Aminocarbonylation of 1,1′-diiodoferrocene, two-step synthesis of heterodisubstituted ferrocene derivatives via homogeneous catalytic carbonylation/coupling reactions

Article abstract of DOI:10.1016/j.jorganchem.2004.05.046

Detailed investigation of the catalytic carbonylation of 1,1′-diiodoferrocene has been carried out. The importance of the 1′-iodo-ferrocenecarboxamide- or 1′-iodo-ferroceneglyoxylic amide-type products as starting materials for the synthesis of various he

Full text of DOI:10.1016/j.jorganchem.2004.05.046

Journal of Organometallic Chemistry 689 (2004) 2770–2775
www.elsevier.com/locate/jorganchem
Aminocarbonylation of 1,10-diiodoferrocene, two-step synthesis of
heterodisubstituted ferrocene derivatives via homogeneous catalytic
carbonylation/coupling reactions
a,b
Zsolt Szarka , Arpad Kuik , Rita Skoda-Foldes
a
a,b,
c
*
´
´
´ ´ ´
, Laszlo Kollar
¨
a
´ ´
Department of Organic Chemistry, University of Veszprem, Egyetem u. 8, P.O. Box 158, H-8201 Veszprem, Hungary
b
´
Research Group for Petrochemistry of the Hungarian Academy of Sciences, P.O. Box 158, H-8201 Veszprem, Hungary
c
´ ´
Department of Inorganic Chemistry, University of Pecs, P.O. Box 266, H-7624 Pecs, Hungary
Received 23 January 2004; accepted 12 May 2004
Abstract
Detailed investigation of the catalytic carbonylation of 1,10-diiodoferrocene has been carried out. The importance of the 10-iodo-
ferrocenecarboxamide- or 10-iodo-ferroceneglyoxylic amide-type products as starting materials for the synthesis of various heterod-
isubstituted ferrocenes, that can serve as starting materials for ferrocene-based biosensors, was also proved. The potential of this
reaction sequence was shown by the high-yielding synthesis of 10-vinyl ferrocenecarboxamide/glyoxylic amide and 10-acyl ferrocen-
carboxamide derivatives.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Disubstituted ferrocenes; Ferrocene amides; Homogeneous catalysis; Carbonylation; Pd-catalysts
1. Introduction
the selective transmetalation of one tributylstannyl
group of 1,10-bis (tributylstannyl)-ferrocene [5], the
reaction of 1,10-ferrocenedicarboxylic acid with oligopr-
oline-benzylesters, hydroxybenzotriazole and 1-ethyl-3-
(3-dimethylaminopropyl) carbodiimide [6], but in most
cases the first step of the syntheses is the selective
monolithiation of 1,10-dibromo- or 1,10-diiodoferrocene
[7–10].
As palladium-catalysed coupling reactions of 1,10-dii-
odoferrocene with organotin [11] and organozinc com-
pounds [12] have been reported to lead to mixtures of
1-substituted-10-iodo-ferrocenes and symmetrical 1,10-
disubstituted derivatives, we decided to explore the
palladium-catalysed aminocarbonylation of the same
substrate in detail.
In the past few years there has been an increasing in-
terest in the design of new compounds incorporating the
ferrocene skeleton, owing to their utility in diverse fields
of chemistry, such as organic synthesis, catalysis and
materials science [1]. At the same time, relatively few re-
ports have been published concerning the synthesis of
unsymmetrically 1,10-disubstituted ferrocene derivatives.
Although there are some examples for the selective func-
tionalisation of the 10-position of a monosubstituted fer-
rocene [2–4], in most cases the heterodisubstituted
compounds are obtained via the transformation of one
of the two substituents of a symmetrical 1,10-disubsi-
tuted ferrocene derivative. These reactions may involve
Recently, we have found that using iodoferrocene as
substrate, either ferrocene a-ketoamides or ferrocene
amides can be synthesised by homogeneous catalytic car-
bonylation in good yields [13,14]. Optimal conversion
*
Corresponding author. Tel.: +36-88-422-022; fax: +36-427-492.
E-mail address: skodane@almos.vein.hu (R. Skoda-Fo¨ldes).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.05.046

Z. Szarka et al. / Journal of Organometallic Chemistry 689 (2004) 2770–2775
2771
was achieved at 40–50 bar CO pressure. The use of rela-
tively low temperatures (40–60 °C) favoured the forma-
tion of a-ketoamides, while amides were formed with
high selectivity at 100 °C in most cases.
Now we report on the investigation of the carbonyla-
tion reaction of 1,10-diiodoferrocene in the presence of
secondary amines. It is shown that by the proper choice
of the reaction conditions the 10-iodo-ferrocenecarboxa-
mide- or 10-iodo-ferroceneglyoxylic amide-type products
can be isolated in reasonable yields. These compounds
can serve as starting material for the synthesis of unsym-
metrical 1,10-disubstituted ferrocene derivatives of prac-
tical importance.
reactivity of this amine compared to Et2NH which was
evident even at 100 °C, 3b could be isolated only in
31% yield.
CO, HNR2
Pd(OAc)2 + 2 PPh3
I
CONR2
CONR2
Fe
Fe
+
+
Fe
Et3N, toluene
I
CONR2
I
1
2
3
COCONR2
+
CONR2
COCONR2
COCONR2
Fe
Fe
+
Fe
I
COCONR2
4
5
6
ð1Þ
2. Results and discussion
In the reaction of the cyclic secondary amines,
morpholine (c) and piperidine (d), double carbonylation
leading to a-ketoamide type products 4c and 4d pre-
vailed over monocarbonylation at lower temperatures.
This is in accordance with our previous results obtained
during the carbonylation of iodoferrocene [14], where
a-ketoamides were the main products of the reaction
of sterically less hindered secondary amines at 60 °C.
In the present case, formation of 4a and 4b may be
not favoured because the flexible alkyl groups of the
amines and the presence of the iodo substituent on the
second ring may lead to a more crowded palladium-
complex which makes the coordination of a second
carbon monoxide less feasible.
From the point of view of synthetic applications, it is
of special interest, that one of the two iodo-aryl moieties
remained intact resulting in the formation of 3d, 4c and
4d, and might serve as an appropriate functionality in
further reactions. The symmetric diamide 2d could not
be detected when the piperidine/1 ratio was kept at 5/1.
After isolation of the monosubstituted products, 3a,
4c and 4d were chosen as substrates for further functio-
nalisation via homogeneous catalytic coupling and car-
bonylation reactions.
2.1. Carbonylation of 1,10-diiodoferrocene in the presence
of secondary amines
As the next step in our series of investigations con-
cerning the carbonylation reactions of ferrocene deriva-
tives, the aminocarbonylation of 1,10-diiodoferrocene
has been explored.
1,10-Diiodoferrocene (1) [15] was reacted with vari-
ous secondary amines in the presence of an in situ Pd-
catalyst in an autoclave under CO pressure Eq. (1). At
100 °C and 40 bar CO pressure 1 could be converted in-
to diamides 2a–d with excellent selectivity. At the same
time, the presence of iodo derivatives 3 and 4 could
also be observed with shorter reaction times. This obser-
vation prompted us to investigate the effects of the
changes in the reaction conditions in order to isolate
these compounds.
Using Et2NH (a) as the nucleophile, it was observed
that although the decrease of the temperature led to a
dramatic decrease of the conversion, products 3a and
4a were obtained in considerable amounts. Beside 2a an-
other disubstituted derivative (5a) featuring simple and
double carbon monoxide insertion was also formed. It
should be mentioned that the 1,10-bis(glyoxylic amide)
type compounds (6) could never be detected using either
Et2NH or other secondary amines.
An increase in the pressure resulted in somewhat low-
er conversion and an increase in the ratio of double car-
bonylated products 4a and 5a, as it was expected
(compare entries 2 and 4). Using a lower amine/1,10-dii-
odoferrocene ratio (3/1 instead of 10/1) led to a marked
improvement in the relative amount of 3a in the reaction
mixture together with a fall of the conversion. Although
higher conversions could be achieved by the use of
longer reaction times, the isolated yield of 3a remained
approximately the same (35–37%) because the second
carbonylation step leading to 2a became more favoured.
Aminocarbonylation of 1 in the presence of Bu2NH
(b) led to 3b with good selectivity, but due to the lower
2.2. Carbonylation and coupling reactions of 10-
iodo-ferrocenecarboxamide- or 10-iodo-ferroceneglyoxylic
amide derivatives
In order to explore the scope of applicability of the
above-mentioned compounds in the synthesis of het-
erodisubstituted derivatives, they were subjected to
various homogeneous catalytic reactions, namely amin-
ocarbonylation, carbonylative coupling in the presence
of NaBPh4 and Stille-coupling.
Monoamide 3a could be totally converted into dia-
mides 7–9 (isolated yields 77–92% after column chroma-
tography) by reacting it with various secondary amines
Eq. (2) under carbonylation conditions (40 bar CO,
100 °C, 8–16 h). It should be mentioned that in this

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Z. Szarka et al. / Journal of Organometallic Chemistry 689 (2004) 2770–2775
reaction no products with ketoamide functionality due
to double carbonylation could be detected even at lower
temperatures (40–60 °C).
3. Conclusion
We have found that 10-iodo-ferrocenecarboxamide-
or 10-iodo-ferroceneglyoxylic amide-type products can
be isolated in reasonable yields from the reaction mix-
tures produced via aminocarbonylation of 1,10-diiodo-
ferrocene under CO pressure. The products were
successfully used as substrates in palladium-catalysed
aminocarbonylation, coupling and carbonylative cou-
pling reactions. These reactions led to the selective for-
mation of unsymmetrical ferrocene 1,10-diamides, or
10-vinyl-1-amide/glyoxylic amide- and 10-benzoyl-1-
amide-type products, respectively.
It should be added, that in spite of the high conver-
sion and excellent selectivity of the aminocarbonylation
reaction, this two-step procedure for the synthesis of un-
symmetrically substituted ferrocene diamides seems to
be inferior to the one-pot aminocarbonylation starting
from 1,10-diiodoferrocene in the presence of two differ-
ent amines, due to the moderate yield of 3a in the first
step [16].
CONEt2
I
CO, HNR2
Pd(OAc)2 + 2 PPh3
o
Fe
Et3N, toluene, 100
C
4. Experimental
The H and 13C NMR spectra were recorded on a
1
3a
ð2Þ
NR2:
7
N
O
VARIAN INOVA 400 spectrometer at 400 and 100.58
MHz, respectively. GLC analyses were carried out with
a HP-5890/II gas chromatograph using a 15 m HP-5 col-
umn. Infrared (IR) spectra were recorded in KBr pellets
using a Specord-IR 75 instrument. GC–MS measure-
ments were performed with a Hewlett–Packard 5971A
GC–MSD using HP-1 column.
CONEt2
8
N
Fe
CONR2
9
NBu2
Stille-coupling of 3a, 4c and 4d with vinyltributyltin
in the presence of Pd(PPh3)4 led to functionalised vinylf-
errocenes 10–12 in a smooth reaction. The formation of
no byproducts was observed.
4.1. Carbonylation of 1,10-diiodoferrocene (1)
1,10-Diiodoferrocene (0.5 mmol), Pd(OAc)2 (0.05
mmol), PPh3 (0.1 mmol), the secondary amine (1.5 or
2.5 or 5 mmol, as indicated in Table 1.), Et3N (0.5
mL) and toluene (12.5 mL) were transferred under an in-
ert atmosphere into a stainless steel autoclave. It was
charged with carbon monoxide and heated with stirring
in an oil bath. Then the volatile components were re-
moved in vacuo. The residue was dissolved in toluene
(20 mL), washed with 5% H3PO4 (20 mL), saturated
aqueous NaHCO3 (20 mL) and brine (20 mL) and dried
over Na2SO4. The products were separated after remov-
al of the solvent by chromatography (aluminium oxide,
benzene/EtOAc=3/1). The structures of the isolated
R'
I
CH2=CHSnBu3
Pd(PPh3)4
o
R'
Fe
Fe
toluene, 100
C
ð3Þ
3a R': CONEt2
4c R': COCO
10 R': CONEt2
11 R': COCO
N
O
N
O
4d R': COCO
12 R': COCO
N
N
1
compounds were determined by H, 13C NMR and IR
The carbonylative coupling reaction elaborated for
the synthesis of steroidal phenyl ketones [17] could also
be successfully used for the conversion of 3a. The sub-
strate was reacted with NaBPh4 under atmospheric
CO pressure using Pd(PPh3)4 catalyst. The reaction re-
sulted in the selective formation of 13 (isolated yield:
78%).
spectroscopy, elemental analysis, and MS.
Physical properties and spectra of 2a, 2c and 2d cor-
responded well to literature data [18].
4b and 5a were not isolated and were characterised by
GC–MS. 4b: MS (m/z/rel. int.): 495(M+)/100; 339/94;
311/22; 247/13; 213/22; 183/81. 5a: MS (m/z/rel. int.):
412(M+)/100; 312/32; 241/75; 220/42; 121/33.
4.1.1. 1,10-Bis(N,N-dibutyl carboxamido) ferrocene(2b)
1H NMR(CDCl3) d: 4.59 (t, 1.9 Hz, 4H, Cp); 4.34 (t,
1.9 Hz, 4H, Cp); 3.35 (t, 7.8Hz, 8H, NCH2); 1.58 (m,
8H, NCH2CH2); 1.15 (m, 8H, N(CH2)2CH2); 0.89 (m,
12H, N(CH2)3CH3). IR (KBr (cmꢀ1)): 1618. MS (m/z/
rel. int.): 496(M+)/100; 368/12; 340/17; 241/32; 128/35;
CO, NaBPh4
Pd(PPh3)4
o
CONEt2
COPh
Fe
3a
toluene, 100
C
ð4Þ
13

Z. Szarka et al. / Journal of Organometallic Chemistry 689 (2004) 2770–2775
2773
Table 1
Carbonylation of 1,10-diiodoferrocene in the presence of amines
Entry
Amine
Temperature
(°C)
Pressure
(bar)
Reaction time
(h)
Conv.a
(%)
Ratio of the productsa (%)
Isolated yields
(%) (compound)
2
3
4
5
1
2
Et2NH (a)
Et2NH (a)
100
60
40
40
40
50
40
40
40
40
40
40
40
40
40
40
8
8
95b
88b
52b
83b
58c
68c
81c
75b
48b
68d
88b
78d
84b
70d
100
64
48
50
28
31
43
100
27
35
91
19
100
–
–
–
–
92 (2a) [14]
18
24
22
66
62
49
–
5
13
8
3
Et2NH (a)
Et2NH (a)
50
60
8
20
16
5
4
8
12
1
11 (4a)
35 (3a)
70 (2b)
5
Et2NH (a)
Et2NH (a)
Et2NH (a)
40
40
26
34
48
8
6
5
2
7
40
6
2
8
Bu2NH (b)
Bu2NH (b)
Bu2NH (b)
Morpholine (c)
Morpholine (c)
Piperidine (d)
Piperidine (d)
100
60
–
–
9
8
66
57
9
7
–
10
11
12
13
14
40
40
8
8
–
31 (3b)
72 (2c)
100
60
–
–
36
8
23
–
58
–
–
14 (3c), 40 (4c)
75 (2d)
19 (3d), 38 (4d)
100
60
–
36
35
65
–
a
Determined by GC.
b
c
mmol R2NH/mmol diiodoferrocene=10/1.
mmol R2NH/mmol diiodoferrocene=3/1.
mmol R2NH/mmol diiodoferrocene=5/1.
d
121/32; 57/38; 56/12. Anal. Calc. for C28H44FeN2O2
(496.52): C, 67.73; H, 8.93; N, 5.64. Found: C, 67.51;
H, 8.79; N, 5.51%. Yield: 70%.
311/8;213/13; 183/13; 56/10. Anal. Calc. for C15H16FeI-
NO2 (425.05): C, 42.39; H, 3.79; N, 3.30. Found: C,
42.60; H, 3.87; N, 3.19%. Yield: 14%.
4.1.2. 10-Iodo-N,N-diethyl ferrocenecarboxamide (3a)
1H NMR(CDCl3) d: 4.58 (brs, 2H, Cp-2,5); 4.45 (brs,
2H, Cp-20,50); 4.25 (brs, 2H, Cp-3,4); 4.20 (brs, 2H, Cp-
30,40); 3.50 (m, 4H, NCH2CH3); 1.20 (m, 6H,
NCH2CH3). 13C NMR(CDCl3) d: 168.7; 81.0; 76.3;
72.9; 72.6; 71.1; 41.2; 40.1; 39.9; 14.2; 13.8. IR (KBr
(cmꢀ1)): 1609. MS (m/z/rel. int.): 411(M+)/100; 339/26;
311/19; 284/37; 247/19; 213/78; 183/63; 56/4. Anal. Calc.
for C15H18FeINO (411.07): C, 43.83; H, 4.41; N, 3.41.
Found: C, 44.05; H, 4.29; N, 3.57%. Yield: 35%.
4.1.5. 10-Iodo-piperidino ferrocenecarboxamide (3d)
1H NMR(CDCl3) d: 4.5 (t, 1.6 Hz, 2H, Cp); 4.43 (t,
1.6 Hz, 2H, Cp); 4.26 (t, 1.6 Hz, 2H, Cp);4.25 (t, 1.6
Hz, 2H, Cp); 3.59 (m, 4H, NCH2); 1.57 (m, 6H,
NCH2(CH2)3). 13C NMR(CDCl3) d: 168.3; 81.5; 76.4;
73.0; 72.4; 71.2; 46.2; 43.1; 40.1; 29.7; 26.1; 24.8. IR
(KBr (cmꢀ1)): 1616. MS (m/z/rel. int.): 423(M+)/100;
339/11; 311/11, 296/35; 247/11; 213/45; 183/35; 56/15.
Anal. Calc. for C16H18FeINO (423.08): C, 45.42; H,
4.29; N, 3.31. Found: C, 45.27; H, 4.12; N, 3.45%. Yield:
19%.
4.1.3. 10-Iodo-N,N-dibutyl ferrocenecarboxamide (3b)
1H NMR(CDCl3) d: 4.53 (t, 1.8 Hz, 2H, Cp); 4.41 (t,
1.8 Hz, 2H, Cp); 4.26 (t, 1.8 Hz, 2H, Cp); 4.22 (t, 1.8 Hz,
2H, Cp); 3.37 (t, 7.9Hz, 4H, NCH2); 1.57 (q, 4H, 7.9 Hz,
NCH2CH2); 1.31 (m, 4H, N(CH2)2CH2); 0.92 (t, 6H,
7.9Hz, N(CH2)3CH3). IR (KBr (cmꢀ1)): 1610. MS (m/
z/rel. int.): 467(M+)/100; 339/92; 311/85; 247/62; 213/
123;183/169. Anal. Calc. for C19H26FeINO (467.17):
C, 48.85; H, 5.61; N, 3.00. Found: C, 48.97; H, 5.47;
N, 3.12%. Yield: 31%.
4.1.6. 10-Iodo-N,N-diethyl ferroceneglyoxylic amide (4a)
1H NMR(CDCl3) d: 4.82 (brs, 2H, Cp); 4.58 (brs, 2H,
Cp); 4.53 (brs, 2H, Cp); 4.38 (brs, 2H, Cp); 3.46 (q, 6.8
Hz, 2H, NCH2CH3); 3.25 (q, 6.8 Hz, 2H, NCH2CH3);
1.23 (t, 6.8 Hz, 3H, NCH2CH3); 1.14 (t, 6.8 Hz, 3H,
NCH2CH3). 13C NMR(CDCl3) d: 197.7; 166.3; 77.5;
76.4; 76.1; 72.4; 72.3; 42.3; 39.9; 39.0; 14.2; 12.8. IR
(KBr (cmꢀ1)): 1642, 1661. MS (m/z/rel. int.): 439(M+)/
100; 339/83; 311/39; 275/15; 183/27; 128/18; 100/43; 72/
68; 56/32. Anal. Calc. for C16H18FeINO2 (439.08): C,
43.77; H, 4.13; N, 3.19. Found: C, 43.52; H, 4.01; N,
3.31%. Yield: 11%.
4.1.4. 10-Iodo-morpholino ferrocenecarboxamide (3c)
1H NMR(CDCl3) d: 4.51 (t, 1.6 Hz, 2H, Cp); 4.43 (t,
1.6 Hz, 2H, Cp); 4.35 (t, 1.6 Hz, 2H, Cp);4.25 (t, 1.6 Hz,
2H, Cp); 3.68 (m, 8H, NCH2CH2O). 13C NMR(CDCl3)
d: 168.8; 80.3; 76.6; 73.1; 72.6; 71.2; 66.9; 40.1. IR (KBr
(cmꢀ1)): 1618. MS (m/z/rel. int.): 425(M+)/100; 339/15;
4.1.7. 10-Iodo-morpholino ferroceneglyoxylic amide (4c)
1H NMR(CDCl3) d: 4.85 (t, 1.5 Hz, 2H, Cp); 4.60
(t, 1.5 Hz, 2H, Cp); 4.52 (t, 1.5 Hz, 2H, Cp); 4.35 (t,

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Z. Szarka et al. / Journal of Organometallic Chemistry 689 (2004) 2770–2775
1.5 Hz, 2H, Cp); 3.69 (m, 6H, morpholine); 3.45 (m,
2H, morpholine). 13C NMR(CDCl3) d: 196.4; 165.0;
76.7; 76.1; 72.6; 72.1; 70.7; 66.8; 66.7; 46.5; 41.7;
39.8. IR (KBr (cmꢀ1)): 1646; 1667. MS (m/z/rel.
int.): 453(M+)/91; 339/100; 311/40; 183/21; 128/15; 56/
12. Anal. Calc. for C16H16FeINO3 (453.06): C,
42.42; H, 3.56; N, 3.09. Found: C, 42.55; H, 3.67;
N, 3.21%. Yield: 40%.
4.3. Stille-coupling of 3a, 4c and 4d
Pd(PPh3)4 (0.005 mmol) and the iodoferrocene-deriv-
ative (0.25 mmol) were added to a flask equipped with a
reflux condenser and a septum inlet. The flask was
flushed with argon and charged with 2.5 mL of toluene.
0.3 mmol of vinyltributyltin was added by means of a
hypodermic syringe through the septum inlet. The mix-
ture was stirred at 100 °C. The reaction was followed by
GC and TLC. After completion of the vinylation an
aqueous solution of 0.6 mmol KF was added and the
mixture was stirred overnight. The organic layer was
separated, dried over Na2SO4. The product was purified
after removal of the solvent by chromatography on alu-
minium oxide (eluent: benzene/EtOAc 85/15). The struc-
tures of the isolated compounds were determined by 1H,
13C NMR and IR spectroscopy, elemental analysis, and
MS.
4.1.8. 10-Iodo-piperidino ferroceneglyoxylic amide (4d)
1H NMR(CDCl3) d: 4.82 (brs, 2H, Cp); 4.55 (brs,
2H, Cp); 4.50 (brs, 2H, Cp); 4.35 (brs, 2H, Cp); 3.59
(m, 2H, NCH2); 3.30 (m, 2H, NCH2); 1.62 (m, 4H,
NCH2CH2); 1.54 (m, 2H, N(CH2)2CH2). IR (KBr
(cmꢀ1)): 1644; 1662. MS (m/z/rel. int.): 451(M+)/22;
339/62; 311/32; 183/48; 128/54; 121/39; 56/100. Anal.
Calc. for C17H18FeINO2 (451.09): C, 45.27; H, 4.02;
N, 3.11. Found: C, 45.45; H, 4.15; N, 3.21%. Yield:
38%.
4.3.1. 10-Vinyl-N,N-diethyl ferrocenecarboxamide (10)
1H NMR(CDCl3) d: 6.42 (dd, 10.8 Hz, 17.6 Hz,
1H, CH‚CH2); 5.35 (dd, 1.2 Hz, 17.6 Hz, 1H,
CH‚CHAHB); 5.05 (dd, 1.2 Hz, 10.8 Hz, 1H,
CH‚CHAHB); 4.53 (t, 2 Hz, 2H, Cp); 4.37 (t, 2 Hz,
2H, Cp); 4.26 (t, 2 Hz, 2H, Cp); 4.22 (t, 2 Hz, 2H,
Cp); 3.49 (q, 6.8 Hz, 4H, NCH2CH3); 1.20 (t, 6.8Hz,
6H, NCH2CH3). 13C NMR(CDCl3) d: 169.2; 133.8;
112.1; 84.7; 79.5; 71.4; 70.7; 70.6; 68.4; 42.6; 40.4; 14.3;
12.8. IR (KBr (cmꢀ1)): 1608. MS (m/z/rel. int.):
311(M+)/100; 239/56; 212/51; 210/50; 121/55; 56/34.
Anal. Calc. for C17H21FeNO (311.21): C, 65.61; H,
6.80; N, 4.50. Found: C, 65.78; H, 6.71; N, 4.57%. Yield:
69%.
4.2. Aminocarbonylation of 3a
3a (0.25 mmol, 203 mg), Pd(OAc)2 (0.0125 mmol,),
PPh3 (0.025 mmol), the secondary amine (1.25 mmol),
Et3N (0.125 mL) and toluene (5 mL) were transferred
under an inert atmosphere into a stainless steel auto-
clave. It was charged with carbon monoxide (40 bar)
and heated with stirring in an oil bath at 100 °C. Then
the volatile components were removed in vacuo. The
residue was dissolved in toluene (15 mL), washed with
5% H3PO4 (15 mL), saturated aqueous NaHCO3 (15
mL) and brine (15 mL) and dried over Na2SO4. The
products were purified after removal of the solvent by
chromatography (aluminium oxide, benzene/EtO-
Ac=3/1). The structures of the isolated compounds were
4.3.2. 10-Vinyl-morpholino ferroceneglyoxylic amide (11)
1H NMR(CDCl3) d: 6.34 (dd, 10.8 Hz, 17.6 Hz, 1H,
CH‚CH2);5.36(dd,1.2Hz,17.6Hz,1H,CH‚CHAHB);
5.11 (dd, 1.2 Hz, 10.8 Hz, 1H, CH‚CHAHB);4.76 (brs,
2H, Cp); 4.55 (brs, 2H, Cp); 4.46 (brs, 2H, Cp); 4.38 (brs,
2H, Cp); 3.74 (m, 2H, morpholine); 3.69 (m, 2H, morpho-
line);3.64(m, 2H, morpholine);3.42(m, 2H, morpholine).
13C NMR(CDCl3) d: 196.9; 165.2; 132.6; 113.4; 86.0; 75.5;
75.2; 71.6; 71.2; 68.9; 66.8; 66.7; 46.4; 41.7. IR (KBr
(cmꢀ1)): 1630, 1652. MS (m/z/rel. int.): 353(M+)/36; 239/
100; 211/82; 121/57; 56/55. Anal. Calc. for C18H19FeNO3
(353.20): C, 61.21; H, 5.42; N, 3.97. Found: C, 61.37; H,
5.31; N, 3.85%. Yield: 85%.
1
determined by H, 13C NMR and IR spectroscopy, ele-
mental analysis, and MS.
Analytical data of 7 and 8 have been reported else-
where [16].
4.2.1. 10-(N0,N0-Dibutyl-carbamoyl)-N,N-diethyl ferro-
cenecarboxamide (9)
1H NMR(CDCl3) d: 4.62 (brs, 2H, Cp); 4.58 (brs, 2H,
Cp); 4.35 (brs, 2H, Cp); 4.27 (brs, 2H, Cp); 3.44 (q, 6.4
Hz, 4H, NCH2CH3); 3.35 (t, 8Hz, 4H, NCH2CH2); 1.54
(m, 4H, NCH2CH2); 1.26 (m, 4H, N(CH2)2CH2); 1.17 (t,
6.4 Hz, 6H, NCH2CH3); 0.91 (t, 8Hz, 6H,
N(CH2)3CH3). 13C NMR(CDCl3) d: 169.2; 169.0; 81.1;
80.6; 71.7; 71.6; 71.5; 71.3; 48.5; 46.4; 42.5; 40.9; 31.4;
29.6; 20.2; 20.1; 13.8. IR (KBr (cmꢀ1)): 1614. MS (m/z/
rel. int.): 440(M+)/100; 241/37; 220/43; 128/65; 121/80;
70/63; 57/35; 56/32. Anal. Calc. for C24H36FeN2O2
(440.41): C, 65.45; H, 8.24; N, 6.36. Found: C, 65.63;
H, 8.31; N, 6.28%. Yield: 77%.
4.3.3. 10-Vinyl-piperidino ferroceneglyoxylic amide
(12)
1H NMR(CDCl3) d: 6.36 (dd, 10.4 Hz, 17.6 Hz,
1H, CH‚CH2); 5.36 (dd, 1.2 Hz, 17.6 Hz, 1H,
CH‚CHAHB); 5.11 (dd, 1.2 Hz, 10.4 Hz, 1H,
CH‚CHAHB); 4.74 (t, 2 Hz, 2H, Cp); 4.52 (t, 2 Hz,
2H, Cp); 4.47 (t, 2 Hz, 2H, Cp); 4.39 (t, 2 Hz, 2H,

Z. Szarka et al. / Journal of Organometallic Chemistry 689 (2004) 2770–2775
2775
Cp); 3.6 (m, 2H, NCH2); 3.31 (m, 2H, NCH2); 1.62 (m,
Acknowledgement
4H, NCH2CH2); 1.55 (m, 2H, N(CH2)2CH2). 13C
NMR(CDCl3) d: 198.0; 165.3; 132.8; 113.2; 85.9; 75.7;
74.9; 71.7; 71.1; 68.9; 47.1; 42.2; 26.2; 25.5; 24.5. IR
(KBr (cmꢀ1)): 1630, 1650. MS (m/z/rel. int.): 351(M+)/
56; 239/100; 211/52; 121/32; 56/27. Anal. Calc. for
C19H21FeNO2 (351.23): C, 64.97; H, 6.03; N, 3.99.
Found: C, 65.11; H, 6.11; N, 4.10%. Yield: 82%.
The authors thank the Hungarian National Science
Foundation for financial support (OTKA T032111,
TS044742, T035047).
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saturated aqueous NaHCO3 (15 mL) and brine (15
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Hz, 1H, Ph); 7.44 (t, 6 Hz, 2H, Ph); 4.93 (brs, 2H, Cp);
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´
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