The reactions of semicarbazide and thiosemicarbazide with ferrocenyl-substituted α,β-enones

Article abstract of DOI:10.1016/S0022-328X(01)01059-2

Semicarbazide (hydrochloride) and thiosemicarbazide react with α,β-unsaturated ketones of the ferrocene series in excess of ^tBuOK to give 1-carbamoyl- and 1-thiocarbamoyl(ferrocenyl)-4,5-dihydropyrazoles. The condensation with thiosemicarbazide

Full text of DOI:10.1016/S0022-328X(01)01059-2

Journal of Organometallic Chemistry 633 (2001) 137–142
www.elsevier.com/locate/jorganchem
The reactions of semicarbazide and thiosemicarbazide with
ferrocenyl-substituted a,b-enones
T. Klimova a,*, E.I. Klimova a, M. Mart´ınez Garc´ıa b,1, J.M. Me´ndez Stivalet a,
L. Ru´ız Ram´ırez a
a Department of Chemistry, National Autonomous Uni6ersity of Mexico, C.P. 04510, Mexico D.F., Mexico
b Institute of Chemistry, National Autonomous Uni6ersity of Mexico, C.P. 04510, Mexico D.F., Mexico
Received 23 April 2001; accepted 1 June 2001
Abstract
Semicarbazide (hydrochloride) and thiosemicarbazide react with a,b-unsaturated ketones of the ferrocene series in excess of
tBuOK to give 1-carbamoyl- and 1-thiocarbamoyl(ferrocenyl)-4,5-dihydropyrazoles. The condensation with thiosemicarbazide is
accompanied by the fragmentation of the starting a,b-enones resulting in ferrocenecarbaldehyde or acetylferrocene thiosemicarba-
zones. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ferrocene; Semicarbazide; Thiosemicarbazide; 1-Carbamoyl-4,5-dihydropyrazole; 1-Thiocarbamoyl-4,5-dihydropyrazole
The use of semicarbazides and thiosemicarbazides for
the construction of heterocyclic systems has not been
studied so far. As a rule, semicarbazides and thiosemi-
carbazides are employed for the identification of car-
bonyl compounds by converting them, in the presence
of acids, into crystalline derivatives, semicarbazones
and thiosemicarbazones, respectively [9,10]. On the
other hand, semicarbazides represent hydrazine and
urea derivatives simultaneously, and thus, these might
react with a,b-unsaturated ketones yielding compounds
of the dihydropyrazole or tetrahydropyrimidine series,
the potentially biologically active structures, which is of
substantial interest.
1. Introduction
The chemistry of hetero- and carbocycles with ferro-
cenyl substituents is based on sufficiently high accessi-
bility of the starting a,b-unsaturated carbonyl
compounds of the ferrocene series. Thus the latter react
with hydrazine in aqueous ethanol to give unstable,
1-nonsubstituted 4,5-dihydropyrazoles, which are con-
verted into stable 1-acetyl derivatives by acylation [1–
3]. Arylhydrazines react with ferrocenyl enones in an
acidic medium [4,5] to give 1-aryl-substituted 4,5-dihy-
dropyrazoles. Under basic conditions, ferrocenylchal-
cones react with thiourea yielding ferrocenyltetrahydro-
pyrimidinethiones [6]. The characteristic features of all
these reactions are their selectivity, high yields of the
final products, and ease of their isolation.
It is known that pyrazole, dyhydropyrazole, pyrim-
idine, dihydro- and tetrahydropyrimidine fragments are
abundant components of the structures of diverse bio-
logically active compounds [2,7,8], which stimulates
further investigations into the synthesis and studies of
pharmacological properties of ferrocenyl-substituted ni-
trogen-containing heterocycles.
2. Results and discussion
Here we report the results of our studies on the
reactions of semicarbazide and thiosemicarbazide with
ferrocenyl-substituted a,b-unsaturated ketones. The
starting compounds used were represented by linear
(1a–g) and cyclic (2–4) chalcones (Scheme 1) prepared
by the condensation of the respective carbaldehydes
and ketones under standard conditions [3,11].
* Corresponding author. Fax: +52-5-622-5366.
E-mail address: klimova@servidor.unam.mx (T. Klimova).
1 Fax: +525-616-2203.
We found that semicarbazides do not react with the
chalcones 1a–g and 2–4 in acidic or neutral aqueous-
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01059-2

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T. Klimo6a et al. / Journal of Organometallic Chemistry 633 (2001) 137–142
ethanolic media. The conditions of choice were boiling
of the reactants in anhydrous isopropyl alcohol in the
presence of BuOK leading to 1-carbamoyl- and 1-thio-
bamoyl-substituted dihydropyrazoles of the type 12. In
all cases, only fragmentation of the chalcones occurs to
give the thiosemicarbazone 11 [9] (ca. 75% yield).
t
1
carbamoyl(ferrocenyl)-4,5-dihydropyrazoles 5a–g, 7a,b,
8a,b, 9a,b, and 6a–g, respectively (Schemes 2 and 3).
It is noteworthy that the reaction of the chalcones
1–4 with semicarbazide occurs without any complica-
tions, and 1-carbamoyl-4,5-dihydropyrazoles 5, 7–9
were isolated in 58–71% yields. Bicyclic carbamoyldi-
hydropyrazoles 7–9 are formed as ca. 1:1 mixtures of
two diastereomers with trans- and cis-orientations of
the H(4) and H(5) protons in dihydropyrazole rings.
The trans- (7a–9a) and cis-isomers (7b–9b) are easily
separated by column chromatography on alumina.
The condensation of the chalcones 1a–g with
thiosemicarbazide is accompanied by the fragmentation
of the starting chalcones, so that the main reaction
products, viz. 1-thiocarbamoyl derivatives 6a–g (yields
ca. 50–65%) were formed along with acetylferrocene
thiosemicarbazone (10) [10] (yields ca. 10–15% from
1a–c), ferrocenecarbaldehyde thiosemicarbazone (11)
[9] (yields 10–20% from 1e–g), or a mixture of 10 (ca.
7%) and 11 (ca. 8%) from 1d.
Compounds 5–9 were characterized by H- and 13C-
NMR spectral data (Tables 1 and 2) and data from
elemental analyses (Table 3) which corroborate com-
pletely their structures as 4,5-dihydropyrazole
derivatives.
1
The H-NMR spectra of compounds 5a–g and 6a–g
contain the characteristic ABX proton spin systems and
differ essentially from each other depending on the
position of the ferrocenyl group in the heterocyclic ring.
Thus the presence of the metallocene substituent at
position 3 of the dihydropyrazole ring (5a–c, 6a–c) is
typical of the pronounced upfield shift of the H(A)
protons (l=ca. 3.0), the difference (lH(B)–lH(A)) being
equal to ca. 0.5–0.6 ppm. In the spectra of dihydropy-
razoles 5e–g and 6e–g with the ferrocenyl group at
position 5, the H(A) protons were present at lower
fields (l=ca. 3.6–3.7). Regarding the signals for the
H(B) and H(X) protons and those for the NH2 group,
these are little affected, being equal to ca. 0.02–0.09
ppm.
Reactions of cyclic enones 2–4 with thiosemicar-
bazide do not result in the formation of 1-thiocar-
For dihydropyrazoles with two ferrocenyl sub-
stituents (5d, 6d), the parameters of the ABX proton
Scheme 1.
Scheme 2.

T. Klimo6a et al. / Journal of Organometallic Chemistry 633 (2001) 137–142
139
Scheme 3.
resonate at 5.31, 5.30, and 5.41, and the vicinal cou-
2JH(4),H(5) are equal to 10.3, 10.4, and
system are similar to those for the 5-ferrocenyl deriva-
tives, which points toward the greater effect of the
ferrocenyl substituent at position 5.
pling constants
10.0 Hz, respectively. Chemical shifts of analogous
protons of compounds 7b–9b are found at higher fields
(l=4.77, 4.70, and 4.87), while the vicinal coupling
constants are smaller (2JH(4),H(5)=6.8, 4.0, and 7.0 Hz,
respectively). Thus, comparison of these spectral data
with those for the previously identified compounds
[13,14] allows one to ascribe the trans-structure to
compounds 7a–9a with pseudo-axial orientation of
H(4) and H(5) and pseudo-equatorial position of the
ferrocene residue. Apparently, protons H(4) and H(5)
in compounds 7b–9b occupy cis-positions.
The isomeric position of the ferrocenyl group in
1-carbamoyl- (5a–g) and 1-thiocarbamoyldihydropyra-
zoles (6a–g) affects strongly the pattern of the signals
for the protons of the ferrocenyl group itself. Thus, all
the protons of the substituted cyclopentadienyl ring in
3-ferrocenyl-substituted dihydropyrazoles (5a–c, 6a–c)
resonate at lower fields than those of the nonsubstituted
cyclopentadienyl ring, i.e. the effect of the dihydropyra-
zole ring in this case is analogous to that of a strong
electron-withdrawing substituent [12]. In 5-ferrocenyldi-
hydropyrazoles (5d–g, 6d–g), the heterocycle acts as a
weak electron acceptor, and some protons of the substi-
tuted cyclopentadienyl ring resonate at higher fields
than the protons of the C5H5 group. The spectral
differences observed between 3- and 5-ferrocenyl-1-car-
bamoyl- (and -1-thiocarbamoyl-) 4,5-dihydropyrazoles
are typical of all the ferrocenyldihydropyrazoles of the
analogous structures obtained so far [3–5], which can
be employed for the NMR-based identification of iso-
meric ferrocenyldihydropyrazoles.
Analysis of the 13C-NMR spectra of compounds
5a–g and 6a–g (Table 2) also allows one to reveal
characteristic differences for 3- and 5-ferrocenyl-substi-
tuted dihydropyrazoles. Thus signals for CipsoFc for
5a–c and 6a–c are located at higher fields (l=ca.
74–76) than the signals of analogous carbon atoms of
5-ferrocenyl derivatives 5e–g and 6e–g (l=ca. 87–89).
The 13C-NMR spectra of 3,5-diferrocenyldihydropyra-
zoles (5d, 6d) contain two types of signals for CipsoFc,
viz. l=75.65, 88.61 and 74.24, 87.45, respectively.
We found that 1-carbamoyl- and 1-thiocarbamoyl-
(ferrocenyl)dihydropyrazoles behave as ligands and
form 2:1 complexes with transition metals (CuII, NiII,
and CoII). Analysis of the structures of these complexes
is now in progress.
Compounds 7a–9a were attributed to trans-isomers
and 7b–9b, to cis-isomers based on the known criteria.
Identification of 1-acetyl-substituted bicyclic ferro-
1
cenyldihydropyrazoles by H-NMR and X-ray diffrac-
tion methods has been described earlier [13,14]. It was
shown that the chemical shift values and spin–spin
coupling constants for the protons H(5) of the ferro-
cenyldihydropyrazole fragments are diagnostic regard-
ing their trans- or cis-orientation with respect to H(4):
the chemical shifts for H(5) of trans-isomers are found
in lower fields, and the coupling constants are larger,
3. Experimental
1
The H- and 13C-NMR spectra were recorded on a
1
Unity Inova Varian spectrometer (300 and 75 MHz) for
solutions in CDCl3 with Me4Si as the internal standard.
than those for the cis-isomers. According to H-NMR
spectral data for compounds 7a–9a, the H(5) protons

140
T. Klimo6a et al. / Journal of Organometallic Chemistry 633 (2001) 137–142
Column chromatography was carried out on alumina
(Brockmann activity III) using hexane–CHCl3 (1:1,
v/v) or hexane–benzene (2:1, v/v) as the eluent.
The chalcones 1a–d were synthesized from acetylfer-
rocene and the corresponding carbaldehydes, com-
pounds 1e–g, 2–4 were prepared from ferrocenecarb-
Table 1
1H-NMR spectral data of compounds 5a–g, 6a–g, 7a,b, 8a,b and 9a,b (l, J (Hz)
Compound C5H5 (s)
C5H4 (m)
ABX (dd), AX (d)
CH2 (m), CH3 (s), NH2
(bs)
Ar
5a
5b
5c
5d
5e
5f
4.09
4.37 (2H), 4.49 (1H), 4.63 2.97 (HA), 3.67 (HB), 5.48 5.40 (2H)
(1H) (HX), (JAB=17.4,
AX=4.5, JBX=11.7)
4.38 (2H), 4.50 (1H), 4.63 2.93 (HA), 3.67 (HB), 5.41 3.77 (3H), 5.28 (2H)
(1H) (HX), (JAB=16.9,
AX=11.6, JBX=10.5)
4.42 (2H), 4.61 (1H), 4.72 2.99 (HA), 3.80 (HB), 6.01 6.98 (2H)
(1H) (HX), (JAB=16.9,
AX=9.0, JBX=10.5)
4.07 (1H), 4.11 (2H), 4.41 3.34 (HA), 3.62 (HB), 5.29 5.23 (2H)
(3H), 4.70 (2H) (HX), (JAB=17.2,
AX=4.0, JBX=11.3)
4.09 (1H), 4.30 (2H), 4.48 3.57 (HA), 3.72 (HB), 5.30 5.25 (2H)
(1H) (HX), (JAB=17.5,
AX=4.0, JBX=11.0)
4.10 (1H), 4.35 (1H), 4.46 3.50 (HA), 3.67 (HB), 5.36 3.87 (3H), 5.30 (2H)
(1H), 4.54 (1H) (HX), (JAB=17.2,
AX=4.0, JBX=10.8)
4.12 (1H), 4.24 (1H), 4.35 3.63 (HA), 3.82 (HB), 5.85 6.81 (2H)
(1H), 4.4.38 (1H) (HX), (JAB=17.0,
AX=3.0, JBX=10.1)
4.46 (2H), 4.53 (1H), 4.67 3.01 (HA), 3.73 (HB), 6.00 6.98 (2H)
(1H) (HX), (JAB=17.4,
AX=3.0, JBX=11.1)
4.45 (2H), 4.54 (1H), 4.67 3.0 (HA), 3.71 (HB), 5.96
(1H) (HX), (JAB=17.3,
AX=3.1, JBX=11.0)
4.48 (2H), 4.58 (1H), 4.69 3.0 (HA), 3.78 (HB), 5.93
7.25–7.60 (m, 5H)
J
4.12
6.87 (d, 2H), 7.19 (d,
2H) (J=7.2)
J
4.20
7.15 (d, 2H), 7.52 (d,
2H) (J=9.1)
J
4.17, 4.22
4.20
–
J
7.48 (m, 3H), 7.78
(m,2H)
J
4.14
6.96 (d, 2H), 7.71 (d,
2H) (J=8.7)
J
5g
6a
6b
6c
6d
6e
6f
4.19
7.66 (d, 2H), 7.77 (d,
2H) (J=8.7)
J
4.07
7.20–7.30 (m, 3H),
7.35–7.43 (m, 2H)
J
4.10
3.77 (3H), 6.99 (2H)
6.84 (2H)
6.88 (d, 2H), 7.16 (d,
2H) (J=8.8)
J
4.20
7.12 (d, 2H), 7.50 (d,
2H) (J=8.5)
(1H)
(HX), (JAB=17.1,
AX=3.0, JBX=11.1)
J
4.17, 4.24
4.18
4.07 (1H), 4.13 (1H),
3.46 (HA), 3.67 (HB), 5.88 6.77 (2H)
–
4.19(1H), 4.49 (2H), 4.65
(1H), 4.71 (1H), 4.71 (1H)
(HX), (JAB=17.1,
J
AX=3.0, JBX=10.5)
4.05 (1H), 4.12 (1H), 4.20 3.68 (HA), 3.80 (HB), 5.95 6.85 (2H)
(1H), 4.79 (1H) (HX), (JAB=17.3,
AX=4.2, JBX=9.04)
4.05 (1H), 4.11 (1H), 4.20 3.65 (HA), 3.74 (HB), 5.93 3.89 (3H), 6.80 (2H)
7.47 (m, 3H), 7.85
(m,2H)
J
4.14
7.01 (d, 2H), 7.70 (d,
(1H), 4.77 (1H)
(HX), (JAB=16.8,
AX=3.3, JBX=10.2)
2H) (J=9.0)
J
6g
7a
7b
4.19
4.0 (1H), 4.03 (1H), 4.06
(1H), 4.74 (1H)
3.62 (HA), 3.81 (HB), 5.91 6.80 (2H)
(HX), (JAB=17.2,
7.64 (d, 2H), 7.73 (d,
2H) (J=9.0)
J
AX=3.3, JBX=10.2)
4.23, 4.30
4.15, 4.17
3.92 (1H), 4.01 (1H), 4.15 3.25 (HA), 5.31 (HX),
(2H), 4.18 (2H), 4.41 (1H), (JAX=10.3)
4.52 (1H)
4.29 (5H), 4.32 (1H), 4.39 3.42 (HA), 4.77 (HX),
(1H), 4.42 (1H)
1.65 (2H), 2.05 (1H), 2.38
(2H), 3.08 (1H), 5.54 (2H),
7.05 (d, 1H, J=1.5)
–
–
1.70 (2H), 1.98 (1H), 2.20
(2H), 3.0 (1H), 5.29 (2H),
6.78 (d, 1H, J=2.0)
(JAX=6.8)
8a
8b
9a
9b
4.25
4.17
4.23
4.14
3.80 (1H), 3.98 (1H),
4.12(2H)
4.07 (1H), 4.16 (1H),
4.36(2H)
3.02 (HA), 5.30 (HX),
(JAX=10.4)
3.24 (HA), 4.70 (HX),
(JAX=4.0)
3.52 (HA), 5.41 (HX),
(JAX=10.0)
1.54–2.67 (8H), 5.51 (2H)
–
–
–
–
1.48–2.07 (8H), 5.14 (2H)
4.21 (2H), 4.42 (2H)
2.2.0 (2H), 2.26 (2H),
2.52.52(2H), 5.30 (2H)
1.89 (2H), 2.20 (2H), 2.48
(2H), 5.18 (2H)
3.91 (1H), 4.09 (1H), 4.16 3.68 (HA), 4.87 (HX),
(2H) (JAX=7.0)

T. Klimo6a et al. / Journal of Organometallic Chemistry 633 (2001) 137–142
141
Table 2
13C-NMR spectral data of compounds 5a–g, 6a,b,d–f and 7b (l)
Compound C5H5
C5H4
CipsoFc
CH2
CH
CH3, Ar
CꢀN, CꢀS,
CꢀO
C
5a
5b
5c
5d
69.3
66.9, 67.6,
70.1, 70.3
66.9, 67.5,
70.1, 70.3
67.0, 67.8,
70.8, 70.9
65.1, 66.6,
67.0, 67.1,
67.2, 69.4,
69.5, 69.5
66.4, 68.8,
68.9, 70.4
68.3, 68.3,
69.2, 70.0
65.6, 67.8,
68.0, 70.7
67.3, 68.1,
70.9, 71.0
67.4, 68.1,
71.0, 71.1
65.6, 67.5,
68.1, 68.1,
68.2, 70.8,
71.0, 71.4
65.9, 68.2
(2C), 71.2
66.1, 68.2
(2C), 71.1
66.9, 67.9,
68.0, 68.3,
68.9, 69.4,
69.4, 70.6
75.3
44.4
44.4
44.6
40.1
59.2
58.8
63.3
54.1
125.1, 127.5,
128.8
55.2, 114.2,
126.4
153.6, 155.2
153.7, 158.8
155.4, 157.9
152.4, 154.7
142.6
69.3
75.4
134.9, 155.7
123.2, 142.0
–
69.3
74.5
127.8, 130.8
68.1, 68.8
75.6, 88.6
–
5e
5f
69.3
89.1
40.6
40.2
40.3
44.4
44.4
41.8
55.9
55.4
58.1
62.9
55.3
58.5
126.7, 129.1,
130.5
55.3, 114.2,
127.9
153.2, 156.5
151.4, 161.1
154.6, 156.7
159.0, 175.4
159.1, 175.3
159.3, 175.0
131.7
69.3
88.4
124.2, 155.4
124.3, 128.8
141.7
5g
6a
6b
6d
68.3
87.5
127.1, 132.0
69.5
74.0
125.1, 127.6,
128.9
62.4, 114.2,
126.4
69.6
74.1
133.9, 158.9
–
68.7, 69.7
74.2, 87.4
–
6e
6f
68.6
87.1
40.7
40.8
59.1
59.1
126.9, 128.9,
131.0
55.5, 114.4,
128.6
156.6, 175.8
162.0, 175.9
157.3, 158.0
130.7
68.6
87.4
123.3, 156.6
127.2
7b
68.3, 69.2
80.4, 90.0
24.6, 29.2, 31.4 55.5, 61.7,
125.8
–
aldehyde, and the corresponding ketones in aqueous-
ethanolic alkali [3,11].
m.p. (dec.): 177–178 °C (literature data [9]: m.p.
(dec.): 176.5–177.5 °C).
2. Dihydropyrazoles 5a–g, 6a–g, trans-7a–9a.
3. cis-Dihydropyrazoles 7b–9b.
3.1. Synthesis of 1-carbamoyl- and
1-thiocarbamoyl( ferrocenyl)-4,5-dihydropyrazoles
(general procedure)
3.2. 2-Carbamoyl-3-ferrocenyl-7-ferrocenylmethylidene-
2,3,3a,4,5,6,7-heptahydroindazole (7a,b)
A mixture of a ferrocenylchalcone (1–4) (3.3 mmol),
semicarbazide hydrochloride or thiosemicarbazide (6
mmol), and BuOK (7 and 4 mmol, respectively) in dry
A mixture of 1.6 g (3.3 mmol) of 2,6-bis-(ferrocenyl-
t
methylidene)cyclohexanone (2), 0.7 g (6 mmol) of semi-
t
isopropyl alcohol (150 ml) was stirred and boiled under
reflux until the bright coloration because of the chal-
cone disappeared (ca. 3–5 h). The reaction mixture was
cooled and partitioned between benzene and water (150
ml each). The organic layer was separated, washed
several times with water, and the solvent was evapo-
rated in vacuo. The residue was chromatographed on a
column with alumina. The following compounds were
isolated:
carbazide hydrochloride and 0.8 g (7 mmol) of BuOK
in 150 ml of dry isopropyl alcohol was stirred and
boiled under reflux for 3 h. The reaction mixture was
cooled and partitioned between benzene and water (150
ml each). The organic layer was separated and washed
with water. The solvent was removed by heating in
vacuum and the remaining oil was separated by chro-
matography on a column with alumina (hexane–
CHCl3, 1:1). The trans-isomer 7a was obtained as
orange crystals (yield: 0.72 g (40.5%); m.p. (dec.): 264–
265 °C) and the cis-isomer 7b was obtained as an
1. Thiosemicarbazones 10, m.p. (dec.): 188–189 °C
(literature data [10]: m.p. (dec.): 190 °C) and 11,

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T. Klimo6a et al. / Journal of Organometallic Chemistry 633 (2001) 137–142
Table 3
Yields, melting point and elemental analysis data for the synthesized compounds
Compound Yield (%)
M.p. (dec.) (°C)
Molecular formula
Found (%)
Calculated (%)
C
H
Br
Fe
N
C
H
Br
Fe
N
5a
5b
5c
5d
5e
5f
5g
6a
6b
6c
6d
6e
6f
6g
7a
7b
8a
8b
9a
9b
65
67
64
56
71
68
69
59
57
59
62
65
58
57.5
40.5
32
30
28
29
30
207–208
231–232
217–218
258–259
219–220
244–245
223–224
204–205
224–225
255–256
258–259
221–222
248–249
231–232
264–265
259–260
256–258
223–224
215–216
199–201
C
20H19FeN3O
64.4 5.3
62.7 5.1
53.3 3.9 17.4 12.5 9.1
60.1 4.7
64.2 5.0
62.3 5.4
52.9 4.2 17.9 12.3 9.4
61.6 5.1
60.3 4.9
–
–
14.7 11.1 64.4 5.1
14.1 10.3 62.5 5.2
–
–
15.0 11.3
13.9 10.4
C21H21FeN3O2
C20H18BrFeN3O
C
C20H19FeN3O
C21H21FeN3O2
53.1 4.0 17.7 12.3 9.3
24H23Fe2N3O
–
–
–
23.4 8.9
59.9 4.8
–
–
–
23.2 8.7
15.0 11.3
13.9 10.4
15.1 11.7 64.4 5.1
13.7 10.6 62.6 5.2
53.1 4.0 17.7 12.3 9.3
14.2 10.9 61.7 4.9
13.5 10.1 60.2 5.1
C
20H18BrFeN3O
C20H19FeN3S
21H21FeN3OS
–
–
–
–
14.4 10.8
13.3 10.0
C
C20H18BrFeN3S
C24H23Fe2N3S
C
C21H21FeN3OS
C20H18BrFeN3S
C29H29Fe2N3O
51.5 4.0 16.9 12.0 9.0
51.3 3.9 17.1 12.0 9.0
57.8 4.9
61.6 4.8
60.3 4.8
–
–
–
22.3 8.3
14.4 11.0 61.7 4.9
13.5 9.8 60.2 5.1
58.0 4.6
–
–
–
22.5 8.4
14.4 10.8
13.3 10.0
20H19FeN3S
51.5 3.7 16.9 12.0 8.8
51.3 3.9 17.1 12.0 9.0
63.8 5.2
63.5 5.5
61.7 5.9
61.4 6.2
60.3 5.9
60.7 5.4
–
–
–
–
–
–
20.3 7.7
20.6 7.4
63.7 5.3
63.7 5.3
–
–
–
–
–
–
20.4 7.7
20.4 7.7
15.9 12.0
15.9 12.0
16.6 12.5
16.6 12.5
C
29H29Fe2N3O
C18H21FeN3O
C18H21FeN3O
C17H19FeN3O
C17H19FeN3O
16.2 12.1 61.6 6.0
15.7 12.1 61.6 6.0
16.7 12.6 60.5 5.7
16.4 12.4 60.5 5.7
orange powder (yield: 0.57 g (32%); m.p. (dec.):
References
259–260 °C).
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3.3. 3,5-Diferrocenyl-1-thiocarbamoyl-4,5-
dihydropyrazole (6d)
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Similarly, a mixture of 1.4 g (3.3 mmol) of 1,3-difer-
.
rocenyl-2-propenone (1d), 0.55
g (3.3 mmol) of
thiosemicarbazide and 0.45 g (4 mmol) of tBuOK in 150
ml of dry isopropyl alcohol was stirred and boiled for 4
h. After the corresponding workup and chromatogra-
phy (a 2:1 hexane–CHCl3 mixture as the eluent)
thiosemicarbazone of acetylferrocene 10 (yield: 0.07 g
(7%)), thiosemicarbazone of ferrocenylcarbaldehyde 11
(yield: 0.075 g (8%)) and dihydropyrazole 6d (yield: 1.02
g (62%); m.p. (dec.): 258–259 °C) were obtained.
Compounds 5a–g, 6a–c, e–g, 8a,b and 9a,b were
synthesized analogously. The yields of compounds 5–9,
their melting points and elemental analysis data are
listed in Table 3.
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Acknowledgements
Financial support from DGAPA-UNAM (Mexico,
grant IN203599) is gratefully acknowledged. We would
like to thank L. Velasco, J. Pe´rez, R. Patin˜o, H. Rios
and A. Pen˜a for their technical assistance.