Synthesis of new 7-ferrocenyl-β-enaminone-coumarins and ferrocenyl-pyrano[3,2-g]quinolin-2-ones from coumarin and ferrocenyl-α- ketoalkynes using Ni(CN)2/NaOH/H2O/CO/KCN aqueous catalytic system

Article abstract of DOI:10.1016/j.jorganchem.2011.11.010

New ferrocenyl-β-enaminone-coumarins (1a-5a) and ferrocenyl-pyrano[3, 2-g]quinolin-2-ones (1b-5b) were obtained through a heterocyclization reaction from 7-amino-4-methyl-2H-chromen-2-one and several ferrocenyl-α- ketoalkynes in a nickel homogeneous aqueo

Full text of DOI:10.1016/j.jorganchem.2011.11.010

Journal of Organometallic Chemistry 700 (2012) 29e35
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of new 7-ferrocenyl-b-enaminone-coumarins and ferrocenyl-pyrano
[3,2-g]quinolin-2-ones from coumarin and ferrocenyl-a-ketoalkynes using
Ni(CN)2/NaOH/H2O/CO/KCN aqueous catalytic system
*
Ivonne Arellano, Pankaj Sharma , Laura Rubio-Perez, Armando Cabrera, Noé Rosas, A. Toscano
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Coyoacan, 04510 México D.F, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
New ferrocenyl-
were obtained through a heterocyclization reaction from 7-amino-4-methyl-2H-chromen-2-one and
several ferrocenyl- -ketoalkynes in a nickel homogeneous aqueous catalytic system formed by Ni(CN)2/
CO/NaOH/KCN. In the absence of this catalytic system neither ferrocenyl substituted chromenone nor
ferrocenyl-heterocycle was obtained. A possible mechanism is suggested for the synthesis of - -enam-
b-enaminone-coumarins (1ae5a) and ferrocenyl-pyrano[3,2-g]quinolin-2-ones (1be5b)
Received 7 October 2011
Received in revised form
11 November 2011
a
Accepted 14 November 2011
b
inone-coumarins and pyrano[3,2-g]quinolinones. Molecular structure of 7-(1-ferrocenyl-3-(4-
bromophenyl)-3-oxoprop-1-enylamino)-4-methyl-2H-chromen-2-one (5a) has been determined.
Ó 2011 Elsevier B.V. All rights reserved.
Keywords:
Ferrocenyl-b-enaminone-coumarins
2H-Chromen-2-one
Pyrano[3,2-g]quinolinones
Aqueous catalytic system
Nickel
1. Introduction
enaminones are versatile reagents and have wide utility in
heterocyclic synthesis. Though a variety of enaminones are re-
Quinolinones are important compounds that are used as drugs
[1e6] more specifically, pyrano-quinolinones show interesting
biological activity such as immunosuppressors [7], antiallergics
[8,9], antibacterials [10], androgen receptor agonists for the treat-
ment of prostate cancer [11], and also form a part of several natural
alkaloids [10,12e14].
Different methods are reported for the synthesis of quinoli-
nones. DielseAlder reactions of aryl amines with different dien-
ophiles in the presence of an acid catalyst [10,14e17];
cyclocondensation of aromatic amines with malonates [18,19],
intramolecular cyclizations of substituted quinolones and couma-
rins [20,21], are some of the reported routes to synthesize quino-
linones. These kind of reactions are carried out in organic solvent,
solvent free or in water but carried out generally in more than two
reaction steps.
ported, enaminone-coumarins are lesser known and ferrocenyl
substituted enaminone-coumarins are unknown in literature.
On the other hand ferrocenyl group has been widely used in the
design or redesign of drugs that can result favorable changes in
their lipophilic and redox properties and biological activities
[24e27]. Considering a synergistic effect between pyrano quinoli-
nones and ferrocene on lipophilic and redox properties and bio-
logical activities, and our interest in nickel catalyzed
heterocyclization reaction to synthesize different heterocycles, this
work was undertaken.
In this work a facile way to obtain new ferrocenyl-
coumarins and ferrocenyl-pyrano[3,2-g]quinolin-2-ones from
coupling and heterocyclization of several ferrocenyl- -ketoalkynes
b-enaminone-
a
and 7-amino-4-methyl-coumarin in water as a reaction medium
under room temperature and atmospheric pressure using the
nickel catalytic system, is reported.
Previously our group has reported one pot catalytic synthesis of
alkyl/phenyl substituted 2H-pyrano[3,2-g]quinolin-2-ones [22]
(Fig. 1) from
a-ketoalkynes and 7-amino-4-methyl-coumarin,
using [Ni(CN)4]ꢀ4 as a catalytic specie, formed in situ in the
2. Results and discussion
Ni(CN)2/NaOH/H2O/CO/KCN aqueous system [23]. Similarly
The new ferrocenyl-b-enaminone-coumarins (1ae5a) and fer-
rocenyl-pyrano[3,2-g]quinolin-2-ones (1be5b) were obtained in
mild reaction conditions at room temperature and atmospheric
pressure as shown in the Scheme 1 and Table 1. a-Ketoalkynes were
* Corresponding author. Fax: þ52 555 6162217.
E-mail address: pankajsh@servidor.unam.mx (P. Sharma).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.11.010

30
I. Arellano et al. / Journal of Organometallic Chemistry 700 (2012) 29e35
Ph
lengths and angles are given in Tables 2 and 3, respectively. In the
molecular structure of compound 5a the unsubstituted cyclo-
pentadienyl ring is disordered. The compound is monomeric. In the
solid state this compound presents
a weak intramolecular
NeH/O]C hydrogen bonding, similar to the ferrocenyl-b-enam-
ino ketones reported earlier by our group [29].
The species [Ni(CN)4]ꢀ4 (I) is obtained when an excess of KCN is
added to an alkaline solution of Ni(CN)2 in CO atmosphere. It is
known that the presence of carbon monoxide in the media attains
an equilibria which involves different carbonylic species in the
solution [23]. In addition, the presence of carbon monoxide in the
system results in a reductive atmosphere, which promotes low
oxidation states of nickel in the reaction [23,28].
O
O
N
Fig. 1. 8-Ethyl-4-methyl-6-phenyl-2H-pyrano[3,2-g]quinolin-2-one.
obtained from ethynylferrocene and acyl chlorides via a palladium
catalyzed coupling as reported earlier by our group [28].
In the IR spectra, C]O and CeN vibrations were observed for all
the compounds synthesized. In the IR spectra of compounds
(1ae5a) a weak band at w3370 cmꢀ1 can be attributed to the
stretching vibration of the hydrogen bonded enamine NeH group.
This band appears at a higher frequency than the NeH frequency
[NiI(CN)(CO)3]-4
-OH/ CN-/CO [NiII(CN)2(CO)2]
NiII(CN)2
CO
CO
-CN
[Ni0(CN)4]-4
[Ni0(CN)(CO)3]-1
observed for similar ferrocenyl-b-enamino ketones [29] which may
I
be due to the absence of NeH/O intramolecular interaction. IR
spectrum of compound (1a) in CHCl3 shows C]O vibration at
1575 cmꢀ1, suggesting the presence of
a
,b
-unsaturated carbonyl
system. In the mass spectra IEþ, the molecular ion peaks were
observed for both ferrocenyl- -enaminone-coumarins (1ae5a) and
In absence of the catalyst [Ni(CN)4]ꢀ4, which was formed in situ
using Ni(CN)2/KCN/NaOH/H2O/EtOH catalytic system, no reaction
was observed and the product was not obtained after 20 days of
reaction. But when the reaction was carried in presence of the
b
ferrocenyl-pyrano[3,2-g]quinolin-2-ones (1be5b) compounds
along with fragments corresponding to the loss of cyclopentadienyl
(Mþ ꢀ 65) group, in each compound. Fragmentation pattern in all
these compounds are similar. For compounds 2b, 3b, 5b and 5a
high resolution mass spectra (HRMS) were also obtained, and
molecular ion peaks at 486.1149 (Calc. m/z 486.1156), 532.1213
(Calc. m/z 532.1211), 550.0109 (Calc. m/z 550.0105) and 568.0204
(Calc. m/z 568.0211) respectively, were observed, confirming the
molecular formulas for these compounds.
active catalytic species [Ni(CN)4]ꢀ4 (I), corresponding
b-enami-
none-coumarin were obtained after 24 h of the reaction, and after 6
days the corresponding quinolinones were obtained. This indicates
the utility of the active catalytic specie to activate the
and facilitates the nucleophilic attack by coumarin nucleophile to
the
-ketoalkyne. The attack of [Ni(CN)4]ꢀ4 occurs at the carbonyl
a-ketoalkyne
a
group of the ketoalkyne instead of to carbon triple bond due to
stereo-electronic effect of the ferrocenyl group. A similar observa-
tion was noted previously also in the heterocyclization reaction for
the formation of ferrocenyl-pyrido[2,3-d]pyrimidines [28].
In the Scheme 2 a proposed reaction pathway for the synthesis
1H NMR spectra of ferrocenyl-pyrano[3,2-g]quinolin-2-ones
(1ae5a) present similar chemical shifts pattern for ferrocenyl
group between 4.09 and 5.11 ppm. In the NOESY spectra, the
correlation between H-10 and the
pentadienyl ring of ferrocene is observed which confirm that the
H
of substituted cyclo-
of the ferrocenyl-pyrano[3,2-g]quinolin-2-ones and ferrocenyl-
enaminone-coumarins is shown. First, the species [Ni(CN)4]ꢀ4
attacks the carbonyl group of the ferrocenyl- -ketoalkyne, whereas
an imine is generated by the basic medium from the 7-amino-4-
methyl-coumarin. Then, the nucleophilic moiety (V) attacks the
triple bond of the activated ketoalkyne (III) and by an addi-
tioneelimination mechanism, the catalyst is regenerated and fer-
b-
ferrocene group is at the C-8, as is shown in the Fig. 2.
a
1H NMR spectra of all the ferrocenyl-
b
-enaminone-coumarins
compounds present similar chemical shifts pattern for ferrocenyl
group between 4.07 and 4.42 ppm. The molecular structure of
compound 5a was unambiguously established by X-ray crystal-
lography and is shown at the Fig. 3. Crystal data and selected bond
rocenyl-b-enaminone-coumarin (VI) is obtained. In the basic
O
O
NH
O
O
Fc
R
Ni(CN)2/NaOH
Fc
+
40-60 %
CO/H2O/KCN
EtOH
R
R
O
O
NH2
Fc= Ferrocenyl
R= m-MePh, p-MePh, 3,5-OMePh, p-EtPh, p-BrPh
O
O
N
Fc
10 %
Scheme 1. General synthesis of ferrocenyl-b-enaminone-coumarins and ferrocenyl-pyrano[3,2-g]quinolin-2-ones.

I. Arellano et al. / Journal of Organometallic Chemistry 700 (2012) 29e35
31
Table 1
Reaction between ferrocenyl-
a
-ketoalkynes and 7-amino-4-methyl-coumarins.
Entry
R of ferrocenyl-
a
-ketoalkyne
b
-Enaminone-coumarins
Yield
Pyrano[3,2-g]quinolinones
Yield
1a
58%
1b
6%
1
p-Tolyl
O
O
NH
O
Fc
O
O
N
Fc
MeO
OMe
O
O
NH
O
2a
2b
2
3,5-Dimethoxy-phenyl
55%
10%
OMe
Fc
O
O
N
Fc
OMe
3a
40%
3b
12%
3
4
5
m-Tolyl
O
O
NH
O
Fc
O
O
N
Fc
Et
4a
60%
4b
5%
O
O
NH
O
p-Ethylphenyl
Fc
Et
O
O
N
Fc
Br
5a
57%
5b
8%
O
O
NH
O
p-Bromophenyl
Fc
Br
O
O
N
Fc
Reaction conditions: Ni(CN)2/CO/5 N NaOH/KCN, room temperature, atmospheric pressure, yielding ferrocenyl-
quinolinones (6 days). No reaction without (NiCN)2/CO/KCN after 20 days.
b-enaminone-coumarins (24 h) and ferrocenyl-pyrano[3,2-g]
medium, ketoimine (VII) anion is generated which promotes the
heterocyclization and re-aromatization, affording the pyrano[3,2-g]
quinolin-2-one (IX).
presence of a nickel catalytic system affords ferrocenyl-b-enami-
none-coumarins and ferrocenyl-pyrano[3,2-g]quinolin-2-ones. It is
to be noted that the substitution at C-8 depends on the nature of
In summary, it was found that the reaction between 7-amino-4-
the
a-ketoalkyne used. When ketoalkyne with a weak electron
methyl-coumarin and several ferrocenyl-a-ketoalkynes in the
donating group e.g. alkyl or phenyl group, the substitution of this

32
I. Arellano et al. / Journal of Organometallic Chemistry 700 (2012) 29e35
3.1. General procedure
A 5 N NaOH solution (10 mL) was degassed and saturated with
CO under atmospheric pressure for 30 min, 0.2 mmol of
Ni(CN)2$4H2O was added to the solution, the mixture was kept at
room temperature overnight, with stirring and slow bubbling of CO
(2e3 mL/min), until a pale yellow solution was obtained. Addition
of 1.5 mmol of KCN resulted in a color change to orange. The species
(1) is obtained when an excess of KCN is added to an alkaline
solution of Ni(CN)2 in CO atmosphere. It is known that the presence
of carbon monoxide in the media attains an equilibria which
involves different carbonylic species in the solution [23]. In addi-
tion, the presence of carbon monoxide in the system results in
a reductive atmosphere, which promotes low oxidation states of
nickel in the reaction [23,28]. After stirring for 0.5 h the corre-
CH3
4
H
5
H
O
6
3
2
7
8
O
10
H
N
H
Fe
sponding ferrocenyl-a-ketoalkyne (1 mmol), 7-amino-4-methyl-
coumarin (2 mmol) and 2 mL of ethanol were added. The evolution
of the reaction was following by TLC. At the end of the reaction,
ethyl acetate was used to extract the product. After evaporation of
the solvent followed by drying over MgSO4, the crude product was
purified by flash chromatography using ethyl acetate:hexane
(80:20) as eluent.
Fig. 2. NOESY correlations for compound 1b.
group will be occurred at C-6 of the pyrano[3,2-g]quinolinone, as
reported earlier [22], and with ferrocenyl group with higher elec-
tron donating capacity, the substitution will be at the C-8 of the
heterocycle as observed in this report.
3.2. X-ray crystallography
3. Experimental
The X-ray intensity data were measured at 298 K on a Bruker
Smart APEX CCD 01-670 diffractometer. The detector was placed at
a distance of 4.837 cm from the crystal. Analysis of the data
Ferrocenyl-ketoalkynes were prepared according to previous
report [28, 29]. 7-Amino-4-methyl-coumarin was purchased from
Aldrich. 1H and 13C spectra were recorded on a JEOL GX3 00
instrument, 300 MHz for 1H and 75 MHz for 13C using CDCl3 as
solvent. IR spectra were recorded in film on a Nicolet FT 5SX
spectrophotometer. MS spectra were obtained using a JEOL JMS-
AX505HA spectrometer.
showed negligible decays during data collections.
A semi-
empirical method based on equivalents absorption correction
was applied. Crystal structure was refined by full-matrix least
squares method. SMART software (data collection and data
reduction) and SHELXTL were used for solution and refinement of
the structure.
Fig. 3. ORTEP diagram of 7-(1-ferrocenyl-3-(4-bromophenyl)-3-oxoprop-1-enylamino)-4-methyl-2H-chromen-2-one.

I. Arellano et al. / Journal of Organometallic Chemistry 700 (2012) 29e35
33
Table 2
(s, 3H, CH3C4), 2.43 (s, 3H, CH3Ph), 4.17 (s, 5H, C5H5), 4.37 (t, 2H,
J ¼ 1.9 Hz, C5H4), 4.42 (t, 2H, J ¼ 1.9 Hz, C5H4), 6.15 (s, 1H, C3-H), 6.68
(s, 1H, C]CHeCO), 6.69 (d, 1H, J ¼ 2.0 Hz, C8-H), 6.80 (dd, 1H,
J ¼ 2.1 Hz, C6-H), 7.30 (d, 2H, J ¼ 8.3 Hz, 3,5-Ph), 7.38 (d, 1H,
J ¼ 8.5 Hz, C5-H), 7.89 (d, 2H, J ¼ 8.1 Hz, 2,6-Ph).
Crystallographic data for compound (5a).
Parameter
Compound (5a)
Parameter
Compound (5a)
Empirical
formula
Formula
weight
Crystal
color
Crystal
system
Space
C29H22BrFeNO3
Z
4
568.24
DCalc (Mg/m3)
1.561
3.2.4. 7-(1-Ferrocenyl-3-(4-ethylphenyl)-3-oxoprop-1-enylamino)-
4-methyl-2H-chromen-2-one (4a)
Red prism
Monoclinic
P2/c
l
(mmꢀ1
)
2.309
2Ө (ꢁ)
1.76e25.41
19,635
4435
The product was obtained as described in the general procedure
as a red-orange solid (60%); Empirical formula: C31H27NO3Fe; mp.
165 ꢁC; IR (film, selected, cmꢀ1) 1587, 1726, 2923, 3088; Mass
spectrum EI: m/z (%) ¼ 517 (97) Mþ, 452 (100) [M ꢀ cp]þ, 1H NMR
Reflections
collected
Independent
reflections
Rint
group
Crystal
size (mm)
a (Å)
0.408 ꢂ 0.158 ꢂ 0.112
(300 MHz, CDCl3,
d in ppm): 1.30 (t, 3H, CH3CH2Ph), 2.37 (s, 3H,
12.415(2)
13.191(2)
15.82(3)
90
0.0521
0.0401
0.0857
1.025
CH3C4), 2.73 (q, 2H, CH2Ph), 4.19 (s, 5H, C5H5), 4.38 (t, 2H, J ¼ 1.8 Hz,
C5H4), 4.44 (t, 2H, J ¼ 1.8 Hz, C5H4), 6.16(s, 1H, C3-H), 6.71(s, 1H, C8-
H), 6.83 (dd, 1H, J ¼ 2.1 Hz, C6-H), 7.26(s, 1H, C]CHeCO), 7.29 (d,
2H, J ¼ 7.9 Hz, 3,5-Ph), 7.39 (d, 1H, J ¼ 8.5 Hz, C5-H), 7.93 (d, 2H,
J ¼ 8.1 Hz, 2,6-Ph), 13.04 (s, 1H, NH).
b (Å)
R1 [I > 2
wR2
s(I)]
c (Å)
a
(ꢁ)
(ꢁ)
GOF
b
9111.646(3)
Max/min Dr
0.692/ꢀ0.584
(e Åꢀ3
)
g
(ꢁ)
90
2417.5(7)
Volume (Å3)
3.2.5. 7-(1-Ferrocenyl-3-(4-bromophenyl)-3-oxoprop-1-enylamino)-
4-methyl-2H-chromen-2-one (5a)
The product was obtained as described in the general procedure
as a red-orange solid (57%); Empirical formula: C29H22NO3BrFe;
mp. 190 ꢁC, decomposition; IR (Film, selected, cmꢀ1) 1583, 1723,
2923, 3416; Mass spectrum EI: m/z (%) ¼ 567 (100) Mþ, 549 (14)
Table 3
Selected bond angles (ꢁ) and selected bond length (Å) for the compound (5a).
Bond angles (ꢁ)
Bond length (Å)
[M ꢀ 18]þ, 502 (98) [M ꢀ cp]þ; 1H NMR (300 MHz, CDCl3,
d in ppm):
O(3)eC(14)eC(13)
N(1)eC(12)eC(13)
C(12)eC(13)eC(14)
C(13)eC(12)eC(15)
122.4(3)
119.4(3)
125.1(3)
119.9(3)
O(3)eC(14)
C(12)eC(13)
C(13)eC(14)
C(12)eN(1)
C(14)-C(25)
C(12)eC(15)
1.254(4)
1.372(4)
1.418(4)
1.359(4)
1.498(4)
1.468(4)
2.32 (s, 3H, CH3C4), 4.12 (s, 5H, C5H5), 4.33 (t, 2H, J ¼ 1.9 Hz, C5H4),
4.38 (t, 2H, J ¼ 1.9 Hz, C5H4), 6.11 (s, 1H, C3-H), 6.56 (s, 1H, C]
CHeCO), 6.68 (d, 1H, J ¼ 2.0 Hz, C8-H), 6.77 (dd, 1H, J ¼ 2.1 Hz, C6-
H), 7.36 (d, 1H, J ¼ 8.5 Hz, C5-H), 7.57 (d, 2H, J ¼ 8.7 Hz, 3,5-Ph), 7.80
(d, 2H, J ¼ 8.5 Hz, 2,6-Ph), 13.04 (s, 1H, NH).
3.2.6. 8-Ferrocenyl-4-methyl-6-p-tolyl-2H-pyrano[3,2-g]quinolin-2-
one (1b)
3.2.1. 7-(1-Ferrocenyl-3-(p-tolyl)-3-oxoprop-1-enylamino)-4-methyl-
2H-chromen-2-one (1a)
The product was obtained as described in the general procedure
The product was obtained as described in the general procedure
as a red-orange solid (58%); Empirical formula: C30H25NO3Fe; mp.
185 ꢁC; IR (KBr, selected, cmꢀ1) 1588, 1718, 2923, 3327; Mass
spectrum EI: m/z (%) ¼ 503 (83) Mþ, 438 (68) [M ꢀ cp]þ, 273 (100)
as a pink-red solid (6%); Empirical formula: C30H23NO2Fe;
mp. > 430 ꢁC decomposition; IR (KBr, selected, cmꢀ1) 3417, 2924,
2854, 1731, 1622, 1588; Mass spectrum EI: m/z (%) ¼ 485 (100) Mþ,
420 (19) [M ꢀ cp]þ; 1H NMR (300 MHz, CDCl3,
d in ppm) 2.39 (s, 3H,
[M ꢀ Fc-C-CHC(]O)tolyl]þ; 1H NMR (300 MHz, CDCl3,
d
in ppm)
CH3C]C), 2.52 (s,3H, CH3Ph), 4.09 (s, 5H, C5H5), 4.54 (t, 2H, C5H4,
J ¼ 1.9 Hz), 5.11 (t, 2H, C5H4, J ¼ 1.9), 6.32 (s, 1H, C]CHeC]OeO),
7.42 (d, 2H, J ¼ 7.9 Hz, 3,5-Ph), 7.45 (s, 1H, C]CHeC), 7.49 (d, 2H,
J ¼ 8.1 Hz, 2,6-Ph), 7.95 (s, 1H, OC]CHeCN), 8.09 (s, 1H, CH3CeC]
CHeC).
2.35 (s, 3H, CH3C4), 2.43 (s, 3H, CH3Ph), 4.17 (s, 5H, C5H5), 4.36 (t,
2H, J ¼ 1.8 Hz, C5H4), 4.42 (t, 2H, J ¼ 1.8 Hz, C5H4), 6.14 (s, 1H, C3-H),
6.68 (s, 1H, C]CHeCO), 6.69 (s, 1H, C8-H), 6.80 (dd, 1H, J ¼ 2.1 Hz,
C6-H), 7.29 (d, 2H, J ¼ 7.9 Hz, 3,5-Ph), 7.37 (d, 1H, J ¼ 8.5 Hz, C5-H),
7.89 (d, 2H, J ¼ 8.1 Hz, 2,6-Ph), 13.02 (s, 1H, NH).
3.2.7. 8-Ferrocenyl-6-(3,5-dimethoxyphenyl)-4-methyl-2H-pyrano
[3,2-g]quinolin-2-one (2b)
3.2.2. 7-(1-Ferrocenyl-3-(3,5-dimethoxyphenyl)-3-oxoprop-1-
enylamino)-4-methyl-2H-chromen-2-one (2a)
The product was obtained as described in the general procedure
The product was obtained as described in the general procedure
as a red-orange solid (55%); Empirical formula: C31H27NO5Fe; mp.
130 ꢁC; IR (film, selected, cmꢀ1) 1590, 1722, 2924, 3356; Mass
spectrum EI: m/z (%) ¼ 549 (100) Mþ, 484 (94) [M ꢀ cp]þ; 1H NMR
as a pink-red solid (10%); Empirical formula: C31H25NO4Fe;
mp. > 430 ꢁC decomposition; IR (KBr, selected, cmꢀ1) 3346, 2923,
2854, 1724, 1587; Mass spectrum EI: m/z (%) ¼ 532 (18), 531 (<5)
Mþ, 466 (<5) [M ꢀ cp]þ; 1H NMR (300 MHz, CDCl3,
d in ppm) 2.39
(300 MHz, CDCl3,
d
in ppm) 2.35 (s, 3H, CH3C4), 3.88 (s, 6H, OCH3),
(s, 3H, CH3C]C), 3.89 (s, 6H, OMe), 4.09 (s, 5H, C5H5), 4.55 (t, 2H,
C5H4, J ¼ 1.9 Hz), 5.11 (t, 2H, C5H4, J ¼ 1.9 Hz), 6.32 (s, 1H, C]
CHeC]OeO), 6.65 (t, 1H, 4-Ph), 6.69 (d, 2H, J ¼ 2.3 Hz, 2,6-Ph), 7.47
(s, 1H, C]CHeC), 7.94 (s, 1H, OC]CHeCN), 8.12 (s, 1H, CH3CeC]
CHeC).
4.07 (s, 5H, C5H5), 4.37 (t, 2H, J ¼ 1.8 Hz, C5H4), 4.42 (t, 2H, J ¼ 1.8 Hz,
C5H4), 6.16 (s, 1H, C3-H), 6.60 (s, 1H, C]CHeCO), 6.63 (s, 1H, 4-Ph),
6.72 (s, 1H, C8-H), 6.81 (dd, 1H, J ¼ 2.4 Hz, C6-H), 7.13 (d, 2H,
J ¼ 2.1 Hz, 2,6-Ph), 7.39 (d, 1H, J ¼ 8.4 Hz, C5-H), 13.07 (s, 1H, NH).
3.2.3. 7-(1-Ferrocenyl-3-(m-tolyl)-3-oxoprop-1-enylamino)-4-methyl-
2H-chromen-2-one (3a)
3.2.8. 8-Ferrocenyl-4-methyl-6-m-tolyl-2H-pyrano[3,2-g]quinolin-2-
one (3b)
The product was obtained as described in the general procedure
as a red-orange solid (40%); Empirical formula: C30H25NO3Fe; mp.
149 ꢁC, decomposition; IR (Film, selected, cmꢀ1) 1575, 1712, 3003,
3391; Mass spectrum EI: m/z (%) ¼ 503 (91) Mþ, 438 (100)
The product was obtained as described in the general procedure
as
a pink-red solid (12%); Empirical formula: C30H23NO2Fe;
mp. > 430 ꢁC decomposition; IR (KBr, selected, cmꢀ1) 3417, 2924,
2854, 1731, 1622, 1588; Mass spectrum EI: m/z (%) ¼ 485 (100) Mþ,
[M ꢀ cp]þ, 28 (44) [CO]þ; 1H NMR (300 MHz, CDCl3,
d
in ppm): 2.36
420 (19) [M-cp]þ; 1H NMR (300 MHz, CDCl3,
d in ppm) 2.37 (s, 3H,

34
I. Arellano et al. / Journal of Organometallic Chemistry 700 (2012) 29e35
-3
Ni0(CN)3
CN-
O
R
[Ni0(CN)4]-4
Fc
+
Fc
R
( II )
( I )
OH
( III )
H2O
OH-
-HN
O
H2N
O
O
O
( IV )
( V )
-3
Ni0(CN)3
O
NH
O
Fc
R
OH
( VI
CN-
[Ni0(CN)4]-4
I
O
O
NH
O
( VII )
Fc
R
OH-
H2O
R
N
O
N
R
OH
R
H2O
O
O
Fc
O
O
Fc
O
O
N
Fc
( VIII )
( IX )
( X )
-enaminone-coumarins.
Scheme 2. Possible reaction pathway for ferrocenyl-heterocycles and ferrocenyl-
b
CH3C]C), 2.51 (s,3H, CH3Ph), 4.10 (s, 5H, C5H5), 4.54 (t, 2H, C5H4,
J ¼ 1.9 Hz), 5.12 (t, 2H, C5H4, J ¼ 1.9), 6.32 (s, 1H, C]CHeC]OeO),
7.39 (s br, 2H, Ph), 7.46 (s, 1H, C]CHeC), 7.91 (s br, 2H, Ph), 7.95 (s,
1H, OeC]CHeCN), 8.06 (s, 1H, CH3CeC]CHeC).
3.2.10. 8-Ferrocenyl-6-(4-bromophenyl)-4-methyl-2H-pyrano[3,2-
g]quinolin-2-one (5b)
The product was obtained as described in the general procedure
as
a pink-red solid (8%); Empirical formula: C29H20NO2Fe;
mp. > 430 ꢁC decomposition; IR (KBr, selected, cmꢀ1) 3417, 2923,
2854, 1729, 1624, 1588; Mass spectrum EI: m/z (%) ¼ 551 (62)
[Mþ2]þ, 549 (63) Mþ, 484 (12) [M ꢀ cp]þ; 1H NMR (300 MHz,
3.2.9. 8-Ferrocenyl-6-(4-ethylphenyl)-4-methyl-2H-pyrano[3,2-g]
quinolin-2-one (4b)
The product was obtained as described in the general procedure
CDCl3, d in ppm) 2.38 (s, 3H, CH3C]C), 4.09 (s, 5H, C5H5), 4.55 (t, 2H,
as
a
pink-red solid (5%); Empirical formula: C35H25NO2Fe;
C5H4, J ¼ 1.9 Hz), 5.11 (t, 2H, C5H4, J ¼ 1.9 Hz), 6.33 (s, 1H, C]
CHeC]OeO), 7.41 (s,1H, C]CHeC), 7.46 (d, 2H, J ¼ 8.2 Hz, Ph), 7.75
(d, 2H, J ¼ 8.4 Hz, Ph), 7.95 (s,1H, OC]CHeCN), 7.97 (s, 1H,
CH3CeC]CHeC).
mp. > 430 ꢁC decomposition; IR (KBr, selected, cmꢀ1) 3417, 2923,
2854,1729,1624,1588; Mass spectrum EI: m/z (%) ¼ 499 (100) [M]þ,
434(15) [M ꢀ cp]þ; 1H NMR (300 MHz, CDCl3,
d in ppm) 1.37 (t, 3H,
J ¼ 7.6 Hz, CH3CH2), 2.82 (c, 2H, J ¼ 7.6 Hz, CH3CH2), 4.09 (s, 5H,
C5H5), 4.54 (t, 2H, J ¼ 1.9 Hz, C5H4), 5.11 (t, 2H, J ¼ 1.9 Hz, C5H4), 6.31
(s, 1H, C]CHeC]OeO), 7.43 (s, 1H, C]CHeC), 7.46 (d, 2H,
J ¼ 2.2 Hz, 3,5-Ph), 7.50 (d, 2H, J ¼ 8.3 Hz, 2,6-Ph), 7.95 (s,1H, OC]
CHeCN), 8.10 (s, 1H, CH3CeC]CHeC).
Acknowledgment
We thank to Dirección General de Asuntos del Personal Aca-
démico, DGAPA, Universidad Nacional Autónoma de México UNAM,

I. Arellano et al. / Journal of Organometallic Chemistry 700 (2012) 29e35
35
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(1999) 1003.
for financial support and CONACyT for scholarship CONACyT No.
200409.
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Appendix A. Supplementary material
CCDC No. 846488 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.
uk/data_request/cif.
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