A simple four-component synthesis of ferrocenyl amidodiesters and ferrocenyl triamides

Article abstract of DOI:10.1016/j.jorganchem.2011.07.036

Ferrocenyl amidodiesters and ferrocenyl triamides were synthesized in good yields by a four-component reaction of ferrocenecarboxaldehyde, isocyanides, Meldrom's acid and alcohols or amines in CH₂Cl₂ at room temperature.

Full text of DOI:10.1016/j.jorganchem.2011.07.036

Journal of Organometallic Chemistry 696 (2011) 3421e3424
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
A simple four-component synthesis of ferrocenyl amidodiesters and ferrocenyl
triamides
*
Roya Akbarzadeh, Tayebeh Amanpour, Peiman Mirzaei, Ayoob Bazgir
Department of Chemistry, Shahid Beheshti University, General Campus, Tehran 1983963113, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Ferrocenyl amidodiesters and ferrocenyl triamides were synthesized in good yields by a four-component
reaction of ferrocenecarboxaldehyde, isocyanides, Meldrom’s acid and alcohols or amines in CH2Cl2 at
room temperature.
Received 22 January 2011
Received in revised form
24 April 2011
Ó 2011 Elsevier B.V. All rights reserved.
Accepted 26 July 2011
Keywords:
Ferrocenecarboxaldehyde
Meldrom’s acid
Ferrocenyl amidodiester
Ferrocenyl triamides
Isocyanide
1. Introduction
triamides via IMCRs is useful in functionalizing ferrocenes, because
oxidation can be easily avoided, reaction conditions are mild, and
Within the past decade, the resurgence of interest in multi-
component reactions (MCRs) has been driven, not only due to their
convergent nature, superior atom economy, and straightforward
experimental procedures but also because of their value to the
pharmaceutical industry for construction of low molecular weight
compound libraries through combinatorial strategies and parallel
synthesis [1e4]. Due to the unique reactivity of the isocyanide
functional group, MCRs involving isocyanides are among the most
versatile, in terms of the number and variety of compounds which
can be generated [5e10]. In this context, ferrocene derivatives show
interesting features that make them attractive for use in
isocyanide-based multicomponent reactions (IMCRs).
ester or amide groups may be transformed into a variety of func-
tional groups.
As part of our program aimed at developing new methodologies
for the preparation of new organic compounds [20e24], very
recently, we have reported synthesis of ferrocenyl bis-amides [25].
Herein, we describe an efficient synthetic approach to ferrocenyl
amidodiesters and ferrocenyl triamides by an isocyanide-based
four-component reaction.
2. Results and discussion
The one-pot four-component condensation reactions of ferro-
cenecarboxaldehyde 1, isocyanides 2aec, Meldrom’s acid 3 and
alcohols 4aef proceeded spontaneously at room temperature in
dichloromethane and were complete after 24 h to afford corre-
sponding ferrocenyl amidodiesters 5aek in good yields (Table 1).
To the best of our knowledge, this new four-component strategy
provides the first example of an efficient synthesis of ferrocenyl
amidodiesters and is the most simple and convenient and would be
applicable for the synthesis of different types of ferrocenyl ami-
dodiester derivatives.
Ferrocene derivatives find an ever growing application in many
fields, from chiral catalysis [11,12] to material science [13e17], to
medicinal chemistry [18,19].
A number of reasons may be
enumerated to explain the success of ferrocenes, among which, its
unusual stability for an organometallic species: ferrocenes can be
handled in the air when solid and often in solution also. Ferrocenes
are reactive aromatic compounds, but they are sensitive to
oxidizing agents e as most electrophilic reagents are e as well as to
acids. Thus, formation of ferrocenyl amidoesters or ferrocenyl
Compounds 5 are stable solids whose structures were estab-
lished by IR, 1H and 13C NMR spectroscopy and elemental analysis.
The elucidation of the structure of 5 using IR, 1H and 13C NMR
spectroscopic data is discussed with 5a as an example. The IR
spectrum of 5a exhibited absorption bands due to carbonyl groups
* Correspondence author. Fax: þ98 21 22431661.
E-mail address: a_bazgir@sbu.ac.ir (A. Bazgir).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.07.036

3422
R. Akbarzadeh et al. / Journal of Organometallic Chemistry 696 (2011) 3421e3424
Table 1
Synthesis of ferrocenyl amidodiesters 5
Scheme 2. Synthesis of heterocyclic ferrocenyl amidodiester 10.
.
Products 5
R
R0OH
Yield (%)
To further explore the potential of this protocol for ferrocene
derivatives synthesis, we investigated reaction of ferrocene-
carboxaldehyde 1, isocyanides 2 and Meldrom’s acid 3 in the
presence of aromatic amine 11 and obtained ferrocenyl triamide 12
in good yields (Scheme 3).
Due to the importance of ferrocenyl heterocyclic compounds
[29], we used indole 13 as nucleophile in the reaction. This made it
possible to synthesize new N-cyclohexyl-2-ferrocenyl-4-(1H-indol-
3-yl)-3-(1H-indole-3-carbonyl)-4-oxobutanamide 14 (Scheme 4).
a
b
c
d
e
f
g
h
i
Cyclohexyl
tert-Butyl
2,6-Dimethylphenyl
Cyclohexyl
tert-Butyl
Cyclohexyl
tert-Butyl
Cyclohexyl
Cyclohexyl
Cyclohexyl
tert-Butyl
CH3OH
CH3OH
CH3OH
CH3CH2OH
90
73
80
64
55
75
53
62
68
85
70
CH3CH2OH
CH3CH2CH2OH
CH3CH2CH2OH
CH3CHOHCH3
C6H5CH2OH
4-MeOeC6H4CH2OH
4-MeOeC6H4CH2OH
j
k
3. Conclusion
at 1679 and 1631 cmꢀ1 and the NH absorption of amide group was
observed at 3270 cmꢀ1. The 1H NMR spectrum of 5a consisted of
multiplet signals for the cyclohexyl rings (dH 1.19e1.73 ppm) and
the NHeCH resonance (dH 3.65) and two sharp singlets for the
methoxy groups (dH 3.48 and 3.59 ppm). Two methine groups were
observed as a doublet (dH 3.78, J ¼ 11.3 Hz) and a broad singlet (dH
4.33 ppm). A broad resonance (dH 8.20 ppm) was observed for the
NH group and a multiplet signal for the ferrocenyl hydrogens (dH
4.08e4.14 ppm). The 1H- decoupled 13C-NMR spectrum of 5a
showed 18 distinct signals, in agreement with the proposed
structure.
In conclusion, we have described for the first time a new and
successful strategy for the convenient synthesis of ferrocenyl ami-
dodiesters and ferrocenyl triamides via a isocyanide-based four-
component condensation reaction. The method offers several
advantages including good yields of products and the reaction is
performed under neutral conditions by simple mixing of the
starting materials.
4. Experimental
4.1. General
The formation of product 5 can be rationalized by initial
formation of heterodiene 6 by standard Knoevenagel condensation
of 1 and 3 [26]. Subsequent [1 þ 4] cycloaddition reaction with
isocyanide 2 affords an iminolactone intermediate 7 [27,28], fol-
lowed by reaction with alcohol leads to the vinylogous carbonate 8.
Subsequently loss of acetone from 8 and the reaction with another
molecule of alcohol to afford product 5 (Scheme 1) [24].
When the benzo[d][1,3]dioxol-2-ylmethanol 9 was used as
a heterocyclic benzyl alcohol (Scheme 2), the bis(benzo[d][1,3]
dioxol-2-ylmethyl)2-(2-(cyclohexylamino)-1-ferrocenyl-2-oxoethyl)
malonate 10 was obtained in 53% yield under the same reaction
conditions.
Melting points were measured on an Electrothermal 9100
apparatus and are uncorrected. IR spectra were recorded on a Shi-
madzu IR-470 spectrometer. 1H and 13C NMR spectra were recorded
on a BRUKER DRX-300 AVANCE spectrometer at 300.13 and
75.47 MHz, respectively. Elemental analyses were performed using
a Heracus CHNeO-Rapid analyzer. Chemicals were purchased from
Fluka or Merck and used as received.
4.2. General procedure for the preparation of ferrocene derivatives
A mixture of ferrocenecarboxaldehyde (1 mmol), Meldrom’s
acid (1 mmol), isocyanide (1 mmol) and alcohol or amine or indole
Scheme 1. Mechanism of the reaction.
Scheme 3. Synthesis of ferrocenyl triamide 12.

R. Akbarzadeh et al. / Journal of Organometallic Chemistry 696 (2011) 3421e3424
3423
4.2.6. Compound 5f
Cream powder (75%); mp 186e189 ꢁC. IR (KBr) (nmax/cmꢀ1):
3289 (NH), 1752 and 1636 (CO). 1H NMR (300 MHz, DMSO-d6): dH
0.76 (t, J ¼ 8.1 Hz, Me, 3H), 0.83 (t, J ¼ 7.8 Hz, Me, 3H), 1.19e1.31 (m,
3CH2 of cyclohexyl, 6H), 1.40e1.59 (m, 2CH2, 4H), 1.71e1.79 (m,
2CH2 of cyclohexyl, 4H), 3.41 (m, CHeN of cyclohexyl, 1H), 3.63 (d,
J ¼ 9.1 Hz, CH, 1H), 3.75 (d, J ¼ 9.2 Hz, CH, 1H), 3.84 (t, J ¼ 6.7, CH2,
2H), 3.97 (t, J ¼ 8.2, CH2, 2H), 4.07e4.15 (m, CHfer, 9H), 8.22 (d,
J ¼ 8.7 Hz, NH,1H). Anal. Calcd for C27H37FeNO5: C, 63.41; H, 7.29; N,
2.74%. Found: C, 63.54; H, 7.20; N, 2.65% (due to the very low
solubility of product 5f, we were unable to obtain a 13C NMR
spectrum for this product).
Scheme 4. Synthesis of ferrocene containing indole moiety 14.
(2 mmol) in CH2Cl2 (3 mL) was stirred for 24 h (the progress of
reaction was monitored by TLC). After completion of reaction, the
reaction mixture was filtered and the precipitate washed with
ether (5 mL) to afford the pure product.
4.2.7. Compound 5g
Dark purple oil (53%). IR (KBr) (nmax/cmꢀ1): 3330 (NH), 1738 and
1699 (CO). 1H NMR (300 MHz, DMSO-d6): dH 0.77 (t, J ¼ 7.5 Hz, Me,
3H), 0.83 (t, J ¼ 7.2 Hz, Me, 3H), 1.30 (s, CMe3, 9H), 1.39e1.57 (m,
2CH2, 4H), 3.57 (d, J ¼ 11.9 Hz, CH, 1H), 3.79 (bs, CH, 1H), 3.86e3.99
(m, 2OCH2, 4H), 4.07e4.18 (m, CHfer, 9H), 7.97 (s, NH, 1H). 13C NMR
(75 MHz, DMSO-d6): dC 10.5, 10.6, 21.7, 21.8, 28.8, 45.7, 50.7, 58.1,
66.7, 66.9, 67.3, 67.8, 68.0, 69.1, 69.8, 85.3, 167.4, 168.1, 169.9. Anal.
Calcd for C25H35FeNO5: C, 61.86; H, 7.27; N, 2.89%. Found: C, 61.94;
H, 7.21; N, 2.35%.
4.2.1. Compound 5a
Cream powder (90%); mp 209e211 ꢁC. IR (KBr) (nmax/cmꢀ1):
3270 (NH), 1679 and 1631 (CO). 1H NMR (300 MHz, DMSO-d6): dH
1.19e1.73 (m, 5CH2 of cyclohexyl, 10H), 3.48 (s, MeO, 3H), 3.59 (s,
MeO, 3H), 3.65 (bs, CHeN of cyclohexyl,1H), 3.78 (d, J ¼ 11.3 Hz, CH,
1H), 3.86 (bs, CH,1H), 4.08e4.14 (m, CHfer, 9H), 8.20 (bs, NH,1H). 13
C
NMR (75 MHz, DMSO-d6): dC 24.9, 25.1, 25.7, 32.6, 32.9, 45.6, 48.2,
52.8, 57.6, 66.9, 67.4, 68.1, 68.2, 69.2, 84.7, 167.6, 168.7, 169.3. Anal.
Calcd for C23H29FeNO5: C, 60.67; H, 6.42; N, 3.08%. Found: C, 60.58;
H, 6.47; N, 3.02%.
4.2.8. Compound 5h
Dark purple oil (62%). IR (KBr) (nmax/cmꢀ1): 3447 (NH), 1713 and
1699 (CO). 1H NMR (300 MHz, DMSO-d6): dH 0.96e1.69 (m, 5CH2 of
cyclohexyl and 4Me, 22H), 3.68 (m, CHeN of cyclohexyl, 1H), 3.71
(bs, CH, 1H), 3.86 (bs, CH, 1H), 4.04e4.27 (m, CHfer, 9H), 4.71 (m,
CHO, 1H), 4.79 (m, CHO, 1H), 8.19 (bs, NH, 1H). 13C NMR (75 MHz,
DMSO-d6): dC 21.7, 21.8, 24.9, 25.1, 25.7, 32.6, 32.8, 45.1, 48.3, 58.2,
66.9, 67.1, 67.9, 68.8, 68.9, 69.1, 84.9, 166.8, 167.3, 169.5. Anal. Calcd
for C27H37FeNO5: C, 63.41; H, 7.29; N, 2.74%. Found: C, 63.32; H,
7.22; N, 2.65%.
4.2.2. Compound 5b
Light brown powder (73%); mp 159e161 ꢁC. IR (KBr) (nmax
/
cmꢀ1): 3397 (NH), 1747 and 1672 (CO). 1H NMR (300 MHz, DMSO-
d6): dH 1.29 (s, CMe3, 9H), 3.48 (s, MeO, 3H), 3.58 (s, MeO, 3H), 3.82
(d, J ¼ 9.9 Hz, CH, 1H), 3.84 (bs, CH, 1H), 4.07e4.17 (m, CHfer, 9H),
7.97 (s, NH, 1H). 13C NMR (75 MHz, DMSO-d6): dC 28.8, 45.9, 50.7,
52.8, 57.7, 66.8, 67.4, 67.8, 67.9, 69.1, 85.2, 167.7, 168.5, 169.8. Anal.
Calcd for C21H27FeNO5: C, 58.75; H, 6.34; N, 3.26%. Found: C, 58.65;
H, 6.26; N, 3.18%.
4.2.9. Compound 5i
4.2.3. Compound 5c
Dark purple oil (68%). IR (KBr) (nmax/cmꢀ1): 3273 (NH), 1749 and
1731 (CO). 1H NMR (300 MHz, DMSO-d6): dH 1.09e1.81 (m, 5CH2 of
cyclohexyl, 10H), 3.57 (m, CHeN of cyclohexyl, 1H), 3.78 (d,
J ¼ 9.1 Hz, CH, 1H), 3.84 (bs, CH, 1H), 4.05e4.14 (m,CHfer, 9H), 4.90
and 4.98 (ABq, J ¼ 14.6 Hz, CH2O, 2H), 5.06 and 5.11 (ABq,
J ¼ 12.9 Hz, CH2O, 2H), 7.16e7.34 (m, HeAr, 10H), 8.24 (d, J ¼ 8.3 Hz,
NH, 1H). 13C NMR (75 MHz, DMSO-d6): dC 24.9, 25.1, 25.7, 32.6, 32.8,
45.4, 48.3, 57.9, 66.8, 67.0, 67.5, 68.1, 68.4, 69.2, 84.8, 128.11, 128.5,
128.7, 128.8, 135.5, 135.9, 167.0, 167.5, 169.2, 180.1. Anal. Calcd for
C35H37FeNO5: C, 69.20; H, 6.14; N, 2.31%. Found: C, 69.32; H, 6.07; N,
2.40%.
Cream powder (80%); mp 179e181 ꢁC. IR (KBr) (nmax/cmꢀ1):
3428 (NH), 1747 and 1711 (CO). 1H NMR (300 MHz, DMSO-d6): dH
2.17 (s, 2Me, 6H), 3.60 (s, MeO, 3H), 3.70 (s, MeO, 3H), 3.92 (d,
J ¼ 10.3 Hz, CH, 1H), 3.94 (bs, CH, 1H), 4.08e4.30 (m, CHfer, 9H), 7.03
(bs, HeAr, 3H), 9.64 (s, NH, 1H). Anal. Calcd for C25H27FeNO5: C,
62.91; H, 5.70; N, 2.93%. Found: C, 62.82; H, 5.77; N, 2.87% (due to
the very low solubility of product 5c, we were unable to obtain a 13C
NMR spectrum for this product).
4.2.4. Compound 5d
Brown powder (64%). IR (KBr) (nmax/cmꢀ1): 3442 (NH), 1738 and
1645 (CO). 1H NMR (300 MHz, DMSO-d6): dH 1.12e2.12 (m, 5CH2 of
cyclohexyl, 10H), 1.38 (bs, 2Me, 6H), 3.39e383 (m, CHeN of cyclo-
hexyl and 2OCH2, 5H), 4.12e462 (m, CHfer, 9H), 9.57 (bs, NH, 1H).
Anal. Calcd for C25H33FeNO5: C, 62.12; H, 6.88; N, 2.90%. Found: C,
62.23; H, 6.80; N, 2.83% (due to the very low solubility of product
5d, we were unable to obtain a 13C NMR spectrum for this product).
4.2.10. Compound 5j
Light brownpowder (85%); mp 140e143 ꢁC. IR (KBr) (nmax/cmꢀ1):
3278 (NH), 1749 and 1732 (CO). 1H NMR (300 MHz, DMSO-d6): dH
1.12e1.80 (m, 5CH2 of cyclohexyl,10H), 3.56 (m, CHeN of cyclohexyl,
1H), 3.66 (bs, CH,1H), 3.73 (s, 2MeO, 6H), 3.82 (bs, CH,1H), 4.05e4.13
(m, CHfer, 9), 4.80 and 4.85 (ABq, J ¼ 15.1 Hz, CH2O, 2H), 4.98 (bs,
CH2O, 2H), 6.85e7.19 (m, HeAr, 8H), 8.21 (d, J ¼ 6.4 Hz, NH,1H). Anal.
Calcd for C37H41FeNO7: C, 66.57; H, 6.19; N, 2.10%. Found: C, 66.44; H,
6.09; N, 2.02% (due to the very low solubility of product 5j, we were
unable to obtain a 13C NMR spectrum for this product).
4.2.5. Compound 5e
Dark purple powder (55%). IR (KBr) (nmax/cmꢀ1): 3406 (NH),
1757 and 1700 (CO). 1H NMR (300 MHz, DMSO-d6): dH 1.04 (t,
J ¼ 7 Hz, Me, 3H), 1.14 (t, J ¼ 7.2 Hz, Me, 3H), 1.30 (s, CMe3, 9H), 3.80
(d, J ¼ 11.6 Hz, CH, 1H), 3.86 (bs, CH, 1H), 3.95 (q, J ¼ 7.2 Hz, OCH2,
2H), 4.03e4.08 (m, OCH2, 2H), 4.09e4.18 (m, CHfer, 9H), 7.98 (s, NH,
1H). 13C NMR (75 MHz, DMSO-d6): dC 14.2,14.3, 28.8, 45.8, 50.7, 58.1,
61.5, 66.7, 67.2, 67.9, 68.1, 69.1, 69.9, 85.2, 167.3, 168.0, 169.9. Anal.
Calcd for C23H31FeNO5: C, 60.40; H, 6.83; N, 3.06%. Found: C, 60.32;
H, 6.76; N, 2.98%.
4.2.11. Compound 5k
Dark purple oil (70%). IR (KBr) (nmax/cmꢀ1): 3430 (NH), 1738 and
1700 (CO). 1H NMR (300 MHz, DMSO-d6): dH 1.31 (s, CMe3, 9H), 3.67
(d, J ¼ 11.5 Hz, CH, 1H), 3.74 (s, 2MeO, 6H), 3.84 (bs, CH, 1H),
4.06e4.43 (m, CHfer, 9H), 4.83 and 4.92 (ABq, J ¼ 15.7 Hz, CH2O, 2H),
4.99 and 5.03 (ABq, J ¼ 14.3 Hz, CH2O, 2H), 6.87e7.28 (m, HeAr,

3424
R. Akbarzadeh et al. / Journal of Organometallic Chemistry 696 (2011) 3421e3424
8H), 7.99 (s, NH, 1H). 13C NMR (75 MHz, DMSO-d6): dC 28.7, 50.7,
55.5, 58.2, 63.0, 66.6, 66.8, 66.9, 67.4, 67.9, 68.1, 69.1, 69.8, 85.3,
113.9, 114.2, 127.5, 127.9, 128.4, 130.3, 130.4, 130.5, 159.6, 159.7, 167.1.
Anal. Calcd for C35H39FeNO7: C, 65.53; H, 6.13; N, 2.18%. Found: C,
65.45; H, 6.08; N, 2.11%.
HeAr, 14H), 8.32 (bs, NH, 1H), 9.90 (s, 2NH, 2H), 9.76 (s, NH, 1H). 13
C
NMR (75 MHz, DMSO-d6): dC 24.8, 25.1, 25.7, 32.8, 32.9, 46.3, 48.2,
60.6, 67.3, 67.8, 69.1, 85.8, 119.5, 121.5, 122.0, 122.8, 126.0, 126.3,
126.6, 128.0, 128.6, 133.2, 133.5, 134.0, 134.1, 166.8, 167.4, 170.3. Anal.
Calcd for C41H39FeN3O3: C, 72.67; H, 5.80; N, 6.20%. Found: C, 72.58;
H, 5.72; N, 6.26%.
4.2.12. Compound 10
Dark purple oil (53%). IR (KBr) (nmax/cmꢀ1): 3437 (NH), 1738 and
1686 (CO). 1H NMR (300 MHz, DMSO-d6): dH 1.13e1.79 (m, 5CH2 of
cyclohexyl, 10H), 3.53 (bs, CHeN of cyclohexyl, 1H), 3.69 (d,
J ¼ 10.8 Hz, CH, 1H), 3.77 (bs, CH, 1H), 4.04e4.37 (m, CHfer, 9H),
4.82e4.87 (m, CH2O, 2H), 4.88e5.01 (m, CH2O, 2H), 6.00 (bs, CH2O2,
4H), 6.68e6.84 (m, HeAr, 8H), 8.21 (d, J ¼ 6.1 Hz, NH, 1H). 13C NMR
(75 MHz, DMSO-d6): dC 24.9, 25.7, 32.6, 32.8, 45.4, 48.2, 57.9, 66.9,
67.0, 67.4, 68.0, 68.4, 69.2, 84.8, 101.5, 108.4, 108.9, 109.2, 122.3,
122.7, 129.1, 129.6, 147.7, 167.0, 167.5, 169.2. Anal. Calcd for
C37H37FeNO9: C, 63.89; H, 5.36; N, 2.01%. Found: C, 63.77; H, 5.44;
N, 2.12%.
4.2.17. Compound 14
Brown powder (65%); mp 223e225 ꢁC. IR (KBr) (nmax/cmꢀ1):
3423 and 3403 (NH), 1679 and 1649 (CO). 1H NMR (300 MHz,
DMSO-d6): dH 1.23e1.68 (m, 5CH2 of cyclohexyl, 10H), 3.44 (bs,
CHeN of cyclohexyl, 1H), 3.92 (bs, CHfer, 5H), 4.08 (bs, CHfer, 2H),
4.13 (bs, CH,1H), 4.21 (bs, CHfer, 2H), 5.60 (bs, CH,1H), 6.81e7.40 (m,
HeAr and 2CH, 10H), 7.96 bs, NH, 1H), 10.76 (bs, 2NH, 2H). Anal.
Calcd for C37H35FeN3O3: C, 71.04; H, 5.64; N, 6.72%. Found: C, 70.93;
H, 5.56; N, 6.33%.
Acknowledgements
4.2.13. Compound 12a
We gratefully acknowledge financial support from the Research
Council of Shahid Beheshti University.
Cream powder (88%). mp 276e278 ꢁC. IR (KBr) (nmax/cmꢀ1):
3298 (bs, NH), 1679 and 1631 (CO). 1H NMR (300 MHz, DMSO-d6):
dH 1.10e1.77 (m, 5CH2 of cyclohexyl, 10H), 3.58 (m, CHeN of
cyclohexyl, 1H), 3.82 (d, J ¼ 8.7 Hz, CH, 1H), 4.02 (bs, CH, 1H),
4.05e4.28 (m, CHfer, 9H), 7.03e7.55 (m, HeAr, 10H), 8.20 (d,
J ¼ 6.1 Hz, NH, 1H), 9.62 (s, NH, 1H), 9.76 (s, NH, 1H). 13C NMR
(75 MHz, DMSO-d6): dC 24.9, 25.6, 32.7, 45.8, 47.9, 61.1, 67.2, 67.6,
68.6, 69.0, 85.6, 119.5, 119.6, 123.9, 124.1, 129.1, 139.0, 165.8, 166.2,
170.1. Anal. Calcd for C33H35FeN3O3: C, 68.63; H, 6.11; N, 7.28%.
Found: C, 68.51; H, 6.19; N, 7.21%.
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4.2.14. Compound 12b
Cream powder (83%). mp 265e265 ꢁC. IR (KBr) (nmax/cmꢀ1):
3284 (bs, NH), 1672 and 1649 (CO). 1H NMR (300 MHz, DMSO-d6):
dH 1.24 (s, CMe3, 9H), 3.74 (d, J ¼ 9.1 Hz, CH, 1H), 4.01 (bs, CH, 1H),
4.06e4.31 (m, CHfer, 9H), 7.03e7.59 (m, HeAr, 10H), 7.86 (bs, NH,
1H), 9.50 (s, NH, 1H), 9.81 (s, NH, 1H). 13C NMR (75 MHz, DMSO-d6):
dC 28.8, 46.3, 50.5, 61.7, 67.2, 67.6, 68.4, 69.0, 85.8, 119.5, 119.7, 123.9,
124.2, 129.2, 138.9, 139.1, 165.8, 166.5, 170.5. Anal. Calcd for
C31H33FeN3O3: C, 67.52; H, 6.03; N, 7.62%. Found: C, 67.63; H, 5.93;
N, 7.55%.
4.2.15. Compound 12c
Cream powder (82%). mp 273e274 ꢁC. IR (KBr) (nmax/cmꢀ1):
3280 (bs, NH), 1675 and 1648 (CO). 1H NMR (300 MHz, DMSO-d6):
dH 2.15 (s, 2Me, 6H), 4.09 (bs, CH, 1H), 4.14 (bs, CH, 1H), 4.16e4.51
(m, CHfer, 9H), 6.98e7.67 (m, HeAr, 13H), 9.65 (s, NH, 1H), 9.78 (s,
NH,1H), 9.96 (s, NH,1H). 13C NMR (75 MHz, DMSO-d6): dC 18.8, 45.1,
58.9, 66.8, 67.3, 67.4, 67.7, 69.3, 87.0, 119.2, 119.6, 123.9, 124.2, 126.5,
128.0,129.2,129.4,135.5,135.7,139.2,166.3,166.5,170.3. Anal. Calcd
for C35H33FeN3O3: C, 70.12; H, 5.55; N, 7.01%. Found: C, 70.4; H,
5.49; N, 7.11%.
4.2.16. Compound 12d
Light brownpowder (81%). mp 250e252 ꢁC. IR (KBr) (nmax/cmꢀ1):
3298 (bs, NH),1675 and 1639 (CO).1H NMR (300 MHz, DMSO-d6): dH
1.15e1.89 (m, 5CH2 of cyclohexyl,10H), 3.72 (bs, CHeN of cyclohexyl,
1H), 4.11 (bs, CH,1H), 4.20e4.47 (m, CH andCHfer,10H), 7.50e8.11 (m,
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