An efficient synthesis of ferrocenyl substituted 1,5-diketone and cyclic α,β-unsaturated ketones under ultrasound irradiation

Article abstract of DOI:10.1016/j.jorganchem.2004.03.006

Michael reactions of deoxybenzoin or dibenzyl ketone with ferrocenyl substituted chalcones catalyzed by sodium hydroxide under ultrasound irradiation can afford the corresponding Michael adducts with excellent yields. It presents a convenient, efficient and simple method for the preparation of ferrocenyl substituted 1,5-diketone compounds in the presence of ultrasound irradiation. In addition, the formation of cyclic, α,β-unsaturated ketones via the reactions of dibenzyl ketone with ferrocenyl substituted chalcones were found, and characterized by X-ray crystal structure analysis.

Full text of DOI:10.1016/j.jorganchem.2004.03.006

Journal of Organometallic Chemistry 689 (2004) 1843–1848
www.elsevier.com/locate/jorganchem
An efficient synthesis of ferrocenyl substituted 1,5-diketone and
cyclic a; b-unsaturated ketones under ultrasound irradiation
*
Shun-Jun Ji , Zhi-Liang Shen, Da-Gong Gu, Shun-Yi Wang
College of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006, China
The Key Laboratory of Organic Synthesis of Jiangsu Province, Suzhou University, Suzhou 215006, China
Received 13 January 2004; accepted 2 March 2004
Abstract
Michael reactions of deoxybenzoin or dibenzyl ketone with ferrocenyl substituted chalcones catalyzed by sodium hydroxide
under ultrasound irradiation can afford the corresponding Michael adducts with excellent yields. It presents a convenient, efficient
and simple method for the preparation of ferrocenyl substituted 1,5-diketone compounds in the presence of ultrasound irradiation.
In addition, the formation of cyclic, a; b-unsaturated ketones via the reactions of dibenzyl ketone with ferrocenyl substituted
chalcones were found, and characterized by X-ray crystal structure analysis.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Ferrocene; Chalcone; 1,5-Diketone; Michael reaction; Ultrasound; Crystal structure
1. Introduction
available directly; longer reaction time and complicated
manipulation et al.
1,5-Diketone compounds are very important inter-
mediates in organic syntheses due to their applications
as fundamental starting materials in the preparation of
many heterocyclic [1–3] and polyfunctional compounds
[4–7]. These compounds, such as a; b-oligopyridines [4],
terpyridylferrocene and bis(terpyridinylferrocene) [5]
have potential applications in coordination chemistry,
molecular sensing, catalytic reactions, the chemical
modification of electrodes, and redox active self-assem-
bly devices. In past reports, one of the methods to pre-
pare 1,5-diketone compounds is via the Michael
reactions of deoxybenzoin or dibenzyl ketone with
chalcones using conventional heating method and em-
ploying strong organic bases such as ethoxide [8] or
methoxide [9] as catalyst. However, these methods more
or less have the following limitations: the use of strong
organic base which is moisture-sensitive and is not
Recently, ultrasound has been utilized in organic
synthesis as a new reaction media. Compared with tra-
ditional heating methods, this approach is more conve-
nient, efficient and can be controlled easily. It has been
reported that a large number of organic reactions could
be facilitated by ultrasound irradiation with higher
yields, shorter reaction time and milder conditions [10–
21].
The bright prospects of the applications of ultra-
sound in organic synthesis spurred us to investigate or-
ganic reactions which are operated under ultrasound
irradiation. In past reports, Ma and co-workers [22] had
described the syntheses of 1,5-diketone derivatives such
as 1 by Michael reaction of acetophenone with ferro-
cenylenones. However, to our knowledge, there is no
report about the reaction of deoxybenzoin and dibenzyl
ketone with ferrocenyl substituted chalcones (1). Herein,
we wish to report the syntheses of a new series of ferr-
ocenyl substituted 1,5-diketones using deoxybenzoin
and dibenzyl ketone as Michael donors promoted by
inorganic base under ultrasound irradiation, and afford
the corresponding Michael adducts with excellent yields.
At the same time, some cyclic a; b-unsaturated ketones
* Corresponding author. Tel.: +86-512-65112853/65112372; fax:
+86-512-65224783/65112371.
E-mail address: shunjun@suda.edu.cn (S.-J. Ji).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.03.006

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S.-J. Ji et al. / Journal of Organometallic Chemistry 689 (2004) 1843–1848
Table 1
The Michael reactions of deoxybenzoin with ferrocenyl substituted
chalcones catalyzed by sodium hydroxide at 60 °C under ultrasound
irradiation
Entry Reactant
Ar
Time Product Yielda
(h)
(%)
1
2
1a
1b
1c
1d
1e
1f
4-NO2–C6H4
4-Cl–C6H4
2-Cl–C6H4
C6H5
1
1
2
2
2
2
2
2
2
1
1
2a
2b
2c
2d
2e
2f
89
93
3
86
92
4
5
4-CH3–C6H4
4-OCH3–C6H4
3,4-O2CH2–C6H3
2-C5H4N
85
6
93b
82b
85
7
1g
1h
1i
2g
2h
2i
8
9
2-C4H3S
3-C4H3S
2-C4H3O
81
10
11
1j
1k
2j
2k
96b
85b
a Isolated yields.
b The amount of solvent-ethanol used is 5 ml (others are 30 ml).
Fig. 1. X-ray crystal structure of 3a.
accelerating the reaction rate and improving the yields.
In addition, we found that reaction rate could also be
accelerated if the amount of solvent (ethanol) has been
decreased from 30 to 5 ml, which might be due to the
concentration of substrates and catalyst enhanced.
Compared with literature reported methods which
are operated under traditional homogeneous conditions
catalyzed by ethoxide, current methods have a series of
advantages, such as mild conditions, short reaction time,
excellent yields, low cost and manipulative simplicity.
Furthermore, we discovered that the Michael reac-
tions could also be promoted effectively by potassium
hydroxide and lithium hydroxide since the reaction of
chalcone 1i with deoxybenzoin could afford Michael
adduct 2i with both excellent yields of 88% under ul-
trasonication (Table 2). At the same time, we can see
from Table 2 that strong base can accelerate the reaction
rate evidently since potassium hydroxide only takes
0.5 h to drive the above Michael reaction to completion,
while under the catalysis of potassium carbonate, only
42% yield of product 2i was attained even after reacting
for 1 h.
were obtained via the reactions of dibenzyl ketone with
1, its structure was characterized by X-ray crystal
structure analysis (Fig. 1).
2. Results and discussion
In our initial research, we found that the Michael
reactions of deoxybenzoin with 1 (Scheme 1) could be
performed easily and the reactions proceeded efficiently
simply by irradiating the mixture of substrates in the
presence of ultrasound irradiation at 60 °C, and afforded
the corresponding Michael adducts with excellent yields
of 81–96%. All the results are summarized in Table 1. In
the meantime, compound 1 (a–k) could transform into
compound 2 (a–k) almost completely when an excess of
deoxybenzoin (two equivalent) was added. However,
when we stirred the mixture of 1-ferrocenyl-3-phenyl-
prop-2-ene-1-one (1d) (0.5 mmol), deoxybenzoin (1
mmol), sodium hydroxide (2 mmol) and ethanol (30 ml)
at 60 °C for 2 h without the involvement of ultrasound
irradiation, we could only get 69% yield of compound
2d. And the yield of the 2d was not increase greatly even
prolonged the reaction time or increased the tempera-
ture of the reaction mixture (It can lead the decompo-
siton of 1 at higher temperature in the base conditions).
It indicates obviously that the participation of
ultrasound irradiation plays a very important role for
In the following work, the reactions of dibenzyl ke-
tone with various ferrocenylenones (1b, 1d, 1e, 1g, 1l) in
Table 2
The Michael reaction of deoxybenzoin with chalcone (1i) promoted by
different bases at 60 °C under ultrasound irradiation
O
Ph
S
O
O
Ph
O
Catalyst/EtOH
Ultrasound
Ph
+
Fc
Ph
S
60 oC
Fc
1i
2i
O
Entry
Catalyst
Time (h)
Yielda (%)
Ph
Ar
O
O
Ph
O
NaOH/EtOH
Ultrasound
60 oC
+
Ph
1
2
3
K2CO3
LiOH
KOH
1
42
88
88
Fc
Ar
Ph
1
0.5
Fc
1(a-k)
2(a-k)
a Isolated yields.
Scheme 1.

S.-J. Ji et al. / Journal of Organometallic Chemistry 689 (2004) 1843–1848
1845
the presence of sodium hydroxide have been investi-
gated. For example, when the mixture of chalcone 1b (0.5
mmol), dibenzyl ketone (1.2 mmol), sodium hydroxide (2
mmol) and ethanol (5 ml) were irradiated at 60 °C for 1
h, the red solid turned orange–yellow eventually and
obtained the corresponding Michael adduct 2l with ex-
cellent yield of 89% after subsequent simple manipula-
tion. And the results are listed in Table 3.
Nevertheless, when we conducted the reactions of
dibenzyl ketone with some ferrocene-containing chal-
cones using sodium hydroxide as catalyst (Table 4), we
discovered the formation of cyclic a; b-unsaturated ke-
tones which formed by base-induced further Aldol
condensation after the first-step Michael addition. In
other words, the formed Michael adducts could undergo
further Aldol condensation and closed-ring products
generated eventually. A case in point is the reaction of 1-
ferrocenyl-3-(a-thienyl)prop-2-ene-1-one (1i) with dib-
enzyl ketone catalyzed by sodium hydroxide in the
presence of ultrasound irradiation at 60 °C, we observed
that the red color of the solution turned orange–yellow
gradually (explain: the formation of Michael adduct
requires the transformation of double-bond of chalcone
into single-bond and the process leads to blue shift of
absorption wavelength, which thus causes the color of
mixture turn orange–yellow). However, with the pro-
longation of time, the color became red again (explain:
the subsequent occurrence of Aldol condensation which
takes place in situ under the additive of sodium hy-
droxide effects a cyclic a; b-unsaturated ketone 3a and
the formation of the new cyclic compound (a new cyclic
conjugate system) results in red shift of absorption
wavelength and consequently explains the change of
color reasonably).
At the present stage of experiments, we really was
puzzled by the results we had obtained, for it was very
much difficult for us to present a rational explanation
for following truth: why for these chalcones bearing a
five-membered heteroatomic ring (entries 1–4, Table 4)
favor the formation of cyclic compounds while for other
chalcones (entries 1–5, Table 3) only Michael adducts
have been furnished? When we compare with the facts
that two different types of products have been got for
two similar substrates-chalcone 1l (entry 5, Table 3) and
chalcone 1i (entry 1, Table 4), we could make sure that
the electronic nature of the chalcone plays a dominant
influence on the type of the final product.
Further investigations reveal that the basicity of base
used also plays a very important role for the formation
of final products as well as the electronic nature of
chalcone itself.
To examine the effects of different bases on the re-
action, several other bases, including potassium hy-
droxide, lithium hydroxide and potassium carbonate,
were applied to the reaction of chalcone 1 (b, i) with
dibenzyl ketone under ultrasonication. And the results
are outlined in Table 5 below.
Table 3
The Michael reactions of dibenzyl ketone with ferrocenyl substituted
chalcones 1 under ultrasound irradiation
From entries 1–2 (Table 5), we can see that lithium
hydroxide can also promote the cyclization of chalcone
1i with dibenzyl ketone, although the yield (76%) is a
bitter lower in contrast with the yields obtained using
sodium hydroxide or potassium hydroxide as additive.
In the meantime, we also found in our experiments that
only Michael adduct has been yielded when we carried
out the reaction of chalcone 1i with dibenzyl ketone
under the additive of potassium carbonate, and the yield
O
Ph
Ph
Ar
O
O
NaOH/EtOH
Ultrasound
+
Ph
Ph
O
Fc
Ar
60 oC, 1 h Fc
1(b-l)
2(l-q)
Entry
Reactant
Ar
Product
Yielda (%)
1
2
3
4
5
1b
1d
1e
1g
1l
4-Cl–C6H4
C6H5
2l
89
92
81
91
92
2m
2n
2o
2p
4-CH3–C6H4
3,4-O2CH2–C6H3
4-Br–2-C4H2S
a Isolated yields.
Table 5
The reactions of chalcone 1(b, i) with dibenzyl ketone promoted by
different bases under ultrasound irradiation
Ph
O
O
Table 4
The reactions of dibenzyl ketone with 1i–m promoted by sodium hy-
Ph
Fc
Ph Ph
+
Ph
Ar
O
Catalyst/EtOH
+
O
O
Fc
Ar
Ultrasound
60 oC, 1 h
droxide at 60 °C under ultrasound irradiation
Ar Fc
Ph
O
2(l)
1(b, i)
3(e, a)
Ph
Ph
O
O
NaOH/EtOH
Ultrasound
+
Ph
Ph
Entry
Ar
Catalyst
Yielda (%)
Fc
Ar
60 oC, 1 h Fc
Ar
1(i-m)
3(a-d)
Product
1
2
3
4
5
2-C4H3S
2-C4H3S
LiOH
KOH
3a (76)
3a (92)
2l (28)b
2l (61)b
Entry
Reactant
Ar
Yielda (%)
4-Cl–C6H4 K2CO3
4-Cl–C6H4 LiOH
4-Cl–C6H4 KOH
1
2
3
4
1i
2-C4H3S
3-C4H3S
2-C4H3O
3a
3b
3c
85
96
92
78
1j
2l (46)
3e (47)
1k
1m
a Isolated yields.
3-CH3–2-C4H2S 3d
b The reaction proceeded incompletely, and the existence of chalcone
has been tested by TLC.
a Isolated yields.

1846
S.-J. Ji et al. / Journal of Organometallic Chemistry 689 (2004) 1843–1848
was too much lower. We can infer from it that the
basicity of base is also an important factor influencing
the progress of the reaction and the type of final prod-
uct. Results obtained in entries 3–5 demonstrate it fur-
ther that when the reaction of chalcone 1b with dibenzyl
ketone was operated under ultrasound irradiation em-
ploying potassium carbonate and lithium hydroxide as
catalyst, we could achieve the corresponding Michael
adduct 2l with the yields of 28% and 61%, respectively.
While when the mixture of substrates were subjected to
the catalysis of potassium hydroxide, 47% yield of cyclic
a; b-unsaturated ketone 3e has been afforded apart from
giving 46% yield of Michael adduct 2l, that is to say, the
formed Michael adduct 2l could transform into cyclized
ketone partially in the presence of strong base potassium
hydroxide.
In summary, all the results above indicate that the
basicity of the catalysts also have significant influence
for determining the occurrence of the reaction and es-
pecially the final products and their ratios, which is also
an equally important factor for the reactions in contrast
with the electronic nature of chalcone itself. At the same
time, the effects of time, temperature and ultrasound on
the reaction cannot be ignored too.
sonication was performed in a KQ-250E ultrasonic
cleaner with a frequency of 40 KHz and a normal power
of 250 W. The reaction flask was located in the water
bath of the ultrasonic cleaner, and the temperature of
the water bath was controlled by inherently heating.
Ferrocenyl substituted chalcones 1 are prepared as
previously reported [23].
4.1. General procedure for the reactions of deoxybenzoin
with ferrocenyl substituted chalcones
The mixture of ferrocenyl substituted chalcones 1 (0.5
mmol), deoxybenzoin (1 mmol), sodium hydroxide (2
mmol) and ethanol was added to a flask. Then it was
immersed into the water bath of an ultrasonic cleaner at
60 °C for a special time as shown in Table 1. And the
progress of the reaction is monitored by TLC. After the
completion of the reaction, 30 ml water is added to the
final products and stirred for a while, then it was filtered
under reduced pressure and the solid was washed with
water and aqueous ethanol (1:1). Further purification
was accomplished by crystallization from 95% ethanol
and yield product 2.
1,2-Diphenyl-3-(4-nitrophenyl)-5-ferrocenyl-pentane-
1,5-dione (2a): m.p.: 215–217 °C; IR (KBr): m 1676, 1664
cmꢀ1; 1H NMR (400 MHz, CDCl3): d 2.95 (q, 2H); 3.81
(s, 5H); 4.40 (s, 2H); 4.46 (m, 1H); 4.57 (s, 2H); 5.25 (d,
J ¼ 11:2 Hz, 1H); 7.26–8.11 (m, 14H); HRMS [Found:
m=z, 557.1266 (Mþ); Calc. for C33H27FeNO4: M,
557.1289].
3. Conclusions
In conclusion, we have developed an convenient, ef-
ficient and economical approach for the preparation of a
series of new ferrocenyl substituted 1,5-diketone com-
pounds 1 and cyclic a; b-unsaturated ketones under ul-
trasound irradiation. And the final products for the
reactions of dibenzyl ketone with 1 are largely depen-
dent on the following factors: the electronic nature of
chalcone itself, the basicity of the base used, reaction
time and temperature et al. And the influence of elec-
tronic nature of chalcone is well under way. This
method proved to be an attractive alternative to existing
methodologies under conventional and moisture-sensi-
tive homogeneous base catalysis with the frequent
troublesome manipulation and work-up. The one pot
synthesis of the ferrocenyl substituted cyclic a; b-unsat-
urated ketones are underway in our laboratory, which to
be continued.
1,2-Diphenyl-3-(4-chlorophenyl)-5-ferrocenyl-pen-
tane-1,5-dione (2b): m.p.: 190–192 °C; IR (KBr): m 1677,
1655 cmꢀ1 1H NMR (400 MHz, CDCl3): d 3.20 (d,
;
J ¼ 4:8 Hz, 2H); 4.01 (s, 5H); 4.24 (s, 1H); 4.44 (s, 2H);
4.72 (d, J ¼ 10 Hz, 2H); 5.03 (d, J ¼ 10 Hz, 1H); 7.09–
8.05 (m, 14H); HRMS [Found: m=z, 546.1019 (Mþ);
Calc. for C33H27ClFeO2: M, 546.1049].
1,2-Diphenyl-3-(2-chlorophenyl)-5-ferrocenyl-pen-
tane-1,5-dione (2c): m.p.: 191–193 °C; IR (KBr): m 1674
1
cmꢀ1; H NMR (400 MHz, CDCl3): d 3.16 (d, J ¼ 14:4
Hz, 1H); 3.56 (s, 1H); 4.00 (s, 5H); 4.44 (s, 2H); 4.74 (s,
3H); 5.55 (d, J ¼ 8:4 Hz, 1H); 6.98–7.51 (m, 11H); 8.04
(d, J ¼ 7:2 Hz, 2H); HRMS [Found: m=z, 546.1011
(Mþ); Calc. for C33H27ClFeO2: M, 546.1049].
1,2,3-Triphenyl-5-ferrocenyl-pentane-1,5-dione (2d):
;
1H
m.p.: 198–201 °C; IR (KBr): m 1669, 1652 cmꢀ1
NMR (400 MHz, CDCl3): d 2.76 (q, 1H); 2.97 (q, 1H);
3.76 (s, 5H); 4.27 (t, J ¼ 9 Hz, 1H); 4.36 (s, 2H); 4.57 (d,
J ¼ 26:4 Hz, 2H); 5.10 (d, J ¼ 10:8 Hz, 1H); 7.00–7.56
(m, 13H); 7.85 (d, J ¼ 8 Hz, 2H); HRMS [Found: m=z,
512.1440 (Mþ); Calc. for C33H28FeO2: M, 512.1439].
1,2-Diphenyl-3-(4-methylphenyl)-5-ferrocenyl-pen-
tane-1,5-dione (2e): m.p.: 203–206 °C; IR (KBr): m 1671,
1655 cmꢀ1; 1H NMR (400 MHz, CDCl3): d 2.18 (s, 3H);
2.75 (t, J ¼ 8:6 Hz, 1H); 2.94 (q, 1H); 3.78 (s, 5H); 4.37
(d, J ¼ 10 Hz, 3H); 4.57 (d, J ¼ 25:6 Hz, 2H); 5.27 (d,
4. Experimental
Melting points were determined on a XT-5A digital
melting points apparatus and uncorrected. IR spectra
were obtained on a Nicolet FT-IR500 spectrophotom-
eter using KBr pellets. Elemental analyses were per-
formed on a Carlo–Erba 1110 Elemental analysis
1
instrument. H NMR spectra were recorded on Varian
Inova 400 MHz NMR spectrometer in CDCl3. Ultra-

S.-J. Ji et al. / Journal of Organometallic Chemistry 689 (2004) 1843–1848
1847
J ¼ 11:6 Hz, 2H); 7.00–7.87 (m, 14H); HRMS [Found:
m=z, 526.1554 (Mþ); Calc. for C34H30FeO2: M,
526.1595].
it was immersed into the water bath of an ultrasonic
cleaner at 60 °C for a special time as shown in Tables 3
and 4. And the progress of the reaction is monitored by
TLC. After the completion of the reaction, 30 ml
aqueous ethanol (50%) was added to the final products
and stirred for a while, then it was filtered under reduced
pressure and the solid was washed with water and
aqueous ethanol (1:1). Further purification was accom-
plished by crystallization from 95% ethanol and yielded
products 2 (l–p) and 3 (a–d).
3-(4-Thlorophenyl)-4,6-diphenyl-1-ferrocenyl-hexane-
1,5-dione (2l): m.p.: 204–206 °C; IR (KBr): m 1718, 1652
cmꢀ1; 1H NMR (400 MHz, CDCl3): d 2.58 (d, 1H); 2.80
(t, 1H); 3.43 (s, 2H); 3.77 (s, 5H); 4.23 (s, q, 2H); 4.35 (s,
2H); 4.51 (d, J ¼ 25:6 Hz, 2H); 6.79 (d, J ¼ 5:2 Hz, 2H);
7.15–7.38 (m, 12H); HRMS [Found: m=z, 560.1209
(Mþ); Calc. for C34H29ClFeO2: M, 560.1205]; Anal.
Calc. for C34H29ClFeO2: C, 72.81; H, 5.21; Found: C,
72.70; H, 5.18%.
1,2-Diphenyl-3-(4-methoxyphenyl)-5-ferrocenyl-pen-
tane-1,5-dione (2f): m.p.: 192–194 °C; IR (KBr): m 1673,
1655 cmꢀ1 1H NMR (400 MHz, CDCl3): d 2.75 (t,
;
J ¼ 10 Hz, 1H); 2.93 (q, 1H); 3.67 (s, 3H); 3.80 (s, 5H);
4.32 (d, J ¼ 2:8 Hz, 1H); 4.36 (s, 2H); 4.57 (d, J ¼ 24:8
Hz, 2H); 5.24 (d, J ¼ 10:8 Hz, 1H); 6.74–7.86 (m, 14H);
HRMS [Found: m=z, 542.1545 (Mþ); Calc. for
C34H30FeO3: M, 542.1544].
1,2-Diphenyl-3-(3,4-methylenedioxyphenyl)-5-ferroce-
nyl-pentane-1,5-dione (2g): m.p.: 190–193 °C; IR (KBr):
1
m 1672 cmꢀ1; H NMR (400 MHz, CDCl3): d 2.73 (t,
J ¼ 8:4 Hz, 1H);2.91 (q, 1H); 3.83 (s, 5H); 4.31 (d,
J ¼ 10:4 Hz, 1H); 4.38 (s, 2H);4.58 (d, J ¼ 25:6 Hz, 2H);
5.19 (d, J ¼ 10:8 Hz, 1H); 5.81 (s, 2H); 6.64–7.88 (m,
13H); HRMS [Found: m=z, 556.1323 (Mþ); Calc. for
C34H28FeO4: M, 556.1337].
1,2-Diphenyl-3-(2-pyridinyl)-5-ferrocenyl-pentane-1,5-
dione (2h): m.p.: 188–190.5 °C; IR (KBr): m 1673, 1660
3,4,6-Triphenyl-1-ferrocenyl-hexane-1,5-dione (2m):
1
m.p.: 201.5–203 °C; IR (KBr): m 1718, 1658 cmꢀ1; H
1
cmꢀ1; H NMR (400 MHz, CDCl3): d 2.72 (d, J ¼ 15:6
NMR (400 MHz, CDCl3): d 2.56 (t, J ¼ 9:8 Hz, 1H);
2.91 (q, 1H); 3.43 (s, 2H); 3.74 (s, 5H); 4.25–4.35 (m,
4H); 4.49 (s, 1H); 4.59 (s, 1H); 6.73–7.42 (m, 15H);
HRMS [Found: m=z, 526.1547 (Mþ); Calc. for
C34H3FeO2: M, 526.1595].
Hz, 1H); 3.48 (s, 1H); 3.80 (s, 5H); 4.38 (s, 2H); 4.59 (s,
2H); 4.65 (s, 1H); 5.45 (s, 1H); 7.07–7.90 (m, 13H); 8.44
(s, 1H); HRMS [Found: m=z, 513.1359 (Mþ); Calc. for
C32H27FeNO2: M, 513.1391].
1,2-Diphenyl-3-(2-thienyl)-5-ferrocenyl-pentane-1,5-
dione (2i): m.p.: 223.5–225 °C; IR (KBr): m 1674, 1652
3-(4-Methylphenyl)-4,6-diphenyl-1-ferrocenyl-hexane-
1,5-dione (2n): m.p.: 209–211 °C; IR (KBr): m 1719, 1656
cmꢀ1; 1H NMR (400 MHz, CDCl3): d 2.28 (s, 3H); 2.56
(d, J ¼ 14:8 Hz, 1H); 2.88 (m, 1H); 3.42 (s, 2H); 3.76 (s,
5H); 4.22 (d, J ¼ 10:4 Hz, 1H); 4.33 (q, 3H); 4.49 (s,
1H); 4.58 (s, 1H); 6.74–7.40 (m, 14H); HRMS [Found:
m=z, 540.1725 (Mþ); Calc. for C35H32ClFeO2: M,
540.1752].
1
cmꢀ1; H NMR (400 MHz, CDCl3): d 2.82 (t, J ¼ 8:8
Hz, 1H); 2.93 (q, 1H); 3.84 (s, 5H); 4.39 (s, 2H); 4.60 (d,
J ¼ 18:4 Hz, 2H); 4.74 (t, J ¼ 8:4 Hz, 1H); 5.33 (d,
J ¼ 11:2 Hz, 1H); 6.79–7.93 (m, 13H); HRMS [Found:
m=z, 518.0997 (Mþ); Calc. for C31H26FeO2S: M,
518.1003].
1,2-Diphenyl-3-(3-thienyl)-5-ferrocenyl-pentane-1,5-
dione (2j): m.p.: 224–225.5 °C; IR (KBr): m 1674, 1651
3-(3,4-Methylenedioxyphenyl)-4,6-diphenyl-1-ferroce-
nyl-hexane-1,5-dione (2o): m.p.: 210–212 °C; IR (KBr):
m 1718, 1655 cmꢀ1; 1H NMR (400 MHz, CDCl3): d 2.51
(d, J ¼ 16:4 Hz, 1H); 2.81 (m, 1H); 3.45 (s, 2H); 3.76 (s,
5H); 4.14–4.25 (m, 2H); 4.35 (d, J ¼ 6:4 Hz, 2H); 4.53
(d, J ¼ 38 Hz, 2H); 5.88 (d, J ¼ 9:2 Hz, 2H); 6.65–7.37
(m, 13H); HRMS [Found: m=z, 570.1494 (Mþ); Calc. for
C35H30FeO4: M, 570.1493].
1
cmꢀ1; H NMR (400 MHz, CDCl3): d 2.83 (t, J ¼ 7:2
Hz, 2H); 3.83 (s, 5H); 4.39 (s, 2H); 4.51 (t, J ¼ 8:2 Hz,
1H); 4.59 (d, J ¼ 14:8 Hz, 2H); 5.32 (d, J ¼ 11:2 Hz,
1H); 7.14–7.89 (m, 13H); HRMS [Found: m=z, 518.0986
(Mþ); Calc. for C31H26FeO2S: M, 518.1003].
1,2-Diphenyl-3-(2-furyl)-5-ferrocenyl-pentane-1,5-di-
one (2k): m.p.: 180.5–182 °C; IR (KBr): m 1676, 1655
3-(4-Bromo-2-thienyl)-4,6-diphenyl-1-ferrocenyl-hex-
ane-1,5-dione (2p): m.p.: 218–220 °C; IR (KBr): m 1719,
1
cmꢀ1; H NMR (400 MHz, CDCl3): d 2.77 (d, J ¼ 14:8
Hz, 1H); 2.98 (d, J ¼ 9:6 Hz, 1H); 3.92 (s, 5H); 4.40 (s,
2H); 4.52 (s, 1H); 4.62 (d, J ¼ 15:6 Hz, 2H); 5.32 (d,
J ¼ 10:8 Hz, 1H); 6.17 (d, J ¼ 3:2 Hz, 2H); 7.20–7.94
(m, 11H); HRMS [Found: m=z, 502.1215 (Mþ); Calc. for
C31H26FeO3: M, 502.1231].
1654 cmꢀ1 1H NMR (400 MHz, CDCl3): d 2.62 (t,
;
J ¼ 1:6 Hz, 1H); 2.79 (q, 1H); 3.54 (s, 2H); 3.84 (s, 5H);
4.36 (t, J ¼ 8 Hz, 3H); 4.46 (t, J ¼ 9:2 Hz, 1H); 4.56 (d,
J ¼ 26:4 Hz, 2H); 6.73–7.38 (m, 13H); HRMS [Found:
m=z, 610.0259 (Mþ); Calc. for C32H27FeO2S: M,
610.0265].
4.2. General procedure for the reactions of dibenzyl
ketone with ferrocenyl substituted chalcones
2,6-Diphenyl-3-ferrocenyl-5-(2-thienyl)-cyclohex-2-
enone (3a): m.p.: 235–238 °C; IR (KBr): m 1655 cmꢀ1
;
1H NMR (400 MHz, CDCl3): d 3.23 (q, 1H); 3.38 (q,
1H); 3.88 (d, J ¼ 5:2 Hz, 2H); 4.05 (q, 7H); 4.27 (s, 2H);
6.85–7.41 (m, 13H); HRMS [Found: m=z, 514.0988
(Mþ); Calc. for C32H26FeOS: M, 514.1054]; Anal. Calc.
The mixture of ferrocenyl substituted chalcones 1 (0.5
mmol), dibenzyl ketone (1.2 mmol), sodium hydroxide
(2 mmol) and ethanol (5 ml) was added to a flask. Then

1848
S.-J. Ji et al. / Journal of Organometallic Chemistry 689 (2004) 1843–1848
for C32H26FeOS: C, 74.94; H, 5.03; Found: C, 74.71; H,
5.09%.
2,6-Diphenyl-3-ferrocenyl-5-(3-thienyl)-cyclohex-2-
Acknowledgements
This work was supported by the National Nature
Science Foundation of China (No. 20172039).
enone (3b): m.p.: 212–214 °C; IR (KBr): m 1657 cmꢀ1
;
1H NMR (400 MHz, CDCl3): d 3.17 (q, 1H); 3.28 (q,
1H); 3.82 (s, 1H); 3.90 (s, 2H); 4.03 (d, 6H); 4.26 (s, 2H);
7.05–7.40 (m, 13H); HRMS [Found: m=z, 514.1047
(Mþ); Calc. for C32H26FeOS: M, 514.1054].
References
2,6-Diphenyl-3-ferrocenyl-5-(2-furyl)-cyclohex-2-en-
one (3c): m.p.: 234.5–237 °C; IR (KBr): m 1655 cmꢀ1; 1H
NMR (400 MHz, CDCl3): d 3.17 (q, 1H); 3.29 (s, 1H);
3.69 (s, 1H); 3.85 (q, 1H); 3.98–4.15 (m, 7H); 4.26 (d,
J ¼ 11:2 Hz, 2H); 6.12 (d, J ¼ 3:2 Hz, 1H); 6.31(s, 1H);
7.08–7.42 (m, 11H); HRMS [Found: m=z, 498.1249
(Mþ); Calc. for C32H26FeO2: M, 498.1282]; Anal. Calc.
For C32H26FeO2: C, 77.12; H, 5.26; Found: C, 77.08; H,
5.25%.
2,6-Diphenyl-3-ferrocenyl-5-(3-methyl-2-thienyl)-cy-
clohex-2-enone (3d): m.p.: 208–210 °C; IR (KBr): m 1645
cmꢀ1; 1H NMR (400 MHz, CDCl3): d 2.03 (s, 3H); 3.20
(q, 1H); 3.32 (q, 1H); 3.90 (t, 3H); 4.07 (d, 6H); 4.27 (s,
2H); 6.69–7.39 (m, 12H); HRMS [Found: m=z, 528.1183
(Mþ); Calc. for C32H28FeOS: M, 528.1210].
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