Ultrasound-irradiated Michael addition of amines to ferrocenylenones under solvent-free and catalyst-free conditions at room temperature

Article abstract of DOI:10.1016/j.jorganchem.2005.03.030

A facile Michael addition of ferrocenylenones with aliphatic amines under ultrasound irradiation in the absence of solvent and catalyst at room temperature can afford 1-ferrocenyl-3-amino carbonyl compounds rapidly in high yields, which is also efficient in the aza-Michael reaction of other α,β-unsaturated carbonyl compounds such as chalcone, carboxylic ester, etc. However, aromatic amines do not undergo the conjugate addition at all, and the reactions under existing methods do not proceed or take place in low yield after a long reaction time. Apart from experimental simplicity, generality and selectivity, the advantages of this methodology are the rapid, environmentally benign and less expensive processes, which will contribute to the progress of green chemistry.

Full text of DOI:10.1016/j.jorganchem.2005.03.030

Journal of Organometallic Chemistry 690 (2005) 2989–2995
www.elsevier.com/locate/jorganchem
Ultrasound-irradiated Michael addition of amines
to ferrocenylenones under solvent-free and catalyst-free
conditions at room temperature
a,
a
a
a
Jin-Ming Yang a,b, Shun-Jun Ji *, Da-Gong Gu , Zhi-Liang Shen , Shun-Yi Wang
a
The Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering,
Suzhou University, Suzhou 215006, China
b
Department of Chemistry, Yancheng TeacherÕs College, Yancheng 224002, China
Received 14 September 2004; revised 17 February 2005; accepted 11 March 2005
Available online 5 May 2005
Abstract
A facile Michael addition of ferrocenylenones with aliphatic amines under ultrasound irradiation in the absence of solvent and
catalyst at room temperature can afford 1-ferrocenyl-3-amino carbonyl compounds rapidly in high yields, which is also efficient in
the aza-Michael reaction of other a,b-unsaturated carbonyl compounds such as chalcone, carboxylic ester, etc. However, aromatic
amines do not undergo the conjugate addition at all, and the reactions under existing methods do not proceed or take place in low
yield after a long reaction time. Apart from experimental simplicity, generality and selectivity, the advantages of this methodology
are the rapid, environmentally benign and less expensive processes, which will contribute to the progress of green chemistry.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Michael addition; Ferrocene, amine; b-amino carbonyl compound; Ultrasound; Solvent-free
1. Introduction
b-amino carbonyl compounds and derivatives has at-
tracted much attention in organic synthesis [4]. Among
the traditional methods for generating b-amino carbonyl
compounds, Mannich-reaction, the reactions of enolates
with imines, are established processes for the synthesis
of these moieties through carbon–carbon bond forma-
tion [5] (Scheme 1). However, due to the harsh reactions
and the long reaction time, the classic Mannich reaction
presents serious disadvantages [6]. Alternatively, the Mi-
chael reaction, acid- or base-induced conjugate addition
of nucleophiles to a,b-unsaturated compounds, can be
used to create carbon–heteroatom bonds by reaction
of a,b-unsaturated carbonyl compounds with amines
[7] (Scheme 1). To avoid many of disadvantages of stoi-
chiometric addition of a Lewis acid-mediated (AlCl3,
SnCl4, or TiCl4) conjugate addition reaction, a number
of reactions that use catalytic quantities of minimally
toxic, readily available, economic reagent have been
b-Amino carbonyl compounds are versatile interme-
diates for a large number of organic compounds, as
exemplified in the preparation of c-amino alcohols,
diamines, b-amino acid derivatives and chiral auxiliaries
[1], many of which are present as a segment of biologi-
cally important natural products such as alkaloids and
polyketides [2]. Other applications of this type of com-
pounds are in the fine chemical and pharmaceutical
fields [3]. As a result of this vast range of applications,
synthesis of b-amino carbonyl compounds has remained
an important objective for a number of years, and the
development of efficient synthetic methods leading to
*
Corresponding author. Tel.: +86 512 65112853/65112372; fax: +86
512 65224783.
E-mail address: shunjun@suda.edu.cn (S.-J. Ji).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.03.030

2990
J.-M. Yang et al. / Journal of Organometallic Chemistry 690 (2005) 2989–2995
O-
of water was really helpful to drive the amine addition
NHR O
NR
O
R
NH2
to completion in accordance with the literature results
[22]. However, more water stopped the reactions, and
copper salts failed to catalyze the reaction. (b) At least
10 mol equivalent of amines were required. (c) High
temperature, microwave and acidic media were all
disadvantageous to this reaction, and even induced
some unwanted side reactions such as polymerization
of vinyl ketones, oxidization of amine moieties or fer-
rocene fragments, and cleavage of b-amino ketones as
desired products. In a typical reaction, ferrocenylenone
(0.1 mol), piperidine (1 mol) and water (1 mol) were
mixed and stirred at room temperature for 16 h under
nitrogen atmosphere. The progress of the reaction was
monitored with TLC. After conventional work-up a
58% yield of the 1,4-adduct was obtained (Scheme 2).
For demonstrating the generality of this methodology
different amines and Michael acceptors were used
(Table 3, stir). But the results did not satisfy our inter-
est of the reaction due to undesirable yields and long
reaction time.
Recently, ultrasound has been utilized in organic syn-
thesis as a new reaction media. Compared with tradi-
tional heating methods, this approach is more
convenient, efficient and can be controlled easily. It
has been reported that a large number of organic reac-
tions could be facilitated by ultrasound irradiation with
high yields, shorter reaction time and milder conditions
[23]. Currently, our research group has also demon-
strated the efficiency of this methodology for different
reactions [24]. We have, therefore, decided to apply this
technique to the above-mentioned reactions. Effective-
ness of ultrasound to promote this conversion was tested
for the reaction of ferrocenylenone and piperidine at
ambient temperature in aqueous medium. To our satis-
faction, the addition products were obtained in almost
quantitative yield (98%) in a very short reaction time
(1 h). Encouraged by this result, we carried out the reac-
tion under solvent-free condition (Scheme 3). To our
R1
R2
R1
R2
R1
R2
H
Scheme 1. Synthesis of b-amino carbonyl compounds.
studied in the past few years. To the best of our
knowledge, palladium [8], InCl3 [9], CeCl3/NaI [10],
Bi(NO3)3 [11], Bi(OTf)3 [12], copper salts [13], and other
acids (Brønsted acids [14], or acidic clays [15]) have been
used successfully in aza-Michael addition. Although
recent advances have made this route more attractive,
development of cheaper, simpler, more efficient and
environmentally benign processes is highly desirable.
The derivatives of ferrocene have being attracted the
attention of scientists all over the word because of their
numerous applications in chemical sensing, asymmetric
catalysis, material science and medical chemistry [16].
As a part of program aiming at the synthesis of poten-
tial biological or pharmacological active compounds
such as ferrocene- or indole-containing fragments and
with the increasing interest of our group in efficient,
economic and environmentally friendly reactions
mediated by metals and their salts, ionic liquids, or
under solvent-free conditions [17], now we wish to
search an optimized route to 1-ferrocenyl-3-amino
carbonyl compounds by Michael-type reaction of
amines to ferrocenylenones, which surprisingly no
other references available in the literature reported to
date.
2. Results and discussion
Traditionally, only simple primary amines can re-
acted with a,b-unsaturated compounds with special
activation, such as high temperature [18], high pressure
[19], the use of appropriate catalysts, etc. [20]. Re-
cently, Meyers reported that, water assist the N-conju-
gate addition of amines to unsaturated bicyclic lactams
[21]. And Matloubi Moghaddam found water can
promote Michael addition of secondary amines to
a,b-unsaturated carbonyl compounds under microwave
irradiation [22]. Chun-Gu Xia also discovered copper-
catalyzed conjugate addition of aliphatic amines to
a,b-unsaturated compounds in water [13]. These meth-
ods are really very fascinating to us because the pro-
cesses are less expensive and performed in green
aqueous solvent, water. The previous findings
prompted us to develop a new protocol that employs
water as medium in the aza-Michael reaction under
mild condition. The starting point of this work was
an examination of the generality of these reactions. Pri-
mary experiments revealed several features for the opti-
mization of the Michael reaction of amines to
ferrocenylenones: (a) the presence of a small amount
O
O
N
H2O / N2
Fc
+
Fc
N
r.t. 16h
58%
H
Scheme 2. Water-assisted Michael reaction of amines to
ferrocenylenones.
O
O
N
Solvent Free
U.S. / r.t.
Ar
Fc
+
Fc
Ar
N
H
2
3(a-i)
1(a-i)
Scheme 3.

J.-M. Yang et al. / Journal of Organometallic Chemistry 690 (2005) 2989–2995
2991
Table 1
Ultrasound irradiated Michael additions of ferrocenylenones with
piperidine under solvent free condition at room temperature
Table 2
Ultrasound irradiated Michael additions of amines to 1-ferrocenyl-3-
(4-chlorophenyl)prop-2-en-1-one under solvent free condition at room
temperature
Reactant
Ar
Time
(h)
Yield a
(%)
Entry
1
Product
O
N
4-NO2-C6H4
0.5
0.5
1
98
98
3a
1a
Fc
NO2
O
O
N
4-Cl-C6H4
2
3
4
5
6
7
8
3b
Fc
1b
Cl
C6H5
1c
N
98
96
97
90
98
82
32b
3c
Fc
O
O
N
4-CH3-C6H4
1.5
1.5
2
3d
Fc
1d
CH3
N
4-OCH3-C6H4
3e
1e
Fc
OCH3
O
2-C5H4N
1f
N
3f
Fc
N
O
2-C4H3S
1g
N
2
3g
Fc
S
a
Isolated yields.
O
2-C4H3O
1h
N
2
3h
Fc
Fc
O
In Table 1 our results from ultrasound irradiated
reactions of piperidine to different ferrocenylenones un-
der solvent-free condition (Scheme 3) reveal that in all
cases the 1,4-adducts are observed as the exclusive prod-
ucts of the reaction and the yields are good to excellent
within 2 h, except for the less reactive Michael acceptor
(Table 1, Entry 9) that reacts poorly due to steric
influence.
O
2-Cl-C6H4
N
Cl
9
2
3i
1i
a
Isolated yields.
Without isolating pure product, the yield resulted from HPLC. The
b
reaction proceeded incompletely, and the existence of chalcone has
been tested with TLC.
As is shown in Table 2, several different types of
amines were subjected for this reaction under the same
conditions (Scheme 4). All the aliphatic amines gave
excellent yields within 2 h such as piperidine and mor-
pholine (Table 2, Entries 1–2), which added better than
other primary amines (Table 2, Entries 3–5) in accor-
dance with their stronger nucleophilicities. However, ani-
line (Table 2, Entry 6) did not undergo the conjugate
addition at all. It is easily found that the new approach
is suitable only to active aliphatic amines and failed for
less nucleophilic aromatic amines. So this selectivity
could be useful to discriminate the two types of amines
for synthetic applications. Interestingly, when the pri-
mary amines such as n-butylamine, ethanolamine, or
benzylamine were treated with ferrocenylenones, highly
chemo-selectivity occurred in this reaction, only mono-
addition products were obtained (Table 2, Entries 3–5).
So we established a condition in aza-Michael reactions
for selective preparation of mono- and bis-addition prod-
ucts, which could also be useful in the synthesis of b-ami-
no carbonyl compounds.
surprise, the result was satisfactory all the same without
any loss of yield. Apart from experimental simplicity,
the advantages of this methodology are that the reaction
mediated by ultrasound without solvent can proceed
well even if the mixture of reactants, one of which is a
liquid, is thick slurry. So the quantities of amines can
be used minimally. The new findings promoted us to fur-
ther utilize this new method of ultrasound irradiated
aza-Michael addition to different ferrocenylenones
(Scheme 3, Table 1) and different amines (Scheme 4,
Table 2).
R1
R2
O
O
N
Solvent Free
U.S. / r.t.
R1
R2
+
Fc
N
Fc
H
Cl
Cl
1b
3(b, j-n)
Scheme 4.

2992
J.-M. Yang et al. / Journal of Organometallic Chemistry 690 (2005) 2989–2995
Table 3
Water-assisted or ultrasound-irradiated aza-Michael reactions of
amines to ferrocenylenones at room temperature
Table 4
Ultrasound irradiated Michael additions of piperidine to a,b-unsatu-
rated carbonyl compounds under solvent free condition at room
temperature
Stirb
Yielda
(%)
U.S.c
Entry
Product
Yielda
(%)
Unsaturated
Compound
Time
(h)
Yield a
(%)
Time
(h)
Time
Entry
1
Product
(h)
0.5
O
O
N
O
0.5
98
83
99
98
98
N
3b
Fc
Fc
1
2
16
16
73
98
98
Cl
3a
Cl
Fc
NO2
O
O
N
O
N
77
54
0.5
1
3b
3o
Fc
2
3
4
2
Fc
Fc
Cl
Cl
Cl
O
O
O
N
3
4
5
6
7
8
9
18
16
18
18
18
20
20
20
91
O
N
3p
0.5
0.5
0.5
3j
Fc
Fc
Cl
O
O
O
O
O
N
O
58
1
98
3q
OEt
3c
N
OEt
N
N
N
68
1.5
1.5
2
96
CN
CN
N
3d
3r
5
Fc
Fc
Fc
CH3
a
Isolated yields.
81
97
3e
OCH3
gate addition of amines to a,b-unsaturated carbonyl
compounds under solvent-free condition.
63
98
3g
We also reasoned that this new approach could be
versatile and universal for the intermolecular aza-
Michael reaction. It was possible to extend the scope
of the reaction to acceptors other than 1-ferrocenyl chal-
cones. Further experiments revealed that the same con-
cept could be applied successfully to 3-ferrocenyl
chalcones, chalcones, ethylacrylates or acrylonitriles
(Table 4, Entries 2–5), which gave corresponding aza-
Michael adducts rapidly in high yields by using ultra-
sound irradiation under solvent free condition. 3q–r
(Table 4, Entries 4–5) are direct precursors of b-amino-
acids. This pathway, therefore, offers a possible route to
b-aminoacid derivatives.
S
O
O
N
57
2
82
3h
Fc
Fc
O
HN
52
2
85
3k
Cl
O
HN
10
Trace
3
Trace
3n
Cl
Fc
a
Isolated yields.
The reactions proceeded in the presence of water at r.t.
The reactions were performed under sonication conditions at r.t.
b
c
3. Conclusion
Table 3 compares the results from ultrasound-irradi-
ated reaction and those obtained from water-assisted
reaction. The reaction proceeded smoothly, giving 3a
in 98% yield under ultrasound condition for 30 minutes.
However, only 73% 3a was obtained in the presence of
water by stir for 16 h (Table 3, Entry 1). Ultrasound
irradiated aza-Michael addition are advantageous not
only in terms of reactivity and simplicity, but also
regarding waste disposal and cost. Furthermore, devel-
opment of organic reactions under solvent-free condi-
tion will contribute to the progress of green chemistry.
Surprisingly, however, there are few reports on conju-
In conclusion, we have first developed a new
methodology using ultrasound irradiation for an inter-
molecular aza-Michael addition of aliphatic amines to
a,b-unsaturated carbonyl compounds under solvent-free
and catalyst-free condition at room temperature. In con-
trast to the existing methods, this technique is very effi-
cient, general, simple, high yielding, environmentally
friendly, and oxygen and moisture tolerant. The neat,
clean, and green process, Therefore, opens a novel entry
to synthesis of b-amino carbonyl compounds and finally
bodes well for the development of industrialization. Fur-

J.-M. Yang et al. / Journal of Organometallic Chemistry 690 (2005) 2989–2995
2993
ther exploration of addition reactions with complex
structure of the biological significance is in progress.
1-Ferrocenyl-3-(4-nitrophenyl)-3-(piperidin-1-yl)pro-
pan-1-one (3a): yellow solid; m.p.: 161–163 °C; IR(KBr):
m 2932, 1661, 1514, 1456, 1346, 1107, 857, 707, 499 cmÀ1
;
1H NMR (400 MHz, CDCl3) d ppm: 7.55–8.22(m, 4H),
4.76(d, J = 6.0 Hz, 2H), 4.51(s, 2H), 4.30(m, 1H), 4.10(s,
5H), 3.27(dd, J1 = 67.6 Hz, J2 = 16.4 Hz, 2H), 2.41(s,
4H), 1.40–1.61(m, 6H); HRMS [Found: m/z, 446.1292
(M+); Calc. for C24H26FeN2O3: M, 446.1293].
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 spectrophotome-
ter using KBr pellets. Elemental analyses were per-
formed on a Carlo-Erba 1110 Elemental analysis
1-Ferrocenyl-3-(4-chlorophenyl)-3-(piperidin-1-yl)-
propan-1-one (3b): yellow solid; m.p.: 143–145 °C;
IR(KBr): m 2932, 1656, 1491, 1455, 1380,1250, 1093,
1
instrument. H NMR was recorded on Varian Inova
820, 494 cmÀ1 1H NMR (400 MHz, CDCl3) d ppm:
;
400 MHz NMR spectrometer in CDCl3. High resolution
mass spectra were obtained using GCT-TOF instru-
ment. HPLC (LC-8A Waters 515). Ultrasonication
was performed in a KQ-250E ultrasonic cleaner with a
frequency of 40 kHz and a normal power of 250 W. Fer-
rocenylenones 1 were prepared as previously reported
[24a]. Other reagents were obtained from commercial
sources and used without purification.
7.28–7.31(m, 4H), 4.75(s, 2H),4.49(s, 2H), 4.17(m, 1H),
4.08(s, 5H), 3.25(dd, J1 = 40.0 Hz, J2 = 10.0 Hz, 2H),
2.40(s, 4H), 1.38–1.57(m, 6H); HRMS [Found: m/z,
435.1060 (M+); Calc. for C24H26ClFeNO: M, 435.1052].
1-Ferrocenyl-3-phenyl-3-(piperidin-1-yl)propan-1-one
(3c): yellow solid; m.p.:137–139 °C; IR(KBr): m 2931,
1660, 1454, 1380, 1094, 821, 706, 496 cmÀ1
;
1H
NMR(400 MHz, CDCl3) d ppm: 7.25–7.36(m, 5H),
4.75(d, J = 5.2 Hz, 2H), 4.47(s, 2H), 4.19(t,
J1 = J2 = 6.4 Hz, 1H), 4.03(s, 5H), 3.25–3.28(m, 2H ),
2.42(s, 4H), 1.37–1.58(m, 6H); Anal. Calc. for
C24H27FeNO: C 71.83, H 6.78, N 3.49, Found: C
71.86, H 6.72, N 3.41.
4.1. General procedure for water-assisted Michael
addition of amines to ferrocenylenones
Ferrocenylenones 1 (0.1 mmol), amines 2 (1 mmol)
and water (1 ml) were mixed and stirred at room temper-
ature for a specific time under nitrogen atmosphere as
shown in Table 3. After the completion of the reaction
(monitored by TLC), 30 mL water was added to the
crude products and stirred for a while. After filtered
and dried under reduced pressure, the excess of amines
and water were removed. Further purification was
accomplished by crystallization (ꢀ10% EtOAc in light
petroleum ether) to get pure products 3, and the isolated
yields were described in Table 3.
1-Ferrocenyl-3-(4-methylphenyl)-3-(piperidin-1-yl)-
propan-1-one (3d): yellow solid; m.p.: 139–141 °C;
IR(KBr): m 2933, 1656, 1454, 1380, 1247, 1106, 815,
496 cmÀ1 1H NMR(400 MHz, CDCl3) d ppm: 7.13–
;
7.27(m, 4H), 4.75(s, 2H), 4.46(s, 2H), 4.18(m, 1H),
4.05(s, 5H), 3.27(s, 2H), 2.42(s, 4H), 2.31(s,3H), 1.36–
1.57(m, 6H); Anal. Calc. for C25 H29 FeNO: C 72.29,
H 7.04, N 3.37, Found: C 72.38, H 6.79, N 3.46.
1-Ferrocenyl-3-(4-methoxyphenyl)-3-(piperidin-1-yl)-
propan-1-one (3e): yellow solid; m.p.: 133–135 °C;
IR(KBr): m 2933, 1656, 1607, 1509, 1453, 1380, 1254,
1106, 824, 499 cmÀ1 1H NMR (400 MHz, CDCl3) d
;
4.2. General procedure for ultrasound-irradiated Michael
addition of amines to ferrocenylenones
ppm: 6.86–7.27(m, 4H), 4.75(s, 2H), 4.46(s, 2H),
4.15(m, 1H), 4.05(s, 5H), 3.77(s, 3H ), 3.27(s, 2H ),
2.42(s, 4H), 1.25–1.58(m, 6H); Anal. Calc. for
C25H29FeNO2: C 69.61, H 6.78, N 3.25, Found: C
69.35, H 6.59, N 3.34.
The mixture of a,b-unsaturated carbonyl compounds
1 (0.5 mmol) and amines 2 (0.5–5 mmol) was added to a
flask which was immersed into the water bath of an
ultrasonic cleaner at room temperature controlled by
circulated water for a specific time as shown in Tables
1–4. After completion of the reaction, the crude product
was washed with petroleum ether to remove the excess
of amines and few unreacted a,b-unsaturated carbonyl
compounds which can be recycled, and the final product
could be obtained if the reactants were pure enough.
Otherwise, further purification as described above could
have been employed to afford products 3, and the yields
were described in Tables 1–4. The analytical data of
compounds 3q–r were in accordance with the reported
values [22], and the spectral data of new compounds
are following:
1-Ferrocenyl-3-(piperidin-1-yl)-3-(pyridin-2-yl)propan-
1-one (3f): yellow solid; m.p.: 114–116 °C; IR(KBr): m
2930, 1665, 1590, 1456, 1379, 1247, 1104, 823, 747,
1
493 cmÀ1; H NMR (400 MHz, CDCl3) d ppm: 7.16–
8.58(m, 4H), 4.79(s, 2H), 4.46(s, 2H), 4.38(m, 1H),
4.11(s, 5H), 3.85(dd, J1 = 17.2 Hz, J2 = 9.2 Hz, 1H),
3.21(d, J = 17.2 Hz, 1H), 2.49(s, 4H), 1.38–1.59(m,
6H); HRMS [Found: m/z, 402.1333 (M+); Calc. for
C23H26FeN2O: M, 402.1395].
1-Ferrocenyl-3-(piperidin-1-yl)-3-(thiophen-2-yl)pro-
pan-1-one (3g): yellow solid; m.p.: 124–126 °C; IR(KBr):
m 2932, 1658, 1456, 1412, 1252, 1105, 880, 715, 497 cmÀ1
;
1H NMR (400 MHz, CDCl3) d ppm: 6.97–7.24(m, 3H),
4.79(d, J = 10.0 Hz, 2H), 4.64(m, 1H), 4.50(s, 2H),

2994
J.-M. Yang et al. / Journal of Organometallic Chemistry 690 (2005) 2989–2995
4.12(s, 5H), 3.27(s, 2H), 2.52(s, 4H), 1.40–1.61(m, 6H);
Anal. Calc. for C22H25FeNOS: C 64.87, H 6.19, N
3.44, Found: C 64.94, H 6.40, N 3.33.
m/z, 435.1050 (M+); Calc. for C24H26ClFeNO: M,
435.1052].
1-Ferrocenyl-3-(furan-2-yl)-3-(piperidin-1-yl)propan-
1-one (3h): yellow solid; m.p.: 105–107 °C; IR(KBr): m
2933, 1660, 1456, 1380, 1252, 1103, 1004, 824, 735,
Acknowledgement
1
499 cmÀ1; H NMR (400 MHz, CDCl3) d ppm: 7.39(s,
This work was supported by the National Nature Sci-
ence Foundation of China (No. 20172039 and
20472062) and Natural Science Foundation of Jiangsu
Province (No. BK2004038).
1H), 6.34(s, 1H), 6.24(s, 1H), 4.80(s, 2H), 4.50(s, 2H),
4.39(dd, J1 = 8.4 Hz, J2 = 4.8 Hz, 1H), 4.14(s, 5H),
3.42(dd, J1 = 16.4 Hz, J2 = 8.8 Hz, 1H), 3.18(d,
J = 15.2 Hz, 1H), 2.40-2.54(m, 4H), 1.38–1.60(m, 6H);
Anal. Calc. for C22H25FeNO2: C 67.53, H 6.44, N
3.58, Found: C 67.47, H 6.47, N 3.40.
References
1-Ferrocenyl-3-(4-chlorophenyl)-3-morpholinopropan-
1-one (3j): yellow solid; m.p.: 173–175 °C; IR(KBr): m
2846, 1662, 1491, 1454, 1266, 1115,1005, 823,
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500 cmÀ1; H NMR (400 MHz, CDCl3) d ppm: 7.27–
(b) S. Hashiguchi, A. Kawada, H. Natsugari, J. Chem. Soc.,
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7.32(m, 4H), 4.72(d, J = 10.4 Hz, 2H), 4.49(s, 2H),
4.05(m, 1H), 4.04(s, 5H), 3.68(s, 4H), 3.18(d,
J = 53.0 Hz, 2H), 2.44(s, 4H); HRMS [Found: m/z,
437.0828 (M+); Calc. for C23H24ClFeNO2: M,
437.0845].
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8 (1997) 3703;
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(1996) 5502;
1-Ferrocenyl-3-(butylamino)-3-(4-chlorophenyl)pro-
pan-1-one (3k): yellow solid; m.p.: 79–81 °C; IR(KBr): m
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983.
3304, 2922, 1661, 1491, 1456, 1378, 1090, 826, 498 cmÀ1
;
1H NMR (400 MHz, CDCl3) d ppm: 7.35–7.40(m,
4H), 4.73(d, J = 9.6 Hz, 2H), 4.51(s, 2H), 4.25(s, 1H),
4.13(s, 5H), 3.05(s, 2H), 2.41–2.47(m, 2H), 1.46(m,
2H), 1.32(m, 2H), 0.88(m, 3H); HRMS [Found:
m/z, 423.1031 (M+); Calc. for C23H26ClFeNO: M,
423.1052].
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1-Ferrocenyl-3-(2-hydroxyethylamino)-3-(4-chloro-
phenyl)propan-1-one (3l): yellow solid; m.p.: 143–145 °C;
IR(KBr): m 3292, 3183, 3122, 2838, 1655, 1493, 1457,
1380, 1079, 832, 500 cmÀ1; 1H NMR (400 MHz, CDCl3)
d ppm: 7.34–7.40(m, 4H), 4.74(d, J = 7.2 Hz, 2H),
4.53(s, 2H), 4.30(t, J = 6.4 Hz, 1H), 4.14(s, 5H),
3.63(d, J = 66.8 Hz, 2H), 3.05(t, J = 4.0Hz, 2H), 2.62–
2.65(m, 2H); HRMS [Found: m/z, 411.0675 (M+); Calc.
for C21H22ClFeNO2: M, 411.0688].
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pan-1-one (3m): yellow solid; m.p.: 113–114 °C;
IR(KBr): m 3314, 2832, 1658, 1456, 1378, 1107, 821,
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738, 701, 482 cmÀ1 1H NMR (400 MHz, CDCl3) d
;
ppm: 7.27–7.46(m, 9H), 4.72(d, J = 11.2 Hz, 2H),
4.50(s, 2H), 4.30(s, 1H), 4.12(s, 5H), 3.62(dd,
J1 = 38.0 Hz, J2 = 13.6 Hz, 2H), 3.06(s, 2H); HRMS
[Found: m/z, 457.0889 (M+); Calc. for C26H24ClFeNO:
M, 457.0896].
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propan-1-one (3o): 128–130 °C; IR(KBr): m 2938, 1679,
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1589, 1401, 1273, 1095, 982, 829, 758, 487 cmÀ1 1H
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NMR (400 MHz, CDCl3) d ppm: 7.97(d, J = 7.4 Hz,
2H), 7.49(d, J = 7.4 Hz, 2H), 4.17(s, 4H), 4.11(s, 5H),
4.10(m, 1H), 3.48(d, J = 96.0 Hz, 2H), 2.40(s, 2H),
2.01–2.06(m, 2H), 1.22–1.34(m, 6H); HRMS [Found:

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