11.5, 17.5
Hz, 1H, CH2 pyrazoline), 5.43 (dd, J＝7, 11.5 Hz, 1H,
CH pyrazoline), 6.56 (d, J＝8.5 Hz, 2H, Ar-H), 7.00 (d,
J＝8.5, 2H, Ar-H), 7.47—7.56 (m, 2H, Ar-H), 7.68—
7.72 (m, 1H, Ar-H); 19F NMR (470 MHz, DMSO-d6) δ:
－135.59—－135.66 (m, 2F), －137.04—－137.11 (m,
1F), －137.85 —－137.94 (m, 1F), －146.83 —
－146.88 (m, 2F); FTIR (KBr) ν: 3449, 2896, 1633,
1615, 1522, 1487, 1442, 1352, 1270, 1191, 1159, 1100,
The physical and spectra data of all the compounds
(Entry 1—12)
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(2-fluoro-
phenyl)-5-(4-(dimethylamino)
phenyl)-2-pyrazoline
1
(5a): White solid, m.p. 189—190 ℃; H NMR (500
MHz, DMSO-d6) δ: 2.78 (s, 6H, 2×NCH3), 3.27 (dd,
J＝6, 17.5 Hz, 1H, CH2 pyrazoline), 3.85 (dd, J＝13,
17.5 Hz, 1H, CH2 pyrazoline), 5.40 (dd, J＝6, 13 Hz,
1H, CH pyrazoline), 6.57 (d, J＝9 Hz, 2H, Ar-H), 7.02
(d, J＝9 Hz, 2H, Ar-H), 7.23—7.28 (m, 2H, Ar-H),
7.41—7.45 (m, 1H, Ar-H), 7.79 (td, J＝1.5, 8 Hz, 1H,
Ar-H); 19F NMR (470 MHz, DMSO-d6) δ: －113.17—
－113.20 (m, 1F), －135.61—－135.68 (m, 2F),
－146.74—－146.80 (m, 2F); FTIR (KBr) ν: 3443,
2893, 2333, 1614, 1523, 1501, 1483, 1453, 1349, 1165,
－
1
965, 817, 772 cm ; EI-MS (70 eV) m/z (%): 527.2
([M] ＋ , 59), 285.2 ([M －C6BrF4N] ＋ , 55), 147.2
([C10H13N]＋, 100); HRMS cacld for C23H16BrF6N3:
527.0435, found 527.0432.
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(2,5-diflu-
orophenyl)-5-(4-(dimethylamino)phenyl)-2-pyrazoline
1
(5e): White solid, m.p. 157—158 ℃; H NMR (500
－
1
1106, 960, 813, 768 cm ; EI-MS (70 eV) m/z (%):
509.2 ([M]＋, 53); 267.2 ([M－C6BrF4N]＋, 38); 147.2
([C10H13N]＋, 100); HRMS calcd for C23H17BrF5N3:
509.0529, found 509.0526.
MHz, DMSO-d6) δ: 2.79 (s, 6H, 2×NCH3), 3.29 (dd,
J＝7, 17.5 Hz, 1H, CH2 pyrazoline), 3.85 (dd, J＝12,
17.5 Hz, 1H, CH2 pyrazoline), 5.42 (dd, J＝7, 12 Hz,
1H, CH pyrazoline), 6.57 (d, J＝9 Hz, 2H, Ar-H), 7.02
(d, J＝9 Hz, 2H, Ar-H), 7.26—7.37 (m, 2H, Ar-H), 7.51
—7.55 (m, 1H, Ar-H); 19F NMR (470 MHz, DMSO-d6)
δ: －118.16—－118.24 (m, 1F), －118.48—－118.54
(m, 1F), －135.47—－135.54 (m, 2F), －146.72—
－146.78 (m, 2F); FTIR (KBr) ν: 3441, 3072, 2804,
1614, 1525, 1488, 1441, 1347, 1177, 1154, 1104, 973,
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(3-fluoro-
phenyl)-5-(4-(dimethylamino)phenyl)-2-pyrazoline (5b):
White solid, m.p. 144 ℃; 1H NMR (500 MHz,
DMSO-d6) δ: 2.79 (s, 6H, 2×NCH3), 3.28 (dd, J＝6.5,
17.5 Hz, 1H, CH2 pyrazoline), 3.78 (dd, J＝11.5, 17.5
Hz, 1H, CH2 pyrazoline), 5.44 (dd, J＝6.5, 11.5 Hz, 1H,
CH pyrazoline), 6.57 (d, J＝9 Hz, 2H, Ar-H), 7.01 (d,
J ＝9 Hz, 2H, Ar-H), 7.21—7.25 (m, 1H, Ar-H),
7.44—7.48 (m, 2H, Ar-H), 7.54 (d, J＝7.5 Hz, 1H,
Ar-H); 19F NMR (470 MHz, DMSO-d6) δ: －112.67—
－112.72 (m, 1F), －135.60 —－135.66 (m, 2F),
－146.85—－146.90 (m, 2F); FTIR (KBr) ν: 3445,
2913, 1615, 1596, 1524, 1503, 1484, 1349, 1162, 1146,
－
＋
1
816, 770 cm ; EI-MS (70 eV) m/z (%): 527.2 ([M] ,
53); 285.2 ([M－C6BrF4N]＋, 50); 147.2 ([C10H13N]＋,
100); HRMS cacld for C23H16BrF6N3: 527.0430, found
527.0432.
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(4-ethyox-
yl-2,3,5,6-tetrafluorophenyl)-5-(4-(dimethylamino)phe-
1
nyl)-2-pyrazoline (5f): White solid, m.p. 147 ℃; H
－
1
1102, 963, 795 cm ; EI-MS (70 eV) m/z (%): 509.2
([M] ＋ , 58), 267.2 ([M －C6BrF4N] ＋ , 51), 147.2
([C10H13N]＋, 100); HRMS calcd for C23H17BrF5N3:
509.0524, found 509.0526.
NMR (500 MHz, DMSO-d6) δ: 1.31 (t, J＝7 Hz, 3H,
CH3), 2.79 (s, 6H, 2×NCH3), 3.24 (dd, J＝6, 17.5 Hz,
1H, CH2 pyrazoline), 3.84 (dd, J＝11.5, 17.5 Hz, 1H,
CH2 pyrazoline), 4.32 (q, J＝7, 14 Hz, 2H, CH2), 5.40
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Chin. J. Chem. 2012, 30, 1345—1350

Synthesis and Fluorescent Property of Pyrazoline Derivatives
(dd, J＝6, 11.5 Hz, 1H, CH pyrazoline) 6.56 (d, J＝8.5
Hz, 2H, Ar-H), 7.02 (d, J＝8.5 Hz, 2H, Ar-H); 19F
NMR (470 MHz, DMSO-d6) δ: －135.38—－135.45
(m, 2F),－140.88—－140.94 (m, 2F), －146.57—
－146.62 (m, 2F), －157.38 —－157.44 (m, 2F); FTIR
(KBr) ν: 3442, 2992, 1614, 1524, 1486, 1429, 1390,
(s, 6H, 2×NCH3), 3.05 (dd, J＝6, 18 Hz, 1H, CH2
pyrazoline), 3.87 (dd, J＝12, 18 Hz, 1H, CH2 pyra-
zoline), 5.31 (dd, J＝6, 12 Hz, 1H, CH pyrazoline), 6.61
(d, J＝8.5 Hz, 2H, Ar-H), 6.96 (d, J＝8.5 Hz, 2H,
Ar-H), 7.02 (d, J＝8.5 Hz, 2H, Ar-H), 7.14 (d, J＝8.5
Hz, 2H, Ar-H), 7.19—7.23 (m, 2H, Ar-H), 7.34—7.36
(m, 1H, Ar-H), 7.84 (t, J＝8 Hz, 1H, Ar-H); 19F NMR
(470 MHz, DMSO-d6) δ: －113.61—－113.63 (m, 1F);
FTIR (KBr) ν: 3442, 2887, 2808, 1615, 1591, 1524,
1498, 1451, 1390, 1323, 1232, 1187, 1128, 1095, 826,
－
1
1351, 1094, 988, 969, 882, 819 cm ; EI-MS (70 eV)
m/z: 607.2 ([M]＋, 46) , 147.2 ([C10H13N]＋, 100); HRMS
cacld for C25H18BrF8N3O: 607.0500, found 607.0505.
Crystal data for 5f, C25H18BrF8N3O (CCDC 825257):
Mr ＝608.33, monoclinic, space group P2(1)/c, a＝
10.23(3) Å, b＝14.83(4) Å, c＝16.92(5) Å, α＝90°, β＝
96.87(4)°, γ＝90°, V＝2548(12) A3, Z＝4, Dc＝1.586
Mg/m3, F(000)＝1216, crystal size 0.20 mm×0.20 mm
×0.10 mm, θ range for data collection 1.83°—25.05°,
limiting indices －10≤h≤12, －17≤k ≤16, －18
≤l≤20, reflections collected/unique 11261/4342 [R(int)
＝0.0639], completeness to θ＝25.05°, 96.1%, max. and
min. transmission 0.8487 and 0.7279, refinement
method full-matrix least-squares on F2, data/restraints/
parameters＝4342/0/347, goodness-of-fit on F2＝0.923,
final R indices [I＞2σ(I)] R1＝0.0855, wR2＝0.2038, R
indices (all data) R1＝0.1756, wR2＝0.3122, extinction
coefficient 0.027(4), largest diff. peak and hole＝0.869
－
1
812, 801, 762 cm ; EI-MS (70 eV) m/z (%): 393.2
([M]＋, 100); HRMS calcd for C23H21ClFN3: 393.1409,
found 393.1408.
1-Phenyl-3-(2-fluorophenyl)-5-(4-(dimethylamino)-
phenyl)-2-pyrazoline (5j): Pale-green solid, m.p. 154
1
℃; H NMR (500 MHz, CDCl3) δ: 2.95 (d, J＝20 Hz
6H, 2×NCH3), 3.25—3.30 (m, 1H, CH2 pyrazoline),
3.72 (dd, J ＝6.5, 13.5 Hz, 1H, CH2 pyrazoline),
3.90—3.94 (m, 1H, Ar-H), 5.21—5.23 (m, 1H, CH
pyrazoline) 6.69 (s, 2H, Ar-H), 6.78 (t, J＝7 Hz, 1H,
Ar-H), 7.03—7.19 (m, 8H, Ar-H), 8.04—8.07 (m, 1H,
Ar-H); 19F NMR (470 MHz, CDCl3) δ: －114.86—
－114.92 (m, 1F); FTIR (KBr) ν: 3446, 3057, 2878,
1614, 1595, 1500, 1450, 1383, 1318, 1118, 1102, 1066,
－
－
3
1
and －0.830 e•A .
809, 763, 738, 684 cm ; EI-MS (70 eV) m/z (%): 359.2
([M]＋, 100); 147.1 ([C10H13N]＋, 50); HRMS cacld for
C23H22FN3: 359.1796, found 359.1798.
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(4-nitrophe-
nyl)-5-(4-(dimethylamino)phenyl)-2-pyrazoline
(5g):
Orange solid, m.p. 194 ℃; 1H NMR (500 MHz,
DMSO-d6) δ: 2.80 (s, 6H, 2×NCH3), 3.35 (dd, J＝7,
17.5 Hz, 1H, CH2 pyrazoline), 3.87 (dd, J＝12, 17.5 Hz,
1H, CH2 pyrazoline), 5.53 (dd, J＝7, 12 Hz, 1H, CH
pyrazoline), 6.58 (d, J＝9 Hz, 2H, Ar-H), 7.03 (d, J＝9
Hz, 2H, Ar-H), 7.93 (d, J＝9 Hz, 2H, Ar-H), 8.27 (d,
J＝9 Hz, 2H, Ar-H); 19F NMR (470 MHz, DMSO-d6) δ:
－135.34—－135.40 (m, 2F), －146.78—－146.82 (m,
2F); FTIR (KBr) ν: 3442, 3078, 2906, 1613, 1565, 1517,
1483, 1334, 1156, 1099, 962, 820, 747 cm ; EI-MS (70
eV) m/z: 536.1 ([M]＋, 78); 146.1 ([C10H12N]＋, 100);
HRMS cacld for C23H17BrF4N4O2: 536.0476, found
536.0471.
1-(4-Methylphenyl)-3-(2-fluorophenyl)-5-(4-(dime-
thylamino)phenyl)-2-pyrazoline (5k): Pale-yellow solid,
m.p. 145—146 ℃; H NMR (500 MHz, DMSO-d6) δ:
1
2.13 (s, 3H, CH3), 2.81 (s, 6H, 2×NCH3), 3.05 (dd, J＝
6.5, 18 Hz, 1H, CH2 pyrazoline), 3.86 (dd, J＝12.5, 18
Hz, 1H, CH2 pyrazoline), 5.29 (dd, J＝6.5, 12.5 Hz, 1H,
CH pyrazoline), 6.63 (d, J＝9 Hz, 2H, Ar-H), 6.91 (q,
J＝8.5, 16 Hz, 4H, Ar-H), 7.05 (d, J＝9 Hz, 2H, Ar-H),
7.21—7.24 (m, 2H, Ar-H), 7.33—7.36 (m, 1H, Ar-H),
7.85—7.88 (m, 1H, Ar-H); 19F NMR (470 MHz,
DMSO-d6) δ:－114.10—－114.11 (m, 1F); FTIR (KBr)
ν: 3446, 3023, 2958, 2917, 2886, 2854, 1614, 1514,
1451, 1387, 1320, 1218, 1129, 1101, 815, 799, 760
cm－1; EI-MS (70 eV) m/z (%): 373.2 ([M]＋, 100);
HRMS calcd for C24H24FN3: 373.1956, found 373.1954.
1-(4-Methyoxylphenyl)-3-(2-fluorophenyl)-5-(4-(di-
methylamino)phenyl)-2-pyrazoline (5l): Yellow solid,
m.p. 148 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 2.82 (s,
6H, 2×NCH3), 3.04 (dd, J＝7.5, 17 Hz, 1H, CH2 pyra-
zoline), 3.65 (s, 3H, OCH3), 3.84 (dd, J＝11.5, 17 Hz,
1H, CH2 pyrazoline), 5.23 (dd, J＝7.5, 11.5 Hz, 1H, CH
pyrazoline), 6.64 (d, J＝9 Hz, 2H, Ar-H), 6.74 (d, J＝9
Hz, 2H, Ar-H), 6.93 (d, J＝9 Hz, 2H, Ar-H), 7.08 (d,
J＝9 Hz, 2H, Ar-H), 7.21—7.24 (m, 2H, Ar-H), 7.33—
7.36 (m, 1H, Ar-H), 7.84 (t, J＝8 Hz, 1H, Ar-H); 19F
NMR (470 MHz, DMSO-d6) δ: －114.19 (s, 1F); FTIR
(KBr) ν: 3443, 2951, 2832, 1614, 1509, 1452, 1381,
－
1
1-(2,3,5,6-Tetrafluoro-4-bromophenyl)-3-(4-methyl-
phenyl)-5-(4-(dimethylamino)phenyl)-2-pyrazoline (5h):
1
White solid, m.p. 178—180 ℃; H NMR (500 MHz,
DMSO-d6) δ: 2.26 (s, 3H), 2.75 (s, 6H, 2×NCH3), 3.18
(dd, J＝6.5, 17 Hz, 1H, CH2 pyrazoline), 3.72 (dd, J＝
11.5, 17 Hz, 1H, CH2 pyrazoline), 5.37 (dd, J＝6.5,
11.5 Hz, 1H, CH pyrazoline), 6.59—6.62 (m, 2H, Ar-H),
6.99 (d, J＝8 Hz, 2H, Ar-H), 7.19 (d, J＝8 Hz, 2H,
Ar-H), 7.55 (d, J＝8 Hz, 2H, Ar-H); 19F NMR (470
MHz, DMSO-d6) δ: －135.80—－135.84 (m, 2F),
－146.90 —－146.94 (m, 2F); FTIR (KBr) ν: 3441,
3023, 2918, 1613, 1524, 1486, 1469, 1363, 1166, 1148,
－
＋
1
963, 813 cm ; EI-MS (70 eV) m/z: 505.1 ([M] , 35);
147.1 ([C10H13N]＋, 100); HRMS cacld for C24H20Br-
F4N3: 505.0780, found 505.0777.
－
1
1237, 1182, 1121, 1097, 1030, 814, 798, 755 cm ;
EI-MS (70 eV) m/z (%): 389.3 ([M] ＋ , 4), 268.2
([M-C7H7NO]＋, 100); HRMS calcd for C24H24FN3O:
389.1902, found 389.1903.
1-(4-Chlorophenyl)-3-(2-fluorophenyl)-5-(4-(dime-
thylamino)phenyl)-2-pyrazoline (5i): Yellow solid, m.p.
1
143—145 ℃; H NMR (500 MHz, DMSO-d6) δ: 2.79
Chin. J. Chem. 2012, 30, 1345—1350
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1349

Lu et al.
FULL PAPER
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Acknowledgement
This work was supported by the National Natural
Science Foundation of China (Nos. 20972092,
21032006). The authors thank the Instrumental Analy-
sis & Research Center of Shanghai University and
Doctor Deng, Hongmei.
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 1345—1350