Synthesis, structure and antibacterial activities of novel ferrocenyl-containing 1-phenyl-3-ferrocenyl-4-triazolyl-5-aryl-dihydropyrazole derivatives

Article abstract of DOI:10.1016/S0022-328X(03)00154-2

A series of substituted ferrocene-containing propenones have been prepared from acetylferrocene. Subsequently, condensation of these propenones with phenylhydrazine gave desired dihydropyrazole derivatives, which structures have been characterized by spectra data and crystal X-ray diffraction analysis. Their antibacterial activities were screened. The mechanism involving 1,4-addition of phenylhydrazine to these propenones by initial reaction at N-1 to give dihydropyrazole derives and by initial reaction at N-2 to give an intermediate has also been discussed.

Full text of DOI:10.1016/S0022-328X(03)00154-2

Journal of Organometallic Chemistry 674 (2003) 1ꢀ9
/
www.elsevier.com/locate/jorganchem
Synthesis, structure and antibacterial activities of novel ferrocenyl-
containing 1-phenyl-3-ferrocenyl-4-triazolyl-5-aryl-dihydropyrazole
derivatives
Jianxin Fang, Zhong Jin *, Zengming Li, Wei Liu
Institute and State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China
Received 20 January 2003; received in revised form 10 March 2003; accepted 13 March 2003
Abstract
A series of substituted ferrocene-containing propenones have been prepared from acetylferrocene. Subsequently, condensation of
these propenones with phenylhydrazine gave desired dihydropyrazole derivatives, which structures have been characterized by
spectra data and crystal X-ray diffraction analysis. Their antibacterial activities were screened. The mechanism involving 1,4-
addition of phenylhydrazine to these propenones by initial reaction at N-1 to give dihydropyrazole derives and by initial reaction at
N-2 to give an intermediate has also been discussed.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Dihydropyrazole; Ferrocene; 1,4-Addition; 1,2,4-Triazole; Biological activity
1. Introduction
9]. Moreover, the stability and nontoxicity of the
ferrocenyl moiety is of particular interest rendering
such drugs compatible with other treatment [10]. In
this sense, the integration of one or more ferrocene units
into a heterocyclic ring molecular has long been
recognized as an attractive way to endow a novel
molecule functionally [11].
It is well known that certain substituted dihydropyr-
azole derivatives have highly biological active as med-
icaments in human and/or veterinary therapy [12,13],
insecticides [14,15], and herbicides [16] in the agriculture
and horticulture, especially in the agricultural field as
exemplified by RH 3421 [15a], PH 60-41 [17], PH 60-42
[18] (Fig. 1). Following our interest in the synthesis of
new analogues of dihydropyrazole with potent biologi-
cal activities, we have sought to develop approaches to
such drugs involving ferrocenyl units.
For many years, much interest has focused on the use
of the transition-metal complexes in medicine and other
biological areas as well [1,2]. A successful example is the
application of platinum complexes as anti-tumor agents
[3]. Therefore, we have expected the potential of
organometallic chemistry when directed at therapeutic
uses.
Ferrocene and its derivatives, since the discovery of it,
have been attracting much attention ranging from the
viewpoint of catalysis, organic synthesis, new materials
such as liquid crystals or polymers [4] and supramole-
cular chemistry [5]. Incorporation of a ferrocene frag-
ment into a molecule of an organic compound often
obtained unexpected biological activity, which is ratio-
nalized as being due to their different membrane-
permeation properties and anomalous metabolism [6ꢀ
/
In the present work, we describe the preparation,
structures and biological activity of a series of highly
substituted dihydropyrazole compounds, which have
been characterized by spectra data and crystal X-ray
diffraction analysis.
* Corresponding author. Tel.: ꢁ
2350-4856.
E-mail address: jinzhong2000@263.net (Z. Jin).
/
86-22-2350-4229; fax: ꢁ86-22-
/
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00154-2

2
J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ9
/
The yields from Z-isomers are very close to the ones
from E-isomers (Table 1). Moreover, it is interesting to
note that, no matter from Z-isomer or E-isomer of 5,
the same conformational (4S, 5R) dihydropyrazole
product, which aryl group and triazole group are always
in the trans-position of dihydropyrazole ring, was
obtained by X-ray crystal structure analysis (Fig. 2). It
is more likely that the same conformation has been
caused as a result of the configuration inversion of the
propenones 5 between Z and E taking place under acid
catalysis.
Fig. 1.
2. Result and discussion
2.1. Synthesis of 4,5-dihydropyrazole derivatives
containing ferrocenyl unit
As above-mentioned, except for target compounds, a
small amount of a-triazolylacetylferrocene (4), substi-
tuted benzaldehyde phenylhydrazones (8), and the
intermediates 7 were also obtained as accompaniments.
The reaction of the propenones 5 with phenylhydrazine
involves competitive 1,2-addition and 1,4-addition reac-
tions of the two nitrogen atoms in the phenylhydrazine.
It has generally been accepted that the reaction does not
proceed via 1,2-addition but 1,4-addition procedure [24].
In our present work, 1,4-addition of N-1 in the
phenylhydrazine to the propenones 5 afforded the
designed dihydropyrazole derivatives 6. In contrast,
1,4-addition of N-2 in the phenylhydrazine caused to
yield the intermediates 7 (Scheme 3). Base catalysis was
observed for reaction at N-2 but not for reaction at N-1
[25]. However, the intermediate 7 isolated explicitly
presented evidence for a mechanism involving 1,4-
addition reaction at N-2 in the phenylhydrazine under
acid catalysis.
With monitoring by GC-MS, equal quantitative a-
triazolylacetylferrocene (4) and substituted benzalde-
hyde phenylhydrazones (8) were also observed and
isolated. In addition, the yields of them varied regularly
with the change of X group in the aryl (Table 2). We
inferred that they are possibly from the cleavage of
intermediates 7 under severe conditions. Because of
massive special resistance of phenyl and ferrocenyl in
compounds 7, the cyclization of the intermediates 7 to
dihydropyrazole was unable to proceed. Alternatively,
they cleaved to the a-triazolylacetylferrocene (4) and
phenylhydrazones (8) at the reacting conditions via a
rearrangement (Scheme 4). As a result, equal quantita-
tive 4 and phenylhydrazone (8) were detected.
The a-chloroacetylferrocene (2) firstly had been pre-
pared from ferrocene and a-haloacetyl chloride by the
Friedel-Crafts acylation [19], which has recently been
used as starting material for the preparation of chiral
ferrocenyl-substituted b-aminocyclopentadienes [20].
Due to its low yield by this way [21], an alternative
process was carried out as described by Ta´rraga et al.
[22]. Therefore, metallation of acetylferrocene 1 with
LDA at ꢂ78 8C followed by sequential treatment with
/
trimethylchlorosilane and an excess of NBS provided
the a-bromoacetylferrocene (3) in 80% yield, along with
a small amount of the a,a-dibromoacetylferrocene.
Conversion of 2 and 3 into a-triazolylacetylferrocene
(4) was achieved in perfect yield (95%) by using
anhydrous potassium carbonate as a base. Sequentially,
preparation of 2-(1,2,4-triazolyl)-3-aryl-1-ferrocenylpro-
penones (5) was achieved in good yield by condensation
of 4 with substituted benzaldehydes under described
conditions [23] (Scheme 1). After separation by silica gel
column chromatography, the Z-isomers and E-isomers
were obtained, respectively. In most cases of this
reaction, the Z-isomers were obtained as the major
products (yield: 45ꢀ75%) and the E-isomer as the minor
/
ones (yield: below 15%).
Treatment of the propenones 5Z and 5E, respectively,
with phenylhydrazine using glacial acetic acid as a
catalyst afforded desired dihydropyrazoles 6 along
with a small amount of by-products [14b] (Scheme 2).
2.2. Biological evaluation
Some selected dihydropyrazole derivatives containing
ferrocenyl unit 6aꢀg were screened for their antibacter-
/
ial activity in vitro against Isariopsis clavispora, Bremia
lactucae, Cladosporium fulvum, Erysiphe graminis, Al-
ternaria mali, and their relative inhibitory ratio (%) were
determined. The results of such studies are reported in
Table 3.
The screening data indicate that compounds 6c, 6g
carrying 3-chloro and 4-methoxy, respectively, show a
Scheme 1.

J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ
/9
3
Scheme 2.
Table 1
The yields of compounds 6 from Z-isomers and E-isomers of 5
Entry Compounds 5
X
H
Yieldsa (%) of compounds 6
1
2
3
4
5a
5c
5d
5f
Z
E
69.0
68.1
Z
E
3-Cl
4-Cl
82.9
83.3
Z
E
54.3
68.5
Z
E
4-CH3 58.6
62.0
a
Isolated yields and 0.5 mol.% AcOH as catalyst.
Fig. 2. Molecular structure and crystallographic numbering scheme
similar degree of antibacterial activity. Compared with
known commercial agents, the antibacterial activities of
this type of compounds were not encouraging, although
some compounds manifested certain antibacterial activ-
ity. The other biological activities such as insecticide
were tested at the moment and the results will be
presented in the future.
˚
for compound 6a. Selected bond lengths (A): Fe(1)Ã
Fe(1)ÃC(7) 2.025(5); N(1)ÃC(11) 1.291(4); N(1)ÃN(2) 1.375(4); N(2)Ã
C(22) 1.378(4); N(2)ÃC(15) 1.456(4); N(3)ÃC(13) 1.317(4); N(3)ÃN(4)
1.354(4); N(3)ÃC(12) 1.454(4); C(13)ÃN(5) 1.307(4); C(1)ÃC(5)
1.385(6); C(6)ÃC(10) 1.421(4); C(10)ÃC(11) 1.428(5); C(12)ÃC(15)
1.528(4); C(16)Ã
N(1)ÃN(2) 108.6(3); N(1)Ã
126.7(3); C(6)ÃC(10)ÃC(11) 125.2(3); N(1)Ã
N(3)ÃC(12)ÃC(11) 108.5(2); N(3)ÃC(12)ÃC(15) 112.4(2); N(2)Ã
C(15)ÃC(16) 114.4(3); N(2)ÃC(15)ÃC(12) 100.7(2); C(16)ÃC(15)Ã
/C(6) 2.022(4);
/
/
/
/
/
/
/
/
/
/
/
/
/
/
C(17) 1.375(5). Selected bond angels (8): C(11)Ã
/
/
/
N(2)Ã
/
C(22) 121.0(3); C(22)Ã
/
N(2)Ã
/
C(5)
/
/
/
C(11)ÃC(10) 123.8(3);
/
/
/
/
/
/
/
/
/
/
/
C(12) 111.3(2).
3. Conclusion
4. Experimental
A series of highly substituted dihydropyrazole deri-
vatives have been synthesized and their structures have
All reactions were carried out under nitrogen and
monitored by TLC. All solvents were distilled prior to
use. All melting points were determined on a Kofler hot-
plate melting point apparatus and are uncorrected. The
1H-NMR spectra were measured on a JEOL-FX-90Q
spectrometer or a Bruker Ac-200 Spectrometer in
CDCl3 and d6-DMSO solution with TMS as internal
standard. Elemental analyses were determined on an
MT-3 elemental analyzer. IR spectra were recorded on a
1
been verified by H-NMR, IR, MS spectra data and
crystal X-ray diffractions analysis. The mechanism
involving 1,4-addition of phenylhydrazine to the ferro-
cenyl-substituted propenones by initial reaction at N-1
to give dihydropyrazole derives and by initial reaction at
N-2 to give an intermediate has been discussed, and
these new dihydropyrazole derivatives were also tested
for their antibacterial activities.

4
J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ9
/
Scheme 3.
mmol) in dry acetone (100 ml), 1H-1,2,4-triazole (1.52 g,
22 mmol) was added under stirring. After refluxed for 8
h, the reacting mixture was filtered and washed with
acetone (30 ml). Evaporation of combined solvent
mixture gave a brown solid, and the residue was isolated
by column chromatography on a silica gel column, to
give a yellow crystal, a-triazolylacetylferrocene (4) (5.6
Table 2
The varied yields of 3 in the syntheses of compounds 6
Entry Compound 6
X
Yields (%) of compound 4
1
2
3
4
5
6d
6a
6f
4-Cl
H
2.5
11.0
11.4
4-CH3
g) in 95% yield, which was crystallized from ethyl
6g
6i
4-OCH3 18.3
4-OH 32.6
1
acetate/petroleum ether. M.p. 116ꢀ
/
118 8C. H-NMR d
(200 MHz, CDCl3): 8.46(s, 1H, triazole), 8.16(s, 1H,
triazole), 5.38(s, 2H, CH2), 4.86(s, 2H, C5H4), 4.56(s,
2H, C5H4), 4.30(s, 5H, C5H5). M/S (70 eV): m/zꢃ295
/
Bruker Equinox 55 spectrometer with KBr discs. Mass
spectra were recorded on an HP-5988A at 70 eV; the
temperature of ionization was 200 8C. a-Chloroacetyl-
ferrocene (2) and a-bromoacetylferrocene (3) were
prepared according to the reported methods [19,22],
respectively.
[Mꢁ], Anal. Calc. for C14H13FeN3O (295.1) C 56.98; H
4.44; N 14.24. Found: C 56.96; H 4.40; N 14.09.
4.2. General procedure for syntheses of 2-(1,2,4-
triazolyl)-3-aryl-1-ferrocenylpropenones (5)
4.1. Synthesis of a-triazolylacetylferrocene (4)
To a stirred solution of the a-triazolylacetylferrocene
(4) (2.95 g, 10 mmol), piperidine (0.1 ml), glacial acetic
acid (0.5 mol.%) in dry toluene (30 ml) was added
substituted benzaldehyde (10 mmol) at room tempera-
To a suspension of a-chloroacetylferrocene (5.6 g, 21
mmol) and anhydrous potassium carbonate (3.0 g, 22
Scheme 4.

J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ
/9
5
Table 3
Antibacterial activity of ferrocenyl-substituted dihydropyrazole derivatives
Entry
Substituent X
Relative inhibitory ratio (%)
I. clavispora
B. lactucae
C. fulvum
E. graminis
A. mali
6a
6b
6c
6d
6e
6f
H
2-Cl
6.7
0
22.2
0
4.5
13.6
9.1
13.6
0
7.7
0
0
6.5
0
3-Cl
4-Cl
13.3
0
22.2
0
11.5
3.8
3.2
0
2,4-Cl2
4-CH3
4-OCH3
6.7
13.3
6.7
0
7.7
0
11.1
4.5
9.1
11.5
11.5
0
6g
0
ture under nitrogen. The mixture was then heated to
reflux and kept at this temperature until completion of
the reaction, while the water generated was evaporated
off. The solvent was evaporated off in vacuum and the
residue was purified by chromatography on silica gel
with the solvent system of ethyl acetate/petroleum ether.
The Z-ketone analogs 5 were obtained as the first elute
and the E-ketone analogs 5 were obtained as the second
elute of the chromatography.
4.2.3. 2-(1,2,4-Triazolyl)-3-(3?-chlorophenyl)-1-
ferrocenylpropenone (5c)
(Z)-5c: yield: 50.3%; deep red solid; m.p. 123ꢀ
IR (KBr): nꢃ
(200 MHz, d6-DMSO): 8.77(s, 1H), 8.40(s, 1H), 7.93(s,
1H), 7.64ꢀ6.90(m, 4H), 4.70(s, 2H), 4.53(s, 2H), 4.31(s,
5H). MS (EI): m/z (%): 417 [100, Mꢁ], 419 [33.3, Mꢁ
2].
/
124 8C.
/
1630.5, 1010.2, 1005.4 cmꢂ1. 1H-NMR d
/
/
Anal. Calc. for C21H16ClFeN3O C 60.39; H 3.86; N
10.06. Found: C 60.35; H 4.00; N 9.95.
(E)-5c: yield: 11.7%; red solid; m.p. 122ꢀ
(KBr): nꢃ
1619.2, 1092.7, 1003.9 cmꢂ1 1H-NMR d
(200 MHz, d6-DMSO): 9.09(s, 1H), 8.24(s, 1H), 7.51(s,
1H), 7.50ꢀ7.35(m, 4H), 4.56(m, 4H), 4.14(s, 5H). MS
(EI): m/z (%): 417 [100, Mꢁ], 419 [33.3, Mꢁ
2]. Anal.
/
123 8C. IR
/
.
4.2.1. 2-(1,2,4-Triazolyl)-3-phenyl-1-
ferrocenylpropenone (5a)
/
(Z)-5a: yield: 57.2%; purple solid; m.p. 128ꢀ
IR (KBr): nꢃ
1629.2, 1096.7, 1001.6 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 8.04(m, 2H), 7.84(s, 1H), 7.48ꢀ
/
130 8C.
/
/
Calc. for C21H16ClFeN3O C 60.39; H 3.86; N 10.06.
Found: C 60.40; H 3.76; N 9.85.
/
7.36(m, 5H), 4.66(m, 4H), 4.34(s, 5H). MS (EI): m/z
(%): 383 [Mꢁ]. Anal. Calc. for C21H17FeN3O C 65.82;
H 4.47; N 10.96. Found: C 65.70; H 4.47; N 10.86.
4.2.4. 2-(1,2,4-Triazolyl)-3-(4?-chlorophenyl)-1-
ferrocenylpropenone (5d)
(E)-5a: yield: 10.1%; deep red solid; m.p. 140ꢀ
IR (KBr): nꢃ
1625.2, 1102.7, 1008.3 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 8.77(s, 1H), 8.39(s, 1H), 7.53(s,
/
141 8C.
/
(Z)-5d: yield: 65.2%; purple solid; m.p. 149ꢀ
/
151 8C.
1624.5, 1103.2, 998.4 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.76(s, 1H), 8.37(s, 1H), 7.95(s,
1H), 7.42(d, Jꢃ5 Hz, 2H), 6.96(d, Jꢃ5 Hz, 2H), 4.69(s,
2H), 4.51(s, 2H), 4.31(s, 5H). MS (EI): m/z (%): 417
[100, Mꢁ], 419 [33.3, Mꢁ
2]. Anal. Calc. for
1
IR (KBr): nꢃ
/
1H), 6.61ꢀ6.59(m, 5H), 4.58(s, 2H), 4.33(s, 2H), 4.26(s,
/
5H). MS (EI): m/z (%): 383 [Mꢁ]. Anal. Calc. for
C21H17FeN3O C 65.82; H 4.47; N 10.96. Found: C
65.60; H 4.71; N 10.79.
/
/
/
C21H16ClFeN3O C 60.39; H 3.86; N 10.06. Found: C
60.14; H 3.52; N 9.97.
4.2.2. 2-(1,2,4-Triazolyl)-3-(2?-chlorophenyl)-1-
ferrocenylpropenone (5b)
(E)-5d: yield: 12.5%; deep red solid; m.p. 133ꢀ
/
134 8C.
IR (KBr): nꢃ
/
1623.6, 1099.5, 1001.9 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 9.08(s, 1H), 8.24(s, 1H), 7.51(s,
1H), 7.40(m, 4H), 4.56(s, 2H), 4.53(s, 2H), 4.16(s, 5H).
(Z)-5b: yield: 47.6%; purple solid; m.p. 127ꢀ
IR (KBr): nꢃ
1627.0, 1099.9, 1001.1 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 7.96(m, 2H), 7.64(s, 1H), 7.44ꢀ
7.00(m, 4H), 4.68(s, 2H), 4.58(s, 2H), 4.26(s, 5H). MS
(EI): m/z (%): 417 [100, Mꢁ], 419 [33.3, Mꢁ
2]. Anal.
/
129 8C.
/
/
MS (EI): m/z (%): 417 [100, Mꢁ], 419 [33.3, Mꢁ
2].
Anal. Calc. for C21H16ClFeN3O C 60.39; H 3.86; N
10.06. Found: C 60.15; H 3.71; N 9.94.
/
/
Calc. for C21H16ClFeN3O C 60.39; H 3.86; N 10.06.
Found: C 60.30; H 3.70; N 9.95.
(E)-5b: yield: 7.2%; deep red solid; m.p. 138ꢀ
IR (KBr): nꢃ
1619.2, 1092.7, 1003.9 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 8.32(s, 1H), 8.09(s, 1H), 7.23(s,
1H), 6.66ꢀ6.50(m, 4H), 4.49(s, 2H), 4.36(s, 2H), 4.20(s,
5H). MS (EI): m/z (%): 417 [100, Mꢁ], 419 [33.3, Mꢁ
2].
/
139 8C.
4.2.5. 2-(1,2,4-Triazolyl)-3-(2?,4?-dichlorophenyl)-1-
ferrocenylpropenone (5e)
/
(Z)-5e: yield: 62.3%; purple solid; m.p. 195ꢀ
/
196 8C.
1630.5, 1109.2, 996.8 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.36ꢀ8.16(m, 2H), 8.00(s, 1H),
7.58(s, 1H), 7.18(d, Jꢃ5 Hz, 1H), 6.67(d, Jꢃ5 Hz, 1H),
4.73(m, 4H), 4.44(s, 5H). MS (EI): m/z (%): 452 [100,
1
/
IR (KBr): nꢃ
/
/
/
Anal. Calc. for C21H16ClFeN3O C 60.39; H 3.86; N
10.06. Found: C 60.32; H 3.90; N 10.09.
/
/

6
J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ9
/
Mꢁ]. Anal. Calc. for C21H15Cl2FeN3O C 55.79; H 3.34;
N 9.29. Found: C 55.66; H 3.35; N 8.89.
(E)-5h: yield: 8.2%; red solid; m.p. 161ꢀ
(KBr): nꢃ
1628.0, 1093.6, 1002.0 cmꢂ1 1H-NMR d
(200 MHz, d6-DMSO): 8.50ꢀ8.20(m, 2H), 7.95(s, 1H),
/
163 8C. IR
/
.
(E)-5e: yield: 10.3%; deep red solid; m.p. 173ꢀ
IR (KBr): nꢃ
1626.7, 1092.1, 1004.2 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 8.92(s, 1H) 8.30(s, 1H), 7.70(s,
/
174 8C.
/
/
6.80ꢀ
/
6.40(m, 4H), 4.33(m, 4H), 4.15(s, 5H), 2.60ꢀ
/
2.40(m, 1H). MS (EI): m/z (%): 399 [100, Mꢁ]. Anal.
Calc. for C21H17FeN3O2 C 63.18; H 4.29; N 10.53.
Found: C 63.21; H 4.20; N 10.61.
1H), 7.60ꢀ7.40(m, 3H), 4.52(s, 2H), 4.49(s, 2H), 4.20(s,
/
5H). MS (EI): m/z (%): 452 [100, Mꢁ]. Anal. Calc. for
C21H15Cl2FeN3O C 55.79; H 3.34; N 9.29. Found: C
55.76; H 3.62; N 9.21.
4.2.9. 2-(1,2,4-Triazolyl)-3-(4?-hydroxyphenyl)-1-
ferrocenylpropenone (5i)
(Z)-5i: yield: 45.1%; purple solid; m.p. 190ꢀ
/
192 8C.
1640.1, 1092.1, 989.4 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.76(s, 1H), 8.37(s, 1H), 7.92(s,
1H), 6.80ꢀ6.60(m, 4H), 4.66(s, 2H), 4.42(s, 2H), 4.27(s,
5H), 1.80ꢀ
4.2.6. 2-(1,2,4-Triazolyl)-3-(4?-methylphenyl)-1-
ferrocenylpropenone (5f)
1
IR (KBr): nꢃ
/
(Z)-5f: yield: 61.5%; purple solid; m.p. 156ꢀ
IR (KBr): nꢃ
1615.5, 1098.0, 1009.4 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 8.38ꢀ8.22(m, 2H), 7.96(s, 1H),
5 Hz, 2H), 4.66(m,
/
157 8C.
/
/
/
1.70(m, 1H). MS (EI): m/z (%): 399 [100,
/
Mꢁ]. Anal. Calc. for C21H17FeN3O2 C 63.18; H 4.29; N
10.53. Found: C 63.15; H 4.35; N 10.59.
7.20(d, Jꢃ
/
5 Hz, 2H), 6.90(d, Jꢃ
/
4H), 4.34(s, 5H). MS (EI): m/z (%): 397 [100, Mꢁ].
Anal. Calc. for C22H19FeN3O C 66.52; H 4.82; N 10.58.
Found: C 66.47; H 4.79; N 10.59.
(E)-5i: yield: 8.9%; red solid; m.p. 178ꢀ
(KBr): nꢃ
1622.6, 1088.2, 981.3 cmꢂ1. 1H-NMR d (200
MHz, d6-DMSO): 8.42(s, 1H), 8.12(s, 1H), 7.56(s, 1H),
/
180 8C. IR
/
(E)-5f: yield: 11.7%; deep red solid; m.p. 131ꢀ
/
132 8C.
1645.6, 1109.6, 994.5 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.28(s, 1H) 8.02(s, 1H), 7.38(s,
1
6.60ꢀ
/
6.00(m, 4H), 4.13(m, 4H), 4.05(s, 5H), 2.60ꢀ
/
IR (KBr): nꢃ
/
2.40(m, 1H). MS (EI): m/z (%): 399 [100, Mꢁ]. Anal.
Calc. for C21H17FeN3O2 C 63.18; H 4.29; N 10.53.
Found: C 63.13; H 4.26; N 10.32.
1H), 7.60ꢀ7.40(m, 4H), 4.50(m, 4H), 4.18(s, 5H). MS
/
(EI): m/z (%): 397 [100, Mꢁ]. Anal. Calc. for
C22H19FeN3O C 66.52; H 4.82; N 10.58. Found: C
66.49; H 4.83; N 10.39.
4.2.10. 2-(1,2,4-Triazolyl)-3-(4?-N,N-
dimethylaminophenyl)-1-ferrocenylpropenone (5j)
(Z)-5j: yield: 59.2%; deep red solid; m.p. 153ꢀ
/
154 8C.
1635.7, 1090.5, 994.4 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.20ꢀ7.90(m, 2H), 7.35(s, 1H),
6.50(m, 4H), 4.56(m, 4H), 4.30(s, 5H), 3.06(s, 6H).
1
4.2.7. 2-(1,2,4-Triazolyl)-3-(4?-methoxyphenyl)-1-
ferrocenylpropenone (5g)
IR (KBr): nꢃ
/
/
(Z)-5g: yield: 63.2%; purple solid; m.p. 159ꢀ
IR (KBr): nꢃ
1620.6, 1109.0, 1001.4 cmꢂ1. 1H-NMR d
(200 MHz, CDCl3): 8.60ꢀ8.30(m, 2H), 7.87(s, 1H),
/
161 8C.
7.00ꢀ
/
MS (EI): m/z (%): 426 [100, Mꢁ]. Anal. Calc. for
C23H22FeN4O C 64.80; H 5.20; N 13.14. Found: C
64.75; H 5.30; N 13.10.
/
/
6.80(s, 4H), 4.54(s, 4H), 4.24(s, 5H), 3.78(s, 3H). MS
(EI): m/z (%): 413 [100, Mꢁ]. Anal. Calc. for
C22H19FeN3O2 C 63.94; H 4.63; N 10.17. Found: C
63.85; H 4.62; N 10.10.
(E)-5j: yield: 11.2%; red solid; m.p. 144ꢀ
(KBr): nꢃ
1620.6, 1080.0, 993.3 cmꢂ1. 1H-NMR d (200
MHz, d6-DMSO): 8.02(s, 1H), 7.60(s, 1H), 6.96(s, 1H),
/
145 8C. IR
/
(E)-5g: yield: 8.1%; deep red solid; m.p. 134ꢀ
/
136 8C.
1638.0, 1099.6, 998.5 cmꢂ1. H-NMR d
(200 MHz, CDCl3): 8.75(s, 1H), 8.15(s, 1H), 7.37(s, 1H),
7.25(d, Jꢃ5 Hz, 2H), 6.74(d, Jꢃ5 Hz, 2H), 4.63(s, 2H),
6.60ꢀ6.40(m, 4H), 4.35(m, 4H), 4.13(s, 5H), 2.96(s, 6H).
/
1
MS (EI): m/z (%): 426 [100, Mꢁ]. Anal. Calc. for
C23H22FeN4O C 64.80; H 5.20; N 13.14. Found: C
64.78; H 5.25; N 13.06.
IR (KBr): nꢃ
/
/
/
4.45(s, 2H), 4.06(s, 5H), 3.74(s, 3H). MS (EI): m/z (%):
413 [100, Mꢁ].
Anal. Calc. for C22H19FeN3O2 C 63.94; H 4.63; N
10.17. Found: C 63.90; H 4.62; N 10.14.
4.2.11. 2-(1,2,4-Triazolyl)-3-(4?-N,N-
diethylaminophenyl)-1-ferrocenylpropenone (5k)
(Z)-5k: yield: 72.6%; purple solid; m.p. 162ꢀ
/
163 8C.
1633.8, 1091.3, 994.6 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.77(s, 1H), 8.39(s, 1H), 7.92(s,
1H), 7.59(d, Jꢃ5 Hz, 2H), 7.52(d, Jꢃ5 Hz, 2H), 4.58(s,
1
IR (KBr): nꢃ
/
4.2.8. 2-(1,2,4-Triazolyl)-3-(2?-hydroxyphenyl)-1-
ferrocenylpropenone (5h)
/
/
(Z)-5h: yield: 54.8%; deep red solid; m.p. 166ꢀ
/
167 8C.
1643.9, 1102.4, 997.4 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 8.70(s, 1H), 8.37(s, 1H), 8.30(s,
1H), 7.24(t, Jꢃ4 Hz, 1H), 6.96(d, Jꢃ4 Hz, 1H), 6.61(t,
Jꢃ4 Hz, 1H), 6.13(d, Jꢃ4 Hz, 1H), 4.69(s, 2H), 4.56(s,
2.20(m, 1H). MS (EI): m/z (%):
2H), 4.32(s, 2H), 4.26(s, 5H), 3.36(m, 4H), 1.06(t, Jꢃ6
/
1
IR (KBr): nꢃ
/
Hz, 6H). MS (EI): m/z (%): 454 [100, Mꢁ]. Anal. Calc.
for C25H26FeN4O C 66.09; H 5.77; N 12.33. Found: C
66.10; H 5.80; N 12.20.
/
/
/
/
(E)-5k: yield: 7.4%; red solid; m.p. 149ꢀ
(KBr): nꢃ
1628.4, 1082.7, 999.6 cmꢂ1. 1H-NMR d (200
MHz, d6-DMSO): 8.20ꢀ7.92(m, 2H), 7.46(s, 1H), 7.00ꢀ
6.80(m, 4H), 4.32(s, 2H), 4.17(s, 2H), 4.03(s, 5H),
/
150 8C. IR
2H), 4.35(s, 5H), 2.30ꢀ
/
/
399 [100, Mꢁ]. Anal. Calc. for C21H17FeN3O2 C 63.18;
H 4.29; N 10.53. Found: C 63.15; H 4.32; N 10.35.
/
/

J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ
/9
7
3.08(m, 4H), 1.10(m, 6H). MS (EI): m/z (%): 454 [100,
Mꢁ]. Anal. Calc. for C25H26FeN4O C 66.09; H 5.77; N
12.33. Found: C 66.01; H 5.66; N 12.13.
4.3. General procedure for syntheses of 1-phenyl-3-
ferrocenyl-4-triazolyl-5-aryl-dihydropyrazole derivatives
6
4.2.12. 2-(1,2,4-Triazolyl)-3-(3?-bromophenyl)-1-
ferrocenylpropenone (5l)
To a Schlenk reaction flask were added 2-(1,2,4-
triazolyl)-3-aryl-1-ferrocenylpropenone (5) (4 mmol),
phenylhydrazine (5 mmol), ethanol (10 ml), and glacial
acetic acid (0.5 mol.%). The reaction mixture was heated
to refluxing. After stirred at the temperature for 4 h, the
mixture was cooled and the solvent was removed in
vacuum. Chromatography on a silica gel column
afforded the 2-pyrazolin derivatives 6 in modest to
good yields. Only the intermediate 7f was isolated and
characterized, and the others were detected with GC-MS
and HPLC-MS chromatography.
(Z)-5l: yield: 57.6%; deep red solid; m.p. 131ꢀ
IR (KBr): nꢃ
1633.2, 1115.9, 1006.0 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 7.90ꢀ7.80(m, 2H), 7.60(s, 1H),
7.50ꢀ7.10(m, 3H), 7.10ꢀ6.70(m, 1H), 4.65(m, 4H),
4.35(s, 5H). MS (EI): m/z (%): 462 [100, Mꢁ], 464
[33.3, Mꢁ2]. Anal. Calc. for C21H16BrFeN3O C 54.58;
H 3.49; N 9.09. Found: C 54.58; H 3.49; N 8.89.
(E)-5l: yield: 8.8%; light red solid; m.p. 129ꢀ130 8C.
1618.4, 1112.2, 991.4 cmꢂ1. H-NMR d
(200 MHz, d6-DMSO): 7.74(s, 1H), 7.60(s, 1H), 7.28(s,
1H), 7.16ꢀ6.80(m, 4H), 4.56(m, 2H), 4.32(m, 2H),
4.22(s, 5H). MS (EI): m/z (%): 462 [100, Mꢁ],
464(33.3, Mꢁ2). Anal. Calc. for C21H16BrFeN3O C
/
133 8C.
/
/
/
/
/
/
1
IR (KBr): nꢃ
/
/
4.3.1. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-phenyl-
dihydropyrazole (6a)
/
Yield: 69%; red solid; m.p. 197ꢀ
(KBr): nꢃ
1599.2, 1501.3 cmꢂ1. 1H-NMR d (200 MHz,
d6-DMSO): 8.99(s, 1H), 8.07(s, 1H), 7.42ꢀ7.30(m, 5H),
7.15(t, Jꢃ5 Hz, 2H), 6.98(d, Jꢃ5 Hz, 2H), 6.82(t, Jꢃ
Hz, 1H), 6.06(d, Jꢃ5 Hz, 1H), 5.53(d, Jꢃ5 Hz, 1H),
/
199 8C (ethanol) IR
54.58; H 3.49; N 9.09. Found: C 54.36; H 3.46; N 8.93.
/
/
4.2.13. 2-(1,2,4-Triazolyl)-3-(3?-nitrophenyl)-1-
ferrocenylpropenone (5m)
/
/
/
5
/
/
(Z)-5m: yield: 59.8%; purple solid; m.p. 156ꢀ
IR (KBr): nꢃ
1649.7, 1125.0, 1016.3 cmꢂ1. 1H-NMR d
(200 MHz, d6-DMSO): 8.90(s, 1H), 8.40(s, 1H), 8.10(d,
Jꢃ4 Hz, 1H), 8.02(s, 1H), 7.80(s, 1H), 7.70(t, Jꢃ4 Hz,
1H), 7.40(d, Jꢃ4 Hz, 1H), 4.72(s, 2H), 4.58(s, 2H),
/
157 8C.
4.75(s, 1H), 4.39(s, 1H), 4.30(s, 1H), 4.12(s, 1H), 4.02(s,
5H). MS (EI): m/z (%): 473 [100, Mꢁ]. Anal. Calc. for
C27H23FeN5 C 68.50; H 4.90; N 14.80. Found: C 68.74;
H 4.68; N 14.69.
/
/
/
/
4.33(s, 5H). MS (EI): m/z (%): 429 [100, Mꢁ]. Anal.
Calc. for C21H16FeN4O3 C 58.79; H 3.76; N 13.05.
Found: C 58.62; H 3.82; N 13.12.
4.3.2. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(2?-
chlorophenyl)-dihydropyrazole (6b)
Yield: 35.2%; orange solid; m.p. 213ꢀ215 8C (ethanol)
/
1
(E)-5m: yield: 16.7%; red solid; m.p. 144ꢀ
(KBr): nꢃ
1638.4, 1122.2, 1008.4 cmꢂ1 1H-NMR d
(200 MHz, d6-DMSO): 9.10(s, 1H), 8.30(s, 1H), 8.27(s,
1H), 8.08(d, Jꢃ4 Hz, 1H), 7.84(d, Jꢃ4 Hz, 1H), 7.68(s,
1H), 7.60(t, Jꢃ4 Hz, 1H), 4.56(m, 4H), 4.14(s, 5H). MS
/
146 8C. IR
IR (KBr): nꢃ
MHz, CDCl3): 8.10ꢀ
7.35ꢀ7.15(m, 5H), 6.98(d, Jꢃ
Hz, 1H), 5.80ꢀ5.60(m, 2H), 4.77(s, 1H), 4.35(s, 1H),
/
1595.9, 1497.6 cmꢂ1. H-NMR d (200
8.00(m, 2H), 7.61(d, Jꢃ6 Hz, 1H),
6 Hz, 2H), 6.85(t, Jꢃ6
/
.
/
/
/
/
/
/
/
/
/
4.24(s, 1H), 3.92(s, 6H). MS (EI): m/z (%): 508 [100,
Mꢁ]. Anal. Calc. for C27H22ClFeN5 C 63.86; H 4.37; N
13.79. Found: C 63.80; H 4.40; N 13.87.
(EI): m/z (%): 429 [100, Mꢁ]. Anal. Calc. for
C21H16FeN4O3 C 58.79; H 3.76; N 13.05. Found: C
58.79; H 3.85; N 13.12.
4.3.3. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(3?-
chlorophenyl)-dihydropyrazole (6c)
4.2.14. 2-(1,2,4-Triazolyl)-3-(4?-nitrophenyl)-1-
ferrocenylpropenone (5n)
Yield: 83.0%; orange solid; m.p. 149ꢀ150 8C (acetone)
/
1
(Z)-5n: yield: 18.5%; purple solid; m.p. 191 8C. IR
IR (KBr): nꢃ
MHz, CDCl3): 8.06(s, 1H), 8.03(s, 1H), 7.40ꢀ
4H), 7.20(t, Jꢃ5 Hz, 2H), 7.00(d, Jꢃ5 Hz, 2H), 6.84(t,
Jꢃ5 Hz, 1H), 5.64(s, 1H), 5.22(s, 1H), 4.85(s, 1H),
/
1597.3, 1496.9 cmꢂ1. H-NMR d (200
7.30(m,
(KBr): nꢃ
(200 MHz, CDCl3): 8.22(s, 1H), 8.14(s, 1H), 8.10(d, Jꢃ
5 Hz, 1H), 7.71(s, 1H), 7.09(d, Jꢃ5 Hz, 1H), 4.62(s,
/
1654.9, 1128.0, 1012.6 cmꢂ1
.
1H-NMR d
/
/
/
/
/
/
2H), 4.57(s, 2H), 4.25(s, 5H). MS (EI): m/z (%): 429
[100, Mꢁ]. Anal. Calc. for C21H16FeN4O3 C 58.79; H
3.76; N 13.05. Found: C 58.69; H 3.86; N 12.98.
4.40(s, 1H), 4.25(s, 1H), 4.01(s, 1H), 3.98(s, 5H). MS
(EI): m/z (%): 508 [100, Mꢁ]. Anal. Calc. for
C27H22ClFeN5 C 63.86; H 4.37; N 13.79. Found: C
63.42; H 4.40; N 14.10.
(E)-5n: yield: 3.6%; purple solid; m.p. 191ꢀ
(KBr): nꢃ
1639.2, 1120.2, 1010.7 cmꢂ1 1H-NMR d
(200 MHz, CDCl3): 8.70(s, 1H), 8.10(s, 1H), 8.07(d, Jꢃ
5 Hz, 1H), 7.55(s, 1H), 7.45(d, Jꢃ5 Hz, 1H), 4.61(s,
/
193 8C. IR
/
.
/
4.3.4. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(4?-
chlorophenyl)-dihydropyrazole (6d)
/
2H), 4.50(s, 1H), 4.04(s, 5H). MS (EI): m/z (%): 429
[100, Mꢁ]. Anal. Calc. for C21H16FeN4O3 C 58.79; H
3.76; N 13.05. Found: C 58.65; H 3.85; N 13.08.
Yield: 59.4%; orange solid; m.p. 167ꢀ168 8C (ethanol)
/
1
IR (KBr): nꢃ
/
1596.2, 1497.4 cmꢂ1. H-NMR d (200
8.00(m, 2H), 7.40ꢀ7.30(m, 4H),
MHz, CDCl3): 8.10ꢀ
/
/

8
J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ9
/
7.18(d, Jꢃ
/
5 Hz, 2H), 7.00(d, Jꢃ
/
5 Hz, 2H), 6.84(t, Jꢃ
/
1H), 4.03(s, 5H). MS (EI): m/z (%): 489 [100, Mꢁ].
Anal. Calc. for C27H23FeN5O C 66.27; H 4.74; N 14.31.
Found: C 66.20; H 4.75; N 14.34.
5 Hz, 1H), 5.70(s, 1H), 5.20(s, 1H), 4.83(s, 1H), 4.39(s,
1H), 4.25(s, 1H), 3.97(s, 6H). MS (EI): m/z (%): 508
[100, Mꢁ]. Anal. Calc. for C27H22ClFeN5 C 63.86; H
4.37; N 13.79. Found: C 63.85; H 4.60; N 13.97.
4.3.10. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(4?-N,N-
dimethylaminophenyl)-dihydropyrazole (6j)
4.3.5. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(2?,4?-
dichlorophenyl)-dihydropyrazole (6e)
Yield: 63.3%; orange solid; m.p. 166ꢀ168 8C (ethanol)
/
1
IR (KBr): nꢃ
/
1611.0, 1512.6 cmꢂ1. H-NMR d (200
6.75(m, 9H), 5.77(s,
Yield: 53.0%; orange solid; m.p. 200ꢀ
/
201 8C (ethanol)
MHz, CDCl3): 8.03(m, 2H), 7.30ꢀ
/
1
IR (KBr): nꢃ
MHz, CDCl3): 8.10(s, 1H), 8.02(s, 1H), 7.53(s, 1H),
7.24ꢀ6.90(m, 7H), 5.61(m, 2H), 4.82(s, 1H), 4.38(s, 1H),
/
1596.4, 1498.7 cmꢂ1. H-NMR d (200
1H), 5.30(s, 1H), 4.82(s, 1H), 4.36(s, 1H), 4.22(s, 1H),
3.97(m, 6H), 2.95(s, 6H). MS (EI): m/z (%): 516 [100,
Mꢁ]. Anal. Calc. for C29H28FeN6 C 67.45; H 5.42; N
16.27. Found: C 67.28; H 5.40; N 16.35.
/
4.32(s, 1H), 4.26(s, 1H), 3.94(s, 5H). MS (EI): m/z (%):
542 [100, Mꢁ]. Anal. Calc. for C27H21Cl2FeN5 C 59.81;
H 3.90; N 12.92. Found: C 59.42; H 4.26; N 12.87.
4.3.11. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(4?-N,N-
diethylaminophenyl)-dihydropyrazole (6k)
4.3.6. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(4?-
methylphenyl)-dihydropyrazole (6f)
Yield: 30.6%; orange solid; m.p. 181ꢀ183 8C (ethanol)
/
1
IR (KBr): nꢃ
MHz, d6-DMSO): 8.95(s, 1H), 8.05(s, 1H), 7.20ꢀ
9H), 5.96(d, Jꢃ4 Hz, 1H), 5.29(d, Jꢃ4 Hz, 1H), 4.74(s,
1H), 4.38(s, 1H), 4.29(s, 1H), 4.09(s, 1H), 4.05(s, 5H),
/
1610.9, 1511.4 cmꢂ1. H-NMR d (200
6.60(m,
Yield: 59.2%; orange solid; m.p. 173ꢀ
/
175 8C (acetone)
/
1
IR (KBr): nꢃ
MHz, CDCl3): 8.10ꢀ
7.00(d, Jꢃ5 Hz, 2H), 6.82(t, Jꢃ
/
1604.5, 1506.1 cmꢂ1. H-NMR d (200
8.00(m, 2H), 7.30ꢀ7.15(m, 6H),
5 Hz, 1H), 5.64(s, 1H),
/
/
/
/
/
/
3.28(q, Jꢃ
/
4 Hz, 4H), 1.03(t, Jꢃ4 Hz, 6H). MS (EI): m/
/
5.21(s, 1H), 4.84(s, 1H), 4.37(s, 1H), 4.22(s, 1H), 3.98(s,
1H), 3.96(s, 5H), 2.32(s, 3H). MS (EI): m/z (%): 487
[100, Mꢁ]. Anal. Calc. for C28H25FeN5 C 69.00; H 5.30;
N 13.37. Found: C 68.90; H 5.17; N 13.36.
z (%): 545 [100, Mꢁ]. Anal. Calc. for C31H32FeN6 C
68.38; H 5.92; N 15.43. Found: C 68.36; H 6.01; N
15.35.
4.3.12. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(3?-
bromophenyl)-dihydropyrazole (6l)
4.3.7. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(4?-
methoxyphenyl)-dihydropyrazole (6g)
Yield: 74.7%; orange solid; m.p. 154ꢀ155 8C (ethanol)
/
1
Yield: 52.8%; orange solid; m.p. 162ꢀ
/
164 8C (acetone)
IR (KBr): nꢃ
MHz, d6-DMSO): 8.96(s, 1H), 8.06(s, 1H), 7.55ꢀ
5H), 7.20(t, Jꢃ5 Hz, 2H), 6.99(d, Jꢃ5 Hz, 2H), 6.86(t,
Jꢃ5 Hz, 1H), 6.08(d, Jꢃ5 Hz, 1H), 5.60(d, Jꢃ5 Hz,
/
1596.5, 1495.8 cmꢂ1. H-NMR d (200
7.30(m,
1
IR (KBr): nꢃ
MHz, CDCl3): 8.10ꢀ
7.02(d, Jꢃ5 Hz, 2H), 6.90(d, Jꢃ
/
1608.7, 1509.0 cmꢂ1. H-NMR d (200
8.00(m, 2H), 7.30ꢀ7.15(m, 4H),
5 Hz, 2H), 6.62(t, Jꢃ
/
/
/
/
/
/
/
/
/
/
/
5 Hz, 1H), 5.64(s, 1H), 5.21(s, 1H), 4.84(s, 1H), 4.37(s,
1H), 4.23(s, 1H), 4.00(s, 1H), 3.97(s, 5H), 3.77(s, 3H).
MS (EI): m/z (%): 503 [100, Mꢁ]. Anal. Calc. for
C28H25FeN5O C 66.81; H 5.01; N 13.91. Found: C
66.69; H 4.99; N 14.08.
1H), 4.78(s, 1H), 4.40(s, 1H), 4.31(s, 1H), 4.13(s, 1H),
4.04(s, 5H). MS (EI): m/z (%): 552 [100, Mꢁ]. Anal.
Calc. for C27H22BrFeN5 C 58.72; H 4.02; N 12.68.
Found: C 58.60; H 4.04; N 12.70.
4.4. 2-(1,2,4-Triazolyl)-3-(4?-methylphenyl)-3-(N?-
phenylhydrazinyl)-1-ferrocenyl-one (7f)
4.3.8. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(2?-
hydroxyphenyl)-dihydropyrazole (6h)
Yield: 33.9%; red solid; m.p. 195ꢀ
(KBr): nꢃ
1610.2, 1513.7 cmꢂ1. 1H-NMR d (200 MHz,
d6-DMSO): 8.85(s, 1H), 7.90(s, 1H), 7.10ꢀ6.70(m, 9H),
5.43(s, 1H), 5.38(s, 1H), 4.96(s, 1H), 4.88(s, 2H), 4.75(s,
1H), 4.30(m, 1H), 4.20(s, 5H). MS (EI): m/z (%): 489
[100, Mꢁ]. Anal. Calc. for C27H23FeN5O C 66.27; H
4.74; N 14.31. Found: C 66.21; H 4.73; N 14.33.
/
196 8C (acetone) IR
Yield: 17.8%; orange solid; m.p. 138ꢀ
IR (KBr): nꢃ
1655.7 cmꢂ1 1H-NMR d (200 MHz,
CDCl3): 8.85(s, 1H), 8.01(s, 1H), 7.20ꢀ7.05(m, 6H),
6.88(t, Jꢃ5 Hz, 1H), 6.60(d, Jꢃ5 Hz, 2H), 5.92(d, Jꢃ
5 Hz, 1H), 4.75ꢀ4.50(m, 7H), 3.93(s, 5H), 2.27(s, 3H).
/
139 8C (ethanol)
/
/
.
/
/
/
/
/
/
MS (EI): m/z (%): 505 [100, Mꢁ]. Anal. Calc. for
C27H22BrFeN5 C 58.72; H 4.02; N 12.68. Found: C
58.60; H 4.04; N 12.70.
4.3.9. 1-Phenyl-3-ferrocenyl-4-triazolyl-5-(4?-
hydroxyphenyl)-dihydropyrazole (6i)
Yield: 71.2%; orange solid; m.p. 224ꢀ
/
226 8C (acetone)
5. Supplementary material
1
IR (KBr): nꢃ
MHz, d6-DMSO): 9.50(m, 1H), 8.96(s, 1H), 8.06(s, 1H),
7.20ꢀ6.70(m, 9H), 5.97(d, Jꢃ4 Hz, 1H), 5.36(d, Jꢃ
Hz, 1H), 4.74(s, 1H), 4.38(s, 1H), 4.29(s, 1H), 4.09(s,
/
1613.5, 1515.8 cmꢂ1. H-NMR d (200
Crystallographic data for the structures 6a, (E)-5d,
and (Z)-5d have been deposited with the Cambridge
Crystallographic Data Center, CCDC No. 190 329-
/
/
/
4

J. Fang et al. / Journal of Organometallic Chemistry 674 (2003) 1ꢀ
/9
9
1998); C.A. 1999, 130, 52415;
190 331. Copies of this information may be obtained free
of charge from: The Director, CCDC, 12 Union Road,
(b) M.R. Cuberes-Altisent, J.M. Berrocal-Romero, M.M. Con-
tijoch-Llobet, J. Frigola-Constansa, Pyrazoline Derivatives, Their
Preparation and Application as Medicaments. WO99/62884 (May
27, 1999); C.A. 2000, 132, 12302.
Cambridge, CB2 1EZ, UK (Fax: ꢁ44-1223-336033;
/
email: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk.
[13] (a) F.R. Souza, V.T. Souza, V. Ratzlaff, L.P. Borges, M.R.
Oliveria, H.G. Bonacorso, N. Zanatta, M.A.P. Martins, C.F.
Mello, Eur. J. Pharmacol. 451 (2002) 141;
(b) E. Palaska, M. Aytemir, I.T. Uzbay, D. Erol, Eur. J. Med.
Chem. 36 (2001) 539;
Acknowledgements
(c) G. Turan-Zitouni, P. Chevallet, F.S. Kilic, K. Erol, Eur. J.
Med. Chem. 35 (2000) 635.
We gratefully acknowledge the National Natural
Science Foundation of China (NNSFC) (No.
20172030) for financial support.
[14] (a) R. Mulder, K. Wellinga, J.J. Van Daalen, Naturwissenschaf-
ten 62 (1975) 531;
(b) R. Van Hes, K. Wellinga, A.C. Grosscurt, J. Agric. Food
Chem. 26 (1978) 915;
(c) R. Fuchs, B.G. Kamp, C. Erdelen, Pesti. Sci. 50 (1997) 333.
[15] (a) R.M. Jacobson, Recent Advances in the Chemistry of Insect
Control II, Royal Society of Chemistry, Cambridge, 1990, pp.
References
[1] (a) G. Jaouen, A. Vessieres, I. Butler, Acc. Chem. Res. 26 (1993)
361;
206ꢀ211;
/
(b) H.H. Harder, S.L. Riley, S.F. McCann, S.N. Irving, Brighton
Crop Protection Conference-Pests and Diseases-1996, (1996) 449.
[16] (a) K. Wellinga, J.H.H. Eussen, 1-Carbonyl-2-pyrazoline Deriva-
tives Having Herbicidal Activity. EP/269141 (November 28,
1988); C.A. 1989, 110, 8204;
(b) G. Jaouen, A. Vessieres, I. Butler, Chem. Eng. (1995) 32.
[2] A. Vessieres, C. Vaillant, M. Gruselle, D. Vichard, G. Jaouen, J.
Chem. Soc. Chem. Commun. (1990) 837.
[3] P. Kopf-Maier, P. Kopf, Chem. Rev. 87 (1987) 1137.
¨ ¨
[4] A. Togni, T. Hayashi, Ferrocenes. Homogeneous Catalysis.
Organic synthesis. Material Sciences, VCH, Weinheim, 1995.
[5] A.E. Kaifer, J. de Mendoza, Comprehensive Supramolecular
Chemistry, vol. 1, Oxford, Elsevier, 1996, p. 701.
(b) M. Muhlebach, J. Glock, T. Maetzke, A. Stoller, 3-Hydroxy-
¨
4-aryl-5-pyrazoline Derivatives as Herbicides. WO00/47585 (Au-
gust 17, 2000); C.A. 2000, 133, 164053.
[17] K. Wellinga, A.C. Grosscurt, R. Van Hes, J. Agric. Food Chem.
25 (1977) 987.
[6] E.I. Klimova, V.N. Postnov, N.N. Meleshonkova, A.S. Zaks,
V.V. Yushkov, Khim.-Farm. Zh. 26 (1992) 69.
[18] A.C. Grosscurt, R. Van Hes, K. Wellinga, J. Agric. Food Chem.
27 (1979) 406.
[19] L. Schlogl, M. Egger, Monatsh. Chem. 95 (1962) 376.
¨
[7] E.I. Klimova, V.N. Postnov, N.N. Meleshonkova, A.S. Zaks,
E.M. Chukichev, Khim.-Farm. Zh. 26 (1992) 34.
[8] E.I. Klimova, V.N. Postnov, N.N. Meleshonkova, M. Martinex,
M.M. Garcia, A.S. Zaks, Khim.-Farm. Zh. 28 (1994) 33.
[9] R.P. Hanzlik, P. Soine, W.N. Soine, J. Med. Chem. 16 (1979) 989.
[10] (a) C. Biot, L. Delhaes, L.A. Maciejewaski, M. Mortuaire, D.
Camus, D. Dive, J.S. Brocard, Eur. J. Med. Chem. 35 (2000) 707;
(b) C. Biot, G. Glorian, L.A. Maciejewaski, J.S. Brocard, J. Med.
Chem. 40 (1997) 3715;
[20] L. Schwink, P. Knochel, T. Eberle, J. Okuda, J. Organomet.
Chem. 17 (1998) 7.
[21] C. Glidewell, S.Z. Ahmed, M. Gottfried, P. Lighfoot, B.J.L.
Royles, J.P. Scott, J. Wonnenmann, J. Organomet. Chem. 530
(1997) 177.
[22] A. Ta´rraga, P. Molina, D. Curiel, J.L. Lo´pez, M.D. Velasco,
Tetrahedron 55 (1999) 14701.
(c) C. Biot, L. Delhaes, M. N’Diaye, L.A. Maciejewaski, D.
Camus, D. Dive, J.S. Brocard, Bioorg. Med. Chem. 7 (1999) 2843.
[11] (a) H. Sun, Q. Wang, R. Huang, H. Li, Y. Li, J. Organomet.
Chem. 655 (2002) 182;
[23] E. Heinz, M. Himar, H. Reinhard, S. Burkhard, H. Peter, B.
Helmut, Triazolylalkyl Derivatives, Method for Their Prepara-
tion and Their Use as Plant Treating Agents. DE/3406908
(September 4, 1985); C.A. 1986, 104, 68871.
(b) R. Huang, Q. Wang, J. Organomet. Chem. 637ꢀ639 (2001) 94.
/
[12] (a) L.J. Adams, T. Gallagher, I.K. Osifo, Novel Pyrazole and
Pyrazoline Substituted Compounds. WO98/56377 (December 17,
[24] P.W. Kenny, M.J.T. Robinson, Tetrahedron Lett. 27 (1986) 6277.
[25] P.W. Kenny, M.J.T. Robinson, Tetrahedron 43 (1987) 4043.