Design and synthesis of new functional compounds related to ferrocene bearing heterocyclic moieties. A new approach towards electron donor organic materials

Article abstract of DOI:10.1016/S0022-328X(03)00216-X

The synthesis of heterocyclic systems incorporating more than one ferrocene unit was shown to be a facile and convenient route for the synthesis of new ferrocene-heterocycles. Hydrazide 2 was prepared and cyclized to oxadiazole, triazole, and pyrazole using the procedures described in this context with good yields. A pyrazolone derivative could not be obtained and instead a hydrazone derivative 17 was isolated. Hydrazide 2 was condensed with aromatic aldehydes and ferrocene-1,1′-dicarbaldehyde derivatives to give the corresponding hydrazones 11a-c and dihydrazones 12, 14 and 18 in high yields. Cyclic voltammetry (CV) of the selected ferrocene-heterocycles 8 and 9 was studied comparing with the parent ferrocene and acetylferrocene. The CV of the compound 8 revealed an additional, quasireversible, one-electron oxidation wave at 849 mV, corresponding to the second ferrocene unit connected to the oxadiazole ring through the SCH₂CO spacer.

Full text of DOI:10.1016/S0022-328X(03)00216-X

Journal of Organometallic Chemistry 675 (2003) 1ꢀ12
/
www.elsevier.com/locate/jorganchem
Design and synthesis of new functional compounds related to
ferrocene bearing heterocyclic moieties
A new approach towards electron donor organic materials
A.A.O. Sarhan *, T. Izumi
Department of Chemistry and Chemical Engineering, Faculty of Engineering, Yamagata University, 3-16 Jonan 4-Chome, Yonezawa 992-8510, Japan
Received 17 December 2002; received in revised form 25 March 2003; accepted 26 March 2003
Abstract
The synthesis of heterocyclic systems incorporating more than one ferrocene unit was shown to be a facile and convenient route
for the synthesis of new ferrocene-heterocycles. Hydrazide 2 was prepared and cyclized to oxadiazole, triazole, and pyrazole using
the procedures described in this context with good yields. A pyrazolone derivative could not be obtained and instead a hydrazone
derivative 17 was isolated. Hydrazide 2 was condensed with aromatic aldehydes and ferrocene-1,1?-dicarbaldehyde derivatives to
give the corresponding hydrazones 11aꢀc and dihydrazones 12, 14 and 18 in high yields. Cyclic voltammetry (CV) of the selected
/
ferrocene-heterocycles 8 and 9 was studied comparing with the parent ferrocene and acetylferrocene. The CV of the compound 8
revealed an additional, quasireversible, one-electron oxidation wave at 849 mV, corresponding to the second ferrocene unit
connected to the oxadiazole ring through the SCH2CO spacer.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Ferrocene-heterocycles; Hydrazide; Cyclic voltammetry
1. Introduction
increase resistance toward photodegradiation [3]. Fer-
rocene-1,3-butadiene was used as fuel in solid propel-
lants [3]. Polymers containing directly linked ferrocene
centers have been prepared and many studies on linked
ferrocene dimmers and oligomers have also been re-
viewed [4]. Several compounds bearing ferrocenyl moi-
eties have been synthesized and used for chemotherapy
of drug-resistant cancer and tropical diseases [5].
Recently, ferrocenyl-2-thiazolamine [6] and ferrocenyl-
2-oxazolines [7] have been reported by several groups. It
has been found that N-ferrocenylmethyl benzimidazo-
lium iodide exhibited an excellent in vitro activity
against the P. falciparum malarial parasite strain
NF54 [8]. Spectrochemical and electrochemical beha-
viors of ferrocene-heteroaromatic analogues were also
observed [9]. It is also known that ferrocene behaves in
many aspects like an aromatic electron-rich phenol
compound, and this has led to its use as precursors for
synthesis of several crown-ethers, azacrown-ethers and
thiacrown-ethers as well [10]. It has been reported that a
wide variety of macrocycles, cryptands, and cavitands
containing the ferrocene unit have been synthesized and
Ferrocene has attracted the interest of many scientists
and research groups worldwide because its applications
in materials science [1] and asymmetric synthesis [2].
Ferrocene chemistry was revived during the last years
because ferrocenyl derivatives have found numerous
uses in various fields of science from biology to
materials chemistry [1e]. Due to the inherent importance
of ferrocene as a starting material in synthetic organo-
metalic systems and industrial applications, ferrocene
and its derivatives have become a great area of interest
for many researchers and industrial chemists. It was
reported that ferrocenyl alkenes and dienes are impor-
tant substrates for co- and homopolymer synthesis,
which are used as coating materials for aerospace to
* Corresponding author. Present address: Department of
Chemistry, Faculty of Science, Assiut University, Assiut 71516,
Egypt. Fax: ꢁ
E-mail
/
20-88-312564.
addresses:
sarhan@chem.yz.yamagata-u.ac.jp,
elwareth@acc.aun.eun.eg (A.A.O. Sarhan).
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00216-X

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A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ12
/
characterized [1e] as well as some ferrocenes have been
incorporated into a number of anion sensors [11].
Due to the structural and electrochemical properties
of ferrocene-containing tetrathiafulvalene (TTF) deriva-
yield. An attempt to synthesize the thiazolo[3,2-b]tria-
zole (7) using the acidified acetic acid method [16] was
unsuccessful and an unknown black material was
obtained. This might be attributed to the oxidation of
ferrocene unit in the presence of concentrated sulfuric
acid at high temperatures leading to the iron oxide
formation as black material (Scheme 2).
tives, several ferroceneꢀTTFs were constructed as
/
donors for conducting CT complexes. The first com-
pound belongs to this class of heterocyclic donor
conducting materials [12] and very similar type of donor
heterocycles has been reported also in the literature [13].
Several CT complexes of metal bis(arene) compounds
containing the familiar organic acceptor tetracyano-p-
quinodimethane (TCNQ) have also been reported.
Recently, 1,1?-disubstituted ferrocenes were synthesized
as novel donors for the preparation of CT complexes,
which are structurally and electronically related to the
TTFs heterocycles conjugated with ferrocene moiety
[14]. These findings prompted us to synthesize a number
of new heterocyclic systems incorporating ferrocene
moieties separated by aryl rings as conjugated spacers
and to study the electrochemical redox behavior of these
new types of heterocyclic donors comparing with the
parent ferrocene and acetylferrocene.
The reaction of oxadiazole 4 with a-chloroacetylfer-
rocene in the presence of sodium acetate afforded the
oxadiazolyl-5-thiomethylcarbonyl ferrocene derivative 8
as dark red crystals in 73.5% yield. The a-chloroacetyl-
ferrocene was obtained via FriedelꢀCrafts acylation
/
reaction in CH2Cl2 at 0 8C in moderate yield. Introduc-
tion of two-ferrocene units into oxadiazole molecule
seems to be of interest for electrochemical studies,
particularly when these two-ferrocene moieties are not
symmetrical (Chart 1).
Condensation of the hydrazide derivative 2 with
acetylacetone in refluxing ethanol containing a catalytic
amount of acetic acid afforded the corresponding
pyrazol derivative 9 in 69.5% yield. Condensation of
the hydrazide 2 with p-(ferrocenyl)benzaldehyde or
aromatic aldehydes such as benzaldehyde or p-anisalde-
hyde using the same reaction conditions afforded the
2. Results and discussion
hydrazones 11aꢀc in excellent yields. Reaction of 2 with
/
acetylferrocene in ethanol containing acetic acid (20:1)
afforded the corresponding hydrazone 10a in 4.5% yield.
Interestingly, when hydrazide 2 was condensed with
acetylferrocene in acetic acid under severe conditions
(reflux for 36 h) the reaction underwent chemoselec-
tively and the N-acetyl derivative 10b was isolated after
chromatography in 86% yield as red crystals rather than
the formation of 10a (Scheme 3).
On the other hand, ferrocene-1,1?-dihydrazone deri-
vative 12 was synthesized in very high yield (98%) by a
direct condensation of the ferrocene-1,1?-dicarbaldehyde
which was prepared directly from ferrocene by a
previously described procedure [17] with hydrazide 2
in refluxing ethanol in the presence of acetic acid as a
catalyst (Chart 2).
Following the method reported in literature, the 1-(p-
formylphenyl)-1?-(4-formyl-1-naphthyl)ferrocene (13)
was synthesized in good yield [18] and subjected to be
a starting for synthesis of dihydrazone 14. The reaction
of hydrazide 2 with asymmetric ferrocene-1,1?-diaro-
matic aldehydes using the same method described above
afforded the dihydrazone derivative 14 in 84.6% yield
(Scheme 4).
Using the same method the 1-(m-formylphenyl)-1?-(3-
formyl-5-methoxyphenyl)ferrocene (15) was synthesized
according to Gomberg’s arylation of ferrocene with
diazonium salt of the methyl 3-amino-4-methoxybenzo-
ate to afford the corresponding 1-(3-methoxycarbonyl-
2-methoxyphenyl)ferrocene which subjected to diazoti-
zation with diazonium salt derived from methyl 3-
aminobenzoate to give the corresponding diester 16,
The first facile incorporation of heterocyclic ring
system into ferrocene with a phenyl ring as a spacer
was achieved by the use of p-(ferrocenyl)benzoyl
hydrazide (2). The synthesis of ferrocene compounds
bearing heterocyclic rings and the study of the biological
and electrochemical behavior of these new ferrocenyl
heterocycles seem to be of interest since marked
biological activity appeared recently for the ferrocene
derivatives. The ethyl-p-(ferrocenyl)benzoate (1) was
prepared by direct coupling of the diazonium salt of
the methyl p-aminobenzoate in the presence of acetic
acid [15]. Refluxing of compound 1 with hydrazine
hydrate in ethanol for 24 h afforded the expected
hydrazide derivative 2 as orange crystals in 94% yield.
The oxadiazole derivative 4 was obtained as follows. By
refluxing 2 with CS2 in methanol containing a slightly
excess of KOH to give the intermediate xanthate
derivative 3 was obtained, which on acidification with
concentrated hydrochloric acid gave the oxadiazole 4 as
yellow crystals in 92.5% over all yield (Scheme 1). The
structure of hydrazide 2 and oxadiazole 4 was deter-
mined both chemically and using spectral analyses
including IR, 1H-, 13C-NMR, FABMS spectra and
elemental analysis. The analyses of 2 and 4 were found
in satisfactory agreement with the suggested structures.
The reaction of oxadiazole 4 with hydrazine hydrate
in refluxing ethanol afforded the N-aminotriazole 6 in
39.5% yield. On the other hand, the fusion of the
oxadiazole 4 with ammonium acetate at 150 8C afforded
the corresponding 1,2,4-s-triazole derivative 5 in 70%

A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ
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3
Scheme 1. (a) NH2NH2/EtOH, reflux, 24 h, 94%. (b) CS2/KOH, EtOH, reflux, 5 h. (c) Aq HCl, 92.5%.
formation of the ester derivative 21 followed by hydro-
lysis to the corresponding acid 22 and elimination of
CO2 as shown in Scheme 6.
All new compounds were confirmed successfully by
spectral analyses including IR, 1H-, 13C-NMR, FABMS
spectroscopy and elemental analyses. The analytical and
spectroscopic data clearly support the proposed struc-
tures. Details of the analytical spectra are summarized in
the Section 5.
Chart 1.
followed by reduction with LiAlH4 to 17 and oxidation
with activated MnO2 in dry CHCl3. Using the same
method described above condensation of hydrazide 2
with 1-(m-formylphenyl)-1?-(3-formyl-5-methoxyphe-
nyl)ferrocene (15) in ethanol containing few drops of
acetic acid afforded the dihydrazone derivative 18 as
orange crystals in 92.8% yield (Scheme 5).
On reaction of 2 with ethyl acetoacetate under the
same reaction conditions, the unpredictable hydrazone
derivative 20 was isolated in 51.4% yield instead of the
expected pyrazolone derivative 19 (Chart 3).
3. Electrochemistry
The electrochemical behaviors of ferrocene, acetylfer-
rocene, Fc-oxadiazole 8 and Fc-pyrazole 9 were inves-
tigated by cyclic voltammetry (CV) (Fig. 1), which is
sensitive electrochemical method and permit the collec-
tion of excellent data at low concentration of electro-
active substance [19]. The electrochemical results of the
investigated compounds were compared to that of
ferrocene and acetylferrocene. Summaries of cyclic
voltammetric results are given in Table 1. The cyclic
Formation of the hydrazone 20, rather than the
expected pyrazolone 19, can be explained by the
Scheme 2. (a) CH3COONH4, EtOH, reflux, 8 h. (b) NH2NH2, EtOH, reflux, 5 h. (c) Aceteylferrocene, H2SO4/AcOH, reflux, 5 h.

4
A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ12
/
Scheme 3. (a) Acetylacetone, EtOH/AcOH, reflux, 5 h, 69.5%. (b) (i) Acetylferrocene, EtOH/AcOH, reflux, 8 h, 4.5%. (ii) neat, 19%. (c)
Acetylferrocene, EtOH/AcOH, reflux, 36 h, 86%. (d) ArCHO, EtOH/AcOH, reflux, 5ꢀ7 h.
/
voltammetric behavior of these compounds showed one
cathodic peak and the corresponding oxidation peak in
considering the structural difference between these
compounds, namely a single surplus carbonyl group of
compounds Fc-COCH3 and Fc-oxadiazole 8 in com-
pared with ferrocene and Fc-pyrazole 9.
the potential range of 450ꢀ900 mV at the Pt electrode.
/
The separation of the anodic and the cathodic peak
potentials, DEp, were 95, 73, 119 and 130 mV at 20 mV
sꢂ1 for Fc, Fc-pyrazole 9, Fc-COCH3 and Fc-oxadia-
zole 8, respectively. These values are larger than that
expected for a reversible two-electron transfer reaction,
which is given by 57/z mV, where z is the number of
electrons transferred in the process [20], indicating that
the irreversibility of the electron-transfer process was
maintained under this condition. At higher scan rates, n
In all compounds like Fc, acetylferrocene, Fc-Oxa-
diazole 8 and Fc-Pyrazole 9, where the ferrocene is
connected to an oxadiazole or pyrazole ring system
through a conjugated spacer, showed one reversible
electron transfer oxidation within the range ca. 0.5ꢀ0.9
/
V in case of ferrocene, acetylferrocene and Fc-pyrazole 9
and two reversible electron transfer oxidations as Fc-
Fcꢁ ion and to
oxadiazole 8. These correspond to Fc0
/
(n ]
/
600 mV sꢂ1) Fig. 2, broadening of DEp was
150 mV), possibly due to the onset of
the second ferrocene unit in compound 8. As shown in
observed (DEpꢀ
kinetic complications.
/
Fig. 1, the first oxidation in compound 8 belongs to
Fcꢁ+, whereas the second oxidation potential is
Fcꢁ+
The formal potential, E0/, taken as the average of Epc
and Epa, were 518, 582, 584 and 788 mV for Fc, Fc-
pyrazole 9, Fc-oxadiazole 8 and Fc-COCH3, respec-
tively. E0/ shifted to more positive potentials by ca. 200
mV for Fc-COCH3 and Ep2 of Fc-oxadiazole 8 in
compared to Fc and Fc-pyrazole 9, this revealed that
the reduction of carbonyl compounds Fc-COCH3 and 8
become more easily at the Pt electrode. The significant
differences between the E0/ values of Fc-COCH3 and Fc-
oxadiazole 8 and other compounds are highly interesting
Fc0
/
related also to the second ferrocene unit (Fc0
/
)
connected to the oxadiazole ring through SCH2CO
spacer.
The low solubility of the hydrazones and triazoles in
non-polar organic solvent (CH2Cl2, THF) and even in
CH3CN could not allow us to study the electrochemical
properties of those compounds. The biological screen-
ings of these compounds will be in consideration and
will be investigate separately.
Chart 2.

A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ
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5
Scheme 4.
4. Conclusions
behavior was observed as a one wave in 9. The
advantage of introducing ferrocene into these types of
heterocycles is that ferrocene has only a single one-
electron redox process. The cyclic voltammetric beha-
vior of these compounds showed one cathodic peak and
the corresponding oxidation peak in the potential rang
The title compounds were synthesized as new donors
and their structures were confirmed successfully by
spectral analyses. The electrochemical properties of
Fc-oxadiazole 8 and Fc-pyrazole 9 were studied in
comparison with the parent ferrocene and acetylferro-
cene by CV. A two-electron redox behavior was
observed as two waves in 8, while a one-electron redox
of 450ꢀ
n (n ]
600 mV sꢂ1), broadening of DEp was observed
(DEpꢀ150 mV), possibly due to the onset of kinetic
/900 mV at the Pt electrode. At higher scan rate,
/
/
Scheme 5.

6
A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ
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Chart 3.
complications. The significant differences between the
E0/ values of Fc-COCH3 and 9 and other compounds
are highly interesting considering the structural differ-
ence between these compounds, namely a single surplus
carbonyl group of compounds Fc-COCH3 and Fc-
oxadiazole 8 in compared with compounds like Fc and
Fc-pyrazole 9.
5.2. p-(Ferrecenyl)benzoic acid hydrazide (2)
A mixture of the ester 1 (10 g, 29.9 mmol) and
hydrazine hydrate (30 ml) was refluxed in EtOH (100
ml) for 24 h. The reaction mixture was cooled and the
crystals thus formed were collected by filtration and
crystallized from EtOH to give dark yellow crystals of
the corresponding hydrazide 2: 9.0 g, yield 94%, m.p.
189ꢀ
1623s, 1621s, 1558s, 1506s, 1328s, 1282s, 1105s, 950s,
856s, 771s cmꢂ1. 1H-NMR (Me2SO-d6, 500 MHz): dꢃ
9.73 (bs, 1H, NH), 7.78ꢀ7.76 (d, Jꢃ8 Hz, 2H,
aromatic-H), 7.55 (d, Jꢃ8 Hz, 2H, aromatic-H), 4.85
/
192 8C; IR (KBr) n 3320s, 3305s, 3099m, 3095m,
/
5. Experimental
/
/
/
(s, 2H, ferrocene-H), 4.49 (s, 2H, NH2), 4.38 (s, 2H,
ferrocene-H), 4.00 (s, 5H, ferrocene-H); 13C-NMR
5.1. General
(Me2SO-d6, 125 MHz): dꢃ 165.82 (CO), 142.52 (aro-
/
Melting points (m.p.) were recorded on a Gallencamp
melting point apparatus and are uncorrected. Infrared
spectra (IR) were measured on a Hitachi 260-10 spectro-
meter. 1H- and 13C-NMR spectra were recorded at
room temperature (r.t.) on Varian Spectrometer 500
MHz. Chemical shifts are denoted in d units (ppm)
relative to Me4Si as internal standard; J values are given
in Hz. CDCl3 and Me2SO-d6 were used unless otherwise
stated. Mass spectra were obtained using a JEOL JMS-
AX505HA. CV was measured on a cyclic voltammeter
(Model CS-1090/Model CS-1087). Column chromato-
matic-C), 127.16, 125.49 (aromatic-CH), 83.40 (ferro-
cene-C), 69.54, 66.64 (ferrocene-CH); FABMS m/z (%)
[Mꢁ, 320 (100)]. Anal. Calc. for C17H16FeN2O: C,
63.77; H, 5.03; N, 8.74. Found: C, 63.69; H, 5.00; N,
8.56%.
5.3. 2-[(Ferrocenyl)-p-phenyl]oxadiazol-5-thiol (4)
A mixture of the hydrazide 2 (3.2 g, 10 mmol) and
carbon disulfide (10 ml) was refluxed in MeOH (25 ml)
in the presence of KOH (0.84 g, 15 mmol) for 5 h. The
reaction mixture was cooled and the solvents removed
under vacuum to give a dark yellow-red precipitate of
the salt 3, which was used without further purification.
graphy was performed on silica gel 60 (230ꢀ400 Mesh
/
ASTM). Solvents were distilled before use. Acetylferro-
cene, and a-chloroacetylferrocene were prepared follow-
ing the previously reported methods [21].
Scheme 6.

A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ
/12
7
Fig. 1. Cyclic voltammetry (CV) of ferrocene, Fc-oxadiazole 8 and Fc-pyrazole 9 in CH2Cl2 at scan rate 20 mV sꢂ1 using TBAP as the supporting
electrolyte in 0.1 mol concentration on a Pt working electrode, a Pt gauze counter electrode and a Ag/AgCl reference electrode at ambient
temperature.
218 8C; IR (KBr) n 3079s, 2946s, 2767s, 1612s, 1515s,
1504s, 1423s, 1348s, 1284s, 1178s, 1070s, 966s, 885s,
Table 1
Cyclic voltammetric parameters of ferrocene, Fc-COCH3, Fc-pyrazole
9 and Fc-oxadiazole 8
742s, 696s cmꢂ1; 1H-NMR (Me2SO-d6, 500 MHz): dꢃ
/
Compound
Epc (mV) Epa (mV) E0/ (mV) DEp (mV)
7.91 (s, 1H, NH), 7.78 (d, Jꢃ
7.71 (d, Jꢃ8 Hz, 2H, aromatic-H), 4.89 (s, 2H,
ferrocene-H), 4.44 (s, 2H, ferrocene-H), 4.03 (s, 5H,
ferrocene-H); 13C-NMR (Me2SO-d6, 125 MHz): dꢃ
/
8 Hz, 2H, aromatic-H),
/
Ferrocene
Fc-COCH3
481
847
631
647
554
728
536
517
518
788
584
582
73
119
95
130 a
/
Fc-pyrazole 9
Fc-oxadiazole 8
177.35 (C-5), 160.77 (C-2), 144.22, 126.43 (aromatic-C),
126.16, 119.45 (aromatic-CH), 82.67 (ferrocene-C),
69.91, 69.66, 66.84, 66.77 (ferrocene-CH); FABMS m/
z (%) [Mꢁ, 362 (100)]. Anal. Calc. for C18H14FeN2OS:
C, 59.68; H, 3.89; N, 7.73. Found: C, 59.51; H, 3.81; N,
7.68%.
a
DEp2
ꢃ/E
Ox 2ꢂ
/E
Red 2ꢃ
/
849ꢂ
/
712ꢃ
/
137 mV, E0/ꢃ
/
781 mV.
The dark yellow-red product was dissolved in water and
neutralized by HCl solution to give yellow red crystals
of the oxadiazole 4: yield 3.35 g, 92.5%, m.p. 216ꢀ
/
Fig. 2. Cyclic voltammetry (CV) of Fc-oxadiazole 8 in CH2Cl2 at scan rate 20ꢀ .
600 mV sꢂ1
/

8
A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ12
/
5.4. 2-[p-(Ferrocenyl)phenyl]-5-
[(ferrocenyl)carbonylmethylthio]oxadiazole (8)
5.6. 3-[p-(Ferrecenyl)phenyl]-N-amino-1,2,4-s-triazol-
5-thiol (6)
A mixture of oxadiazole 4 (0.362 g, 1.0 mmol) and a-
chloroacetylferrocene (0.269 g, 1.02 mmol) was heated
gently in EtOH containing excess amount of AcONa for
2 h. The EtOH was removed under reduced pressure and
the solid residue was washed with water to remove the
excess AcONa. The brown precipitate was filtered off
and dried on air suction. The crude product was
chromatographed on silica gel using CHCl3 to give the
corresponding oxadiazole-5-thioacetylferrocene deriva-
tive 8 as dark red crystals: yield 0.432 g, 73.5%, m.p.
A mixture of 4 (1.0 g, 2.76 mmol) and hydrazine
hydrate (5 ml) is refluxed in dry EtOH for 5 h. The
resulting precipitate thus formed after cooling was
collected by filtration and crystallized from EtOH to
give a dark yellow crystal of the corresponding N-amino
triazole derivative 6: yield 0.41 g, 39.5%, m.p. 171ꢀ
/
173 8C; IR (KBr) n 3313s, 3089m, 2942w, 1608s,
1508s, 1409m, 1322s, 1280s, 1191w, 1105s, 948s, 887s,
1
846s, 813s, 771m, 696m cmꢂ1; H-NMR (Me2SO-d6,
500 MHz): dꢃ
(s, 1H, NH), 7.65 (m, 3H, aromatic-H), 5.81 (s, 1H,
NH), 4.88 (d, Jꢃ7 Hz, 2H, ferrocene-H), 4.41 (d, Jꢃ
Hz, 2H, ferrocene-H), 4.02 (t, Jꢃ4 Hz, 5H, ferrocene-
H); 13C-NMR (Me2SO-d6, 125 MHz): dꢃ
166.76 (C-5),
/
7.97 (d, Jꢃ/8 Hz, 1H, aromatic-H), 7.75
181ꢀ183 8C; IR (KBr) n 3220w, 3091s, 2960s, 1656s,
/
1608s, 1583s, 1513s, 1477s, 1454s, 1378s, 1340s, 1301s,
1218s, 1182s, 1086s, 1031s, 1000s, 887s, 821s, 742s, 701s
/
/7
/
cmꢂ1; 1H-NMR (CDCl3, 500 MHz): dꢃ
/
7.92 (dd, Jꢃ
2 Hz, 2H, aromatic-H), 7.56 (dd, Jꢃ7, Jꢃ2 Hz,
2H, aromatic-H), 4.91 (t, Jꢃ2 Hz, 2H, ferrocene-H),
4.71 (t, Jꢃ2 Hz, 2H, ferrocene-H), 4.70 (s, 2H, SCH2),
4.62 (t, Jꢃ2 Hz, 2H, ferrocene-H), 4.39 (t, Jꢃ2 Hz,
2H, ferrocene-H), 4.29 (s, 5H, ferrocene-H), 4.05 (s, 5H,
ferrocene-H); 13C-NMR (CDCl3, 125 MHz): dꢃ
196.014 (CꢀO), 166.16 (C-5), 163.58 (C-2), 143.98,
/
7,
/
Jꢃ
/
/
/
149.46 (C-2), 141.913, 127.96, (aromatic-C), 125.68,
122.91 (aromatic-CH), 83.35 (ferrocene-C), 69.53,
69.01, 66.65 (ferrocene-CH); FABMS m/z (%) [Mꢁ,
376 (10)]. Anal. Calc. for C18H16FeN4S: C, 57.46; H,
4.28; N, 14.89. Found: C, 57.61; H, 4.21; N, 14.59%.
/
/
/
/
/
/
5.7. p-(Ferrocenyl)phenyl-(3,5-dimethylpyrazolyl)-
methanone (9)
126.80 (aromatic-C), 126.77, 126.30, 126.23, 120.59
(aromatic-CH), 83.25, 76.54 (ferrocene-C), 70.33,
70.30, 70.27, 69.85, 69.82, 69.69, 69.62, 66.75 (ferro-
cene-CH), 41.45 (SCH2); MS m/z (%) [Mꢁ, 588 (10)].
Anal. Calc. for C30H24Fe2N2O2S: C, 61.23; H, 4.10; N,
4.76. Found: C, 60.94; H, 3.92; N, 4.61%.
A mixture of hydrazide 2 (0.36 g, 1.13 mmol) and
acetylacetone (1 ml) was refluxed in MeOH (25 ml)
containing AcOH (1 ml) for 5 h. The reaction mixture
was cooled and the yellow precipitate was collected by
filtration and washed with water several times. The
crude product was crystallized from MeOH to give 310
mg of golden yellow crystals of pyrazole derivative 9:
5.5. 3-[p-(Ferrocenyl)phenyl]-1,2,4-s-triazol-5-thiol
(5)
yield 69.5%, m.p. 104ꢀ105 8C; IR (KBr) n 2958w,
/
A mixture of 4 (1.0 g, 2.76 mmol) and ammonium
acetate (5 g) is heated gently without solvent for 2 h. The
reaction mixture was cooled and refluxed in dry EtOH
for further 16 h. The resulting precipitate thus formed
after cooling was dissolved in water to remove the excess
ammonium acetate. The residue was collected by filtra-
2923m, 1693s, 1606s, 1523m, 1479m, 1457m, 1411s,
1344s, 1276s, 1189s, 1116s, 1029s, 921s, 759s, 698s
1
cmꢂ1; H-NMR (CDCl3): dꢃ
/
7.96ꢀ
/
7.94 (d, Jꢃ7 Hz,
/
2H, aromatic-H), 7.47ꢀ
/
7.46 (d, Jꢃ7 Hz, 2H, aromatic-
/
H), 6.06 (s, 1H, pyrazole-H), 4.82 (s, 2H, ferrocene-H),
4.5 (s, 2H, ferrocene-H), 4.16 (s, 5H, ferrocene-H), 2.62
(s, 3H, CH3), 2.27 (s, 3H, CH3); 13C-NMR (CDCl3):
tion and chromtographed on silica gel using hexaneꢀ
/
acetone (1:2) to give in the last fraction a yellow crystal
of triazole 5: yield 0.7 g, 70%, m.p. 199 8C (dec.); IR
(KBr) n 3315s, 3099m, 1623s, 1610s, 1558s, 1506s,
dꢃ168.63 (CO), 152.60, 145.76 (C-3, C-5, pyrazole),
/
145.69, 132.54, (aromatic-C), 130.94, 126.12, 111.60
(aromatic-CH), 109.79 (pyrazole-CH), 71.43, 68.41,
58.96 (ferrocene-C), 15.04, 14.63 (2 CH3); FABMS m/
z (%) [Mꢁ 384 (100)]. Anal. Calc. for C22H20FeN2O: C,
68.76; H, 5.24; N, 7.29. Found: C, 68.96; H, 5.29; N,
7.22%.
1409w, 1328s, 1282s, 1105s, 1002m, 950s, 771s cmꢂ1
;
1H-NMR (Me2SO-d6, 500 MHz): dꢃ
NH), 9.86 (s, 1H, NH), 7.81ꢀ7.79 (d, Jꢃ
aromatic-H), 7.64ꢀ7.62 (d, Jꢃ8.5 Hz, 2H, aromatic-H),
4.88 (t, Jꢃ2 Hz, 2H, ferrocene-H), 4.41 (t, Jꢃ1.5 Hz,
2H, ferrocene-H), 4.02 (s, 5H, ferrocene-H); 13C-NMR
(Me2SO-d6, 125 MHz): dꢃ 168.46, 165.22 (C-3, C-5),
/
10.22 (s, 1H,
8.5 Hz, 2H,
/
/
/
/
/
/
5.8. 1-[p-(Ferrocenyl)benzoylhydrazono]-1-
(ferrocenyl)ethane (10a)
/
143.21, 129.40 (aromatic-C), 127.49, 125.33 (aromatic-
CH), 82.95 (ferrocene-C), 69.43, 69.43, 66.54 (ferrocene-
CH); FABMS m/z (%) [Mꢁ1 362 (22)]. Anal. Calc. for
C18H15FeN3S: C, 59.84; H, 4.18; N, 11.63. Found: C,
59.67; H, 4.01; N, 11.51%.
5.8.1. Method A
A mixture of hydrazide 2 (0.5 g, 1.56 mmol) and
acetylferrocene (0.4 g, 1.75 mmol) was refluxed in EtOH
(20 ml) containing AcOH (1 ml) for 8 h. The reaction

A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ
/12
9
mixture was cooled and the yellow precipitate was
collected by filtration and washed with water several
times. The crude product was chromatographed on
(1 ml) for 5ꢀ7 h. The reaction mixture was cooled and
/
the yellow precipitate was collected by filtration and
washed with water several times. The crude products
were crystallized from EtOH to give the corresponding
silica using acetoneꢀhexane (1:3) to give yellow powder
/
in the second fraction, which on crystallization from
EtOH gave 37 mg, 4.5% of hydrazone 10a as orange
hydrazones 11aꢀc as yellow crystals in very good yield.
/
crystals, m.p. 140ꢀ
/
143 8C.
5.10.1. p-(Ferrocenyl)benzoylhydrazono-benzylidene
(11a)
5.8.2. Method B
Rꢃ
/
H: yield 95.6%, m.p. 241ꢀ243 8C; IR (KBr) n
/
A sample of hydrazide 2 (0.32 g, 1 mmol) was
condensed with acetylferrocene (0.228 g, 1 mmol) under
neat conditions for 30 min. The reaction mixture was
further refluxed in EtOH for further 3 h. The precipitate
thus formed was collected by filtration and chromto-
graphed on silica and worked up as described in method
A to give 0.102 g, 19% of 10a. IR (KBr) n 3210w,
3091m, 1648s, 1606s, 1540s, 1511s, 1411m, 1389m,
3266s, 3100m, 3065s, 3010m, 1650s, 1604s, 1552s, 1519s,
1488s, 1448s, 1365s, 1295s, 1274s, 1195s, 1139s, 1058s,
1000s, 954s, 916s, 819s, 759s, 694s cmꢂ1
;
1H-NMR
CH), 7.85ꢀ
6 Hz, 2H, aromatic-H), 7.74 (s, 2H,
(Me2SO-d6, 500 MHz): dꢃ
/
8.48 (s, 1H, Nꢀ
/
/
7.84 (d, Jꢃ
/
aromatic-H), 7.68 (s, 2H, aromatic-H), 7.45 (s, 3H,
aromatic-H), 4.90 (s, 2H, ferrocene-H), 4.42 (s, 2H,
ferrocene-H), 4.03 (s, 5H, ferrocene-H); 13C-NMR
1299s, 1270s, 1181s, 1105s, 887s, 850s, 819s, 765s, 700s
cmꢂ1; H-NMR (CDCl3): dꢃ
7.81 (m, 2H, aromatic-H), 7.65 (m, 2H, aromatic-H),
4.89 (s, 2H, ferrocene-H), 4.71 (s, 2H, ferrocene-H), 4.42
(s, 4H, ferrocene-H), 4.23 (s, 5H, ferrocene-H), 4.04 (s,
5H, ferrocene-H), 2.25 (s, 3H, CH3); 13C-NMR
(Me2SO-d6, 125 MHz): dꢃ 162.91 (CONH), 147.44,
/
1
/
10.53 (s, 1H, CONH),
143.44, 134.41 (aromatic-C), 130.03, 128.86, 127.81,
127.06, 125.54 (aromatic-CH), 83.08 (ferrocene-C),
69.61, 69.55, 66.72 (ferrocene-CH); FABMS m/z (%)
[Mꢁ, 408 (30)]. Anal. Calc. for C24H20FeN2O: C, 70.60;
H, 4.93; N, 6.86. Found: C, 70.49; H, 5.10; N, 6.65%.
(Me2SO-d6): dꢃ167.17 (CO), 144.49, 129.32 (aro-
/
matic-C), 127.65, 127.52, 125.50, 108.39 (aromatic-
CH), 82.80, 82.79 (ferrocene-C), 72.00, 69.59, 69.52,
69.46, 69.08, 66.66, 66.55 (ferrocene-CH), 30.84 (CH3);
FABMS m/z (%) [Mꢁ 530 (15)].
5.10.2. p-(Ferrocenyl)benzoylhydrazono-p-
methoxybenzylidene (11b)
Rꢃ
/
p-OCH3: Yield 98%, m.p. 228ꢀ230 8C; IR (KBr)
/
n 3220s, 3060s, 2900s, 2830s, 1643s, 1610s, 1562s, 1511s,
1421s, 1386s, 1299s, 1253s, 1170s, 1147s, 1105s, 1060s,
1029s, 964s, 916s, 887s, 854s, 831s, 769s, 669s cmꢂ1; 1H-
5.9. 1-[p-(N-Acetylhydrazinoylphenyl)]ferrocene (10b)
NMR (CDCl3ꢁ
NꢀCH), 7.87 (s, 2H, aromatic-H), 7.72 (s, 2H, aromatic-
H), 7.56 (d, Jꢃ6.5 Hz, 2H, aromatic-H), 6.92 (s, 2H,
/
Me2SO-d6, 500 MHz): dꢃ 8.40 (s, 1H,
/
A mixture of hydrazide 2 (0.32 g, 1 mmol) and
acetylferrocene (0.228 g, 1 mmol) was refluxed in
AcOH (20 ml) for 36 h. The excess AcOH was removed
under vacuum and the residue was chromatographed on
/
/
aromatic-H), 4.74 (s, 2H, ferrocene-H), 4.39 (s, 2H,
ferrocene-H), 4.03 (s, 5H, ferrocene-H), 3.85 (s, 3H,
silica gel using CHCl3ꢀ
/
acetone mixture (5:1) to afford
the unexpected N-acetyl derivative 10b (0.32 g in 86%)
OCH3); 13C-NMR (CDCl3ꢁ
/
Me2SO-d6, 125 MHz): dꢃ
/
161.17 (CONH), 148.15, 130.91 (aromatic-C), 129.09,
128.02, 125.54, 114.09 (aromatic-CH), 83.40 (ferrocene-
C), 69.74, 66.72 (ferrocene-CH), 55.35 (OCH3); FABMS
m/z (%) [Mꢁ, 438 (48)]. Anal. Calc. for C25H22FeN2O2:
C, 68.50; H, 5.05; N, 6.39. Found: C, 68.48; H, 4.89; N,
6.23%.
1
as red crystals, m.p. 245 8C (dec.). H-NMR (Me2SO-
d6): dꢃ
7.80ꢀ7.79 (d, Jꢃ
(d, Jꢃ8.5 Hz, 2H, aromatic-H), 4.89 (t, Jꢃ
ferrocene-H), 4.41 (t, Jꢃ1.5 Hz, 2H, ferrocene-H), 4.02
(s, 5H, ferrocene-H), 1.92 (s, 3H, CH3); 13C-NMR
(Me2SO-d6) dꢃ168.45 (CO), 165.21 (CO), 143.21,
/
10.21 (s, 1H, CONH), 9.85 (s, 1H, CONH),
8.5 Hz, 2H, aromatic-H), 7.64ꢀ7.63
1.5 Hz, 2H,
/
/
/
/
/
/
/
5.10.3. p-(Ferrocen-1-yl)benzoylhydrazono-p-(ferrocen-
1-yl)benzylidene (11c)
129.40, (aromatic-C), 127.47, 125.34, (aromatic-CH),
82.93 (ferrocene-C), 69.42, 66.54 (ferrocene-CH), 20.52
(CH3); FABMS m/z (%) [Mꢁ, 362 (20)]. Anal. Calc. for
C19H18FeN2O2: C, 63.00; H, 5.00; N, 7.73. Found: C,
62.86; H, 4.89; N, 7.47%.
Rꢃ
/
p-ferrocenyl: yield 100%, m.p. 209ꢀ211 8C; IR
/
(KBr) n 3089m, 1650s, 1604s, 1546s, 1517s, 1417m,
1353s, 1270s, 1182m, 1139s, 1105s, 998s, 887s, 825s,
;
765s, 696m cmꢂ1 1H-NMR (Me2SO-d6, 500 MHz):
dꢃ
/
11.77 (s, 1H, CONH), 8.45 (s, 1H, Nꢀ
/
CH), 7.87 (d,
8 Hz, 2H, aromatic-H), 7.65 (m, 6H, aromatic-H),
5.10. Synthesis of p-(ferrocenyl)benzoylhydrazono-p-
Jꢃ
/
substituted arylidenes (11aꢀ
/
c)
4.90 (s, 2H, ferrocene-H), 4.85 (s, 2H, ferrocene-H), 4.42
(s, 2H, ferrocene-H), 4.40 (s, 2H, ferrocene-H), 4.04 (s,
A mixture of hydrazide 2 (0.5 g, 1.56 mmol) and
aromatic aldehydes or p-ferrocenylbenzaldehyde (1.7
mmol) was refluxed in EtOH (50 ml) containing AcOH
10H, ferrocene-H); 13C-NMR (CDCl3ꢁ
/
Me2SO-d6, 125
162.89 (CONH), 147.53, 143.27, 141.34,
131.73 (aromatic-C), 127.73, 127.14, 125.84, 125.36
MHz): dꢃ
/

10
A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ12
/
(aromatic-CH), 83.62, 82.90 (ferrocene-C), 69.45, 69.41,
66.55, 66.33 (ferrocene-CH), FABMS m/z (%) [Mꢁ, 592
(8)]. Anal. Calc. for C34H28Fe2N2O: C, 68.95; H, 4.76;
N, 4.73. Found: C, 68.60; H, 5.18; N, 5.15%.
FABMS m/e (%) [Mꢁ, 424 (45)]. Anal. Calc. for
C25H20FeO3: C, 70.77; H, 4.75. Found: C, 71.01; H,
4.51%.
5.11. Synthesis of 1-(p-formylphenyl)-1?-(4-formyl-1-
naphthyl)ferrocene (13) and 1-(m-formylphenyl)-1?-(3-
formyl-5-methoxyphenyl)ferrocene (15)
5.12. Synthesis of the ferrocene-1,1?-dihydrazones 12, 14
and 18
According to the method described above, a mixture
of hydrazide 2 (0.64 g, 2 mmol) and 1,1?-ferrocene-
dialdehyde derivatives (1 mmol) was refluxed in EtOH
(50 ml) in the presence of AcOH (1 ml) for 5 h to give
the corresponding di-hydrazones 12, 14 and 18 in very
good yield.
A mixture of ferrocene-dialcohols (3 g, 6.7 mmol) and
MnO2 (30 g) was stirred at r.t. in CHCl3 (300 ml) for 15
h. The reaction mixture was filtered off through glass
wool and the filtrate was distilled under reduced
pressure at 30 8C. The residue was chromatographed
on silica gel using CHCl3ꢀ/hexane (3:1) to give the
corresponding 1-(p-formylphenyl)-1?-(4-formyl-1-
naphthyl)ferrocene (13) and 1-(m-formylphenyl)-1?-(3-
formyl-5-methoxyphenyl)ferrocene (15), respectively.
5.12.1. Bis-[p-(ferrocenyl)benzoylhydrazono]ferrocen-
1,1?-ylidene (12)
Yield 98%, m.p. 206ꢀ208 8C; IR (KBr) n 3220s,
/
5.11.1. 1-(p-Formylphenyl)-1?-(4-formyl-1-
naphthyl)ferrocene (13)
3090s, 1658s, 1639s, 1604s, 1554s, 1521s, 1465s, 1365s,
1326s, 1295s, 1274s, 1191s, 1143s, 1105s, 1056s, 1000s,
944s, 885s, 850s, 821s, 765s cmꢂ1; 1H-NMR (Me2SO-d6,
Dark red crystals, m.p. 106ꢀ107 8C, yield 2.2 g, 73%,
/
literature (64%) [18]; IR (KBr) n 3089m, 2973m, 1691s,
1602s, 1567s, 1513s, 1216s, 1168s, 1058s, 829s, 765s
500 MHz): dꢃ
/
11.51 (s, 2H, 2 CONH), 8.23 (s, 2H, 2
NꢀCH), 7.77 (s, 4H, aromatic-H), 7.57 (s, 4H, aromatic-
/
1
cmꢂ1. H-NMR (500 MHz, CDCl3): dꢃ
/
10.35 (s, 1H,
8.5, Jꢃ0.5 Hz,
CH (naphthalene-H)], 8.54 [dd, Jꢃ8.5, Jꢃ0.5
Hz, 1H, CHꢀCH (naphthalene-H)], 7.82 (d, Jꢃ1 Hz,
2H, naphthalene-H), 7.66 (m, 3H, aromatic-H), 7.63 (m,
1H, aromatic-H), 7.45 (d, Jꢃ8 Hz, 2H, aromatic-H),
4.72 (t, Jꢃ1.5 Hz, 2H, ferrocene-H), 4.64 (t, Jꢃ1.5 Hz,
2H, ferrocene-H), 4.45 (t, Jꢃ1.5 Hz, 2H, ferrocene-H),
4.37 (t, Jꢃ
1.5 Hz, 2H, ferrocene-H). 13C-NMR (125
MHz, CDCl3): dꢃ192.92, 191.57 (2 CHO), 145.56,
H), 4.85 (s, 4H, ferrocene-H), 4.75 (s, 4H, ferrocene-H),
4.49 (s, 4H, ferrocene-H), 4.41 (s, 4H, ferrocene-H), 4.01
(s, 10H, ferrocene-H); 13C-NMR (Me2SO-d6, 125 MHz):
CHO), 9.92 (s, 1H, CHO), 9.30 [dd, Jꢃ
/
/
1H, CHꢀ
/
/
/
/
/
dꢃ 162.28 (2 CONH), 147.79, 143.00, 130.60 (aromatic-
/
C), 127.76, 125.35 (aromatic-CH), 83.09, 80.40 (ferro-
cene-C), 71.14, 69.52, 68.49, 66.68 (ferrocene-CH);
FABMS m/z (%) [Mꢁ1ꢁ
H, 847 (35)]. Anal. Calc. for
C46H38Fe3N4O2: C, 65.25; H, 4.52; N, 6.61. Found: C,
/
/
/
/
/
/
64.86; H, 4.37; N, 6.40%.
/
143.53 (aromatic-C), 135.55, 134.23 (aromatic-C),
131.85, 131.13 (aromatic-C), 129.81, 129.57, 128.64,
126.85, 126.44, 126.36, 126.32, 125.14 (aromatic-CH),
86.47, 84.30 (ferrocene-C), 72.49, 72.27, 71.40, 68.85
(ferrocene-CH). FABMS m/e [Mꢁ, 444 (92)].
5.12.2. 1-[p-(Ferrocenyl)benzoylhydrazono-4-benz-1-
ylidene]-1?-[p-(ferrocen-1-yl)benzoylhydrazono-4-
naphth-1-ylidene]ferrocene (14)
Yield 84.6%, m.p. 197ꢀ199 8C; IR (KBr) n 3215ms,
/
3087s, 3030m, 1648s, 1606s, 1544s, 1517s, 1417m,
1363m, 1294s, 1272s, 1187s, 1141s, 1105s, 1056m,
5.11.2. 1-(m-Formylphenyl)-1?-(3-formyl-5-
methoxyphenyl)ferrocene (15)
1
1002m, 958w, 887s, 848s, 827s, 763s, 698s cmꢂ1; H-
Orange red crystals, m.p. 87ꢀ
(KBr) n 3095s, 2975w, 2840m, 2800s, 2721s, 1702s,
/
88 8C, yield 71%; IR
NMR (Me2SO-d6, 500 MHz): dꢃ
11.77 (s, 1H, CONH), 8.42 (s, 1H, Nꢀ
NꢀCH), 7.91ꢀ7.84 (m, 6H, aromatic-H), 7.70ꢀ
6H, aromatic-H), 7.59ꢀ7.51 (m, 6H, aromatic-H), 4.91
(m, 6H, ferrocene-H), 4.65 (s, 2H, ferrocene-H), 4.44 (m,
6H, ferrocene-H), 4.36 (s, 2H, ferrocene-H), 4.05ꢀ4.01
(m, 10H, ferrocene-H); 13C-NMR (Me2SO-d6, 125
MHz): dꢃ 164.66 (2 CONH), 144.13, 139.14, 131.07,
130.27, 130.18 (complex aromatic-C), 128.15, 127.18,
125.90, 125.13, 123.83 (complex aromatic-CH), 83.42
(ferrocene-C), 71.76, 69.82, 69.71, 68.18, 66.86, 66.77
(complex ferrocene-CH); FABMS m/z (%) [Mꢁ1, 1049
(30)]. Anal. Calc. for C62H48Fe3N4O2: C, 71.01; H, 4.61;
N, 5.34. Found: C, 70.87; H, 4.48; N, 5.24%.
/
11.88 (s, 1H, CONH),
CH), 8.31 (s, 1H,
7.65 (m,
/
1677s, 1590s, 1504s, 1461s, 1438s, 1388s, 1272s, 1249s,
1186s, 1147s, 1079s, 1018s, 935s, 815s, 790s, 688s cmꢂ1
/
/
/
.
/
1H-NMR (500 MHz, CDCl3): dꢃ
(s, 1H, CHO), 7.62ꢀ7.18 (m, 6H, aromatic-CH), 6.67
/
9.8 (s, 1H, CHO), 9.7
/
/
(m, 1H, aromatic-CH), 4.82 (s, 2H, ferrocene-CH), 4.61
(s, 2H, ferrocene-H), 4.36 (s, 2H, ferrocene-H), 4.32 (s,
2H, ferrocene-H), 3.81 (s, 3H, OCH3). 13C-NMR (125
/
MHz, CDCl3): dꢃ193.24, 191.76 (2 CHO), 162.10
/
(aromatic-C), 139.18, 137.19, 132.63, 130.56 (aromatic-
C), 130.45, 129.55, 128.15, 127.09, 126.81, 111.72
(aromatic-CH), 86.00, 83.79 (ferrocene-C), 71.57,
71.24, 70.89, 68.68 (ferrocene-CH), 56.43 (OCH3).

A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ
/12
11
5.12.3. 1-[p-(Ferrocenyl)benzoylhydrazono-3-benz-1-
ylidene]-1?-[p-(ferrocen-1-yl)benzoylhydrazono-4-
methoxy-3-benz-1-ylidene]ferrocene (18)
162.96, (CON), 159.71 (Nꢀ
/
C), 142.63, 131.03, 127.74,
125.24 (aromatic-C and CH), 83.21 (ferrocene-C), 69.39,
69.36, 66.52 (ferrocene-CH), 25.05 (2 CH3).
Yield 92.8%, m.p. 192ꢀ193 8C; IR (KBr) n 3210m,
/
3085s, 2820s, 1650s, 1606s, 1550s, 1504s, 1463s, 1411s,
1357s, 1295s, 1268s, 1182s, 1141s, 1105s, 1029s, 948s,
885s, 850s, 817s, 765s, 694s cmꢂ1; 1H-NMR (Me2SO-d6,
References
500 MHz): dꢃ
CONH), 8.37 (s, 1H, Nꢀ
7.86ꢀ7.84 (d, Jꢃ7.5 Hz, 4H, aromatic-H), 7.65ꢀ
(m, 8H, aromatic-H), 7.32ꢀ7.19 (m, 2H, aromatic-H),
6.87 (d, Jꢃ8.5 Hz, aromatic-H), 4.88 (m, 4H, ferrocene-
/
11.80 (s, 1H, CONH), 11.70 (s, 1H,
CH), 8.31 (s, 1H, NꢀCH),
7.47
[1] (a) R.D.A. Hudson, J. Organomet. Chem. 637 (2001) 47;
(b) P. Naguyen, P.G. Elipe, I. Manners, Chem. Rev. 99 (1999)
1515;
/
/
/
/
/
/
(c) I.R. Whittall, A.M. McDonagh, M.G. Humphrey, Adv.
Organomet. Chem. 42 (1998) 291;
/
(d) M. Uno, P.H. Dixneuf, Angew. Chem. Int. Ed. Engl. 37 (1998)
1714;
H), 4.77 (s, 2H, ferrocene-H), 4.68 (s, 2H, ferrocene-H),
4.42 (s, 4H, ferrocene-H), 4.31 (s, 2H, ferrocene-H), 4.26
(s, 2H, ferrocene-H), 4.03 (s, 10H, ferrocene-H), 3.81 (s,
(e) A. Togni, T. Hayashi (Eds.), Ferrocene-Homogeneous Cata-
lysis, Organic Synthesis and Materials Science, VCH, New York,
1995;
3H, OCH3); 13C-NMR (Me2SO-d6, 125 MHz): dꢃ
/
(f) G.G.A. Balavoine, J.C. Daran, G. Iftime, P.G. Lacrolx, E.
Manoury, J.A. Delaire, I. Maltey-Fanton, K. Natatani, S.D.
Bella, Organometallics 18 (1999) 21;
162.94, 162.75 (2 CONH), 157.52, 147.70, 143.20,
143.08, 137.50, 134.13, 130.53, 130.38 (complex aro-
matic-C), 128.36, 127.76, 127.69, 127.23, 126.49, 125.78,
125.37, 124.83, 124.24, 123.95, 111.49 (complex aro-
matic-CH), 84.90, 83.04, 82.99, 82.83 (ferrocene-C),
79.07, 70.13, 69.76, 69.43, 69.72, 67.26, 67.17, 66.50
(complex ferrocene-CH), 55.25 (OCH3); FABMS m/z
(%) [Mꢁ1, 1029 (25)]. Anal. Calc. for C59H48Fe3N4O3:
C, 68.89; H, 4.70; N, 5.44. Found: C, 68.67; H, 4.59; N,
5.26%.
(g) J. Liu, R. Castro, K.A. Abboud, A.E. Kaifer, J. Org. Chem. 65
(2000) 6973;
(h) J.F. Biernat, T. Wilczewski, Tetrahedron 36 (1980) 2521;
(i) S. Akabori, Y. Habata, Y. Sakamoto, M. Sato, S. Ebine, Bull.
Chem. Soc. Jpn. 56 (1983) 537.
[2] (a) J.C. Torres, R.A. Pilli, M.D. Vargas, F.A. Violante, S.J.
Garden, A.C. Pinto, Tetrahedron 58 (2002) 4487 (and references
cited therein);
(b) N. Argyropoulos, E.C. Argyropoulou, J. Organomet. Chem.
654 (2002) 117.
[3] (a) E.J. Miller, C.A. Weigelt, J.A. Serth, R. Rusyid, J. Brenner,
L.A. Luck, M.J. Godlewski, J. Organomet. Chem. 440 (1992) 91;
(b) F.W. Grevels, A. Kuran, S. Ozkar, M. Zora, J. Organomet.
Chem. 587 (1999) 122;
5.13. Reaction of hydrazide 2 with ethyl acetoacetate
A mixture of hydrazide 2 (0.5 g, 1.56 mmol) and ethyl
acetoacetate (1 ml) was refluxed in EtOH (25 ml)
containing AcOH (1 ml) for 5 h. The reaction mixture
was cooled and the yellow precipitate was collected by
filtration and washed with water several times. The
crude product was chromatographed on silica gel using
(c) S.J. Jong, J.M. Fang, J. Org. Chem. 66 (2001) 3533.
[4] (a) Y. Zhu, M.O. Wolf, Chem. Mater. 11 (1999) 2995;
(b) S. Barlow, D. O’Hare, Chem. Rev. 97 (1997) 637.
[5] (a) S. Paitayatat, B. Tarnchompoo, Y. Thebtaranonth, Y.
Yuthavong, J. Med. Chem. 40 (1997) 633;
(b) E. Bucci, L. De Napoli, G. Di Fabio, A. Messere, D.
Montesarchio, A. Romanilli, G. Piccialli, M. Varra, Tetrahedron
55 (1999) 14435;
hexaneꢀacetone (1:2) to give in the second fraction 0.31
/
g of the unexpected product 20 as orange crystals.
(c) C. Biot, N. Francois, L. Maciejewski, J. Brocard, D. Poulain,
Bioorg. Med. Chem. Lett. 10 (2000) 839;
5.13.1. Analytical data of p-(ferrocen-1-
yl)benzoylhydrazono-2-propylidene (20)
(d) C. Biot, L. Delhaes, L.A. Maciejewski, M. Mortuaire, D.
Camus, D. Dive, J.S. Brocard, J. Med. Chem. 35 (2000) 707;
(e) T. Itoh, S. Shirakami, N. Ishida, Y. Yamashita, T. Yoshida,
H.-S. Kim, Y. Wataya, Bioorg. Med. Chem. Lett. 10 (2000) 1657;
(f) S. Maricic, A. Ritzen, U. Berg, T. Frejd, Tetrahedron 57 (2001)
6523;
Yield 51.4%, m.p. 203ꢀ205 8C; IR (KBr) n 3200s,
/
3080s, 3020m, 2900m, 1639s, 1608s, 1540s, 1515s, 1419s,
1371s, 1297s, 1263s, 1187s, 1147s, 1105s, 1031s, 1000s,
887s, 852s, 821s, 767s cmꢂ1
;
1H-NMR (CDCl3, 500
6.5 Hz,
(g) G. Jaouen, Chem. Ber. (2001) 36.
[6] H. Ma, Y. Hon, Y. Bai, J. Lu, B. Yang, J. Organomet. Chem.
MHz): dꢃ
/
7.73 (s, 2H, aromatic-H), 7.53 (d, Jꢃ
/
2H, aromatic-H), 4.69 (s, 2H, ferrocene-H), 4.38 (s, 2H,
ferrocene-H), 4.03 (s, 5H, ferrocene-H), 2.16 (s, 3H,
CH3), 1.99 (s, 3H, CH3); FABMS m/z (%) [Mꢁ1, 360
(50)]. Anal. Calc. for C20H20FeN2O: C, 66.68; H, 5.59;
637ꢀ639 (2001) 742.
[7] (a) C.J. Richards, A.W. Mulvaney, Tetrahedron: Asymmetry 7
(1996) 1419;
/
(b) W. Zhang, Y. Adachi, T. Hirao, I. Ikeda, Tetrahedron:
Asymmetry 7 (1996) 451;
1
N, 7.78. Found: C, 66.51; H, 5.42; N, 7.64%; H-NMR
(c) T. Sammakia, H.A. Latham, J. Org. Chem. 60 (1995) 6002;
(d) C.J. Richards, T. Damalidis, D.E. Hibbs, M.B. Hursthouse,
Synlett (1995) 74;
(Me2SO-d6, 500 MHz): dꢃ
7.75 (d, Jꢃ8.5 Hz, 2H, aromatic-H), 7.62ꢀ
8.5 Hz, 2H, aromatic-H), 4.86 (t, Jꢃ1.5 Hz, 2H,
ferrocene-H), 4.40 (t, Jꢃ1.5 Hz, 2H, ferrocene-H),
4.02 (s, 5H, ferrocene-H), 2.01 (s, 3H, CH3), 1.96 (s,
3H, CH3); 13C-NMR (Me2SO-d6, 125 MHz): dꢃ
/
10.39 (s, 1H, CONH), 7.76ꢀ
/
/
/
7.6 (d, Jꢃ
/
(e) Y. Nishibayashi, S. Uemura, Synlett (1995) 79;
(f) Y. Nishibayashi, K. Segawa, Y. Arikawa, K. Ohe, M. Hidai, S.
/
/
Uemura, J. Organomet. Chem. 545ꢀ546 (1997) 381;
(g) A. Chesney, M.R. Bryce, R.W.J. Chubb, A.S. Batsanov,
/
/
J.A.K. Howard, Synthesis (1998) 413;

12
A.A.O. Sarhan, T. Izumi / Journal of Organometallic Chemistry 675 (2003) 1ꢀ12
/
(h) Y. Nishibayashi, K. Segawa, H. Takada, K. Ohe, S. Uemura,
J. Chem. Soc. Chem. Commun. (1996) 847;
(i) T. Sammakia, H.A. Latham, D.R. Schaad, J. Org. Chem. 60
(1995) 10.
[14] A. Togni, M. Hobi, G. Rihs, G. Rist, A. Albinati, P. Zanello, D.
Zech, H. Keller, Organometallics 13 (1994) 1224.
[15] (a) T. Lanez, P.L. Pauson, J. Chem. Soc. Perkin Trans. 1 (1990)
2437;
[8] J. Howarth, K. Hanlon, Tetrahedron Lett. 42 (2001) 751.
[9] (a) M. Sato, S. Tanaka, S. Ebine, K. Morinaga, S. Akabori, J.
Organomet. Chem. 282 (1985) 247;
(b) G.D. Broadhead, P.L. Pauson, J. Chem. Soc. (1955) 367.
[16] (a) A.A.O. Sarhan, H.A.H. El-Sherief, A.M. Mahmoud, Tetra-
hedron 52 (31) (1996) 10485;
(b) M. Sato, S. Tanaka, S. Ebine, K. Morinaga, S. Akabori, J.
Organomet. Chem. 289 (1985) 91.
(b) A.A.O. Sarhan, Heteroat. Chem. 11 (6) (2000) 399;
(c) Z.A. Hozien, A.A.O. Sarhan, H.A.H. El-Sherief, A.M.
Mahmoud, J. Heterocycl. Chem. 37 (2000) 943.
[17] (a) G.G.A. Balavoine, G. Doisneau, T. Fillebeen-Khan, J.
Organomet. Chem. 412 (1991) 381;
[10] (a) M.P. Andrews, C. Blackburn, J.F. McAleer, V.D. Patel, J.
Chem. Soc. Chem. Commun. 29 (1987) 378;
(b) P.D. Beer, H. Sikanyika, C. Blackburn, J.F. McAleer, M.G.B.
Drew, J. Chem. Soc. Dalton Trans. (1990) 3295;
(b) M.A. Carroll, A.J.P. White, D.A. Widdowson, D.J. Williams,
J. Chem. Soc. Perkin Trans. 1 (2000) 1551.
(c) P.D. Beer, H. Sikanyika, Polyhedron 9 (1990) 1091;
(d) P.D. Beer, J.P. Danks, D. Hesek, J.F. McAleer, J. Chem. Soc.
Chem. Commun. (1993) 1735;
[18] A. Kasahara, T. Izumi, I. Shimizu, T. Oikawa, H. Umezawa, M.
Murakami, O. Watanabe, Bull. Chem. Soc. Jpn. 58 (1985) 1560.
[19] (a) X.J. Dang, J. Tong, H.L. Li, J. Inclusion Phenom. 24 (1996)
275;
(e) P.D. Beer, J.E. Martin, S.L.W. McWhinnie, M.E. Harman,
M.B. Hursthouse, M.I. Ogden, A.H. White, J. Chem. Soc. Dalton
Trans. (1991) 2485.
(b) M.Y. Ni, Y. Wang, H.L. Li, Pol. J. Chem. 71 (1997) 816.
[20] P. Hemmerich, C. Veeger, H.C.S. Wood, Angew. Chem. Int. Ed.
Engl. 4 (1984) 671.
[11] (a) P.D. Beer, J. Cadman, Coord. Chem. Rev. 205 (2000) 131;
(b) P.D. Beer, P.A. Gale, G.Z. Chen, Coord. Chem. Rev. 185ꢀ
/186
(1999) 3.
[12] Y. Ueno, H. Sano, M. Okawara, J. Chem. Soc. Chem. Commun.
(1980) 28.
[21] (a) K.L. Rinehart, Jr., K.L. Motz, S. Moon, J. Am. Chem. Soc. 79
(1957) 2749;
(b) G.W. Gokel, I.K. Ugi, J. Chem. Educ. 49 (1972) 294;
(c) R.B. Woodward, M. Rosenblum, M.C. Whiting, J. Am.
Chem. Soc. 74 (1952) 3458;
[13] A.J. Moore, P.J. Skabara, M.R. Bryce, A.S. Batsanov, J.A.K.
Howard, S.T.A.K. Daley, J. Chem. Soc. Chem. Commun. (1993)
417.
(d) K. Schlogl, Monatsh. Chem. 4 (1957) 601.