A tandem synthesis of 4,5-bis(arylimino)-2-(alkylimino)imidazolidines

Article abstract of DOI:10.1007/s00706-016-1909-1

A tandem reaction of aniline derivatives, dialkyl carbodiimides, and bis(imidoyl) chlorides, leads to the formation of functionalized 4,5-bis(arylimino)-2-(alkylimino)imidazolidines, in moderate to good yields. Graphical abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s00706-016-1909-1

Monatsh Chem
DOI 10.1007/s00706-016-1909-1
ORIGINAL PAPER
A tandem synthesis of 4,5-bis(arylimino)-2-
(
alkylimino)imidazolidines
1
1
2
Issa Yavari
•
Nooshin Zahedi
•
Mohammad Reza Halvagar
Received: 14 October 2016 / Accepted: 30 December 2016
Ó Springer-Verlag Wien 2017
Abstract A tandem reaction of aniline derivatives, dialkyl
carbodiimides, and bis(imidoyl) chlorides, leads to the
formation of functionalized 4,5-bis(arylimino)-2-(alkylim-
ino)imidazolidines, in moderate to good yields.
Graphical abstract
as N-heterocyclic carbene precursors [7, 8]. 2-Iminoimida-
zoles are important heterocycles endowed with a broad
spectrum of biological activities, and are emerging as
valuable pharmacophores for biomedical research [9].
The guanidino group is a key feature in many biological
and pharmaceutically relevant compounds [10, 11]. In
addition, the guanidino groups are useful N-based donor
ligands in coordination chemistry [12]. As a consequence,
various methods have been developed for placement of
guanidine moieties in organic molecules [13–15]. Recently,
we reported on the application of copper(II) oxide
nanoparticles for the synthesis of tri-substituted guanidines
from anilines and dialkyl carbodiimides [16, 17]. In view of
the wide spectrum of useful biological activities of imi-
noimidazolidine derivatives further exploratory synthesis of
compounds built up on imidazolidine skeleton has been
carried out [18–22]. As part of our current studies on the
development of new routes to heterocyclic systems [23–25],
herein, we report on the synthesis of functionalized 4,5-
bis(arylimino)-2-(alkylimino)imidazolidines through the
reaction of 1,3-dialkyl-2-arylguanidines 3 and bis(imidoyl)
chlorides 4. The reaction of dianionic compounds with
oxaldiimidoyl dichlorides has been reviewed [26].
Cl
NAr2
R
Ar1
N
1
Ar2
Ar NH
2
N
N
2
CuO-NPs (10 mol%)
toluene, 80 °C, 8 h
R
Ar N
Cl
R
N
N
+
N
H
N
H
N
NaH, reflux, 5 h
N
Ar2
Ar1
R
R
C
N
R
R = Cy, i-Pr
13 Examples
1
Ar = Ph, 4-BrC
6
H
4
, 4-MeC
, 2,4-Cl
6 4
, 4-O NC H
6
H
4
,
Yields: 56-85%
4
3
-MeOC
-O NC
6
H
4
2 6 3
C H ,
2
6
H
4
2
Ar2 = Ph, 4-MeOC
H
6
4
Keywords Guanidines Á Imidazolidines Á
Bis(imidoyl) chlorides Á CuO-NPs
Introduction
The imidazolidine nucleus, among the nitrogen heterocy-
cles, is a prominent motif that exists in numerous natural
products [1, 2] and synthetic bioactive compounds [3–5].
Moreover, imidazolidines are well known as ligand in
coordination chemistry [6], and their salts are widely applied
Results and discussion
Thus, 1,3-dialkyl-2-arylguanidines 3 were prepared from
0
&
Issa Yavari
yavarisa@modares.ac.ir
anilines and N,N -dialkylcarbodiimides, in the presence of
copper(II) oxide nanoparticles as catalyst [16, 17]. Subse-
1
2
quently, the reaction of 3 with bis(imidoyl) chlorides 4
[
Department of Chemistry, Tarbiat Modares University,
PO Box 14115-175, Tehran, Iran
27, 28] afforded the 4,5-bis(arylimino)-2-(alkylimino)im-
idazolidines 5 in moderate to good yields (Table 1).
In addition, the possibility to perform the reaction of the
presynthesized 3 with 4 was investigated. The reactions
Department of Inorganic Chemistry, Chemistry and Chemical
Engineering Research Center of Iran, PO Box 14335-186,
Tehran, Iran
123

I. Yavari et al.
Table 1 Synthesis of products 5
0
1
2
Entry
R
Ar
Ar
Product
Yield/%
a
1
2
3
4
5
6
7
8
9
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
Ph
Ph
Ph
Ph
Ph
Ph
5a
5b
5c
5d
5e
5f
72
67
85
57
60
62
70
65
79
84
59
56
66
4-BrC
4-MeOC
4-O NC
6
H
4
6 4
H
2
6 4
H
2,4-Cl
2,4-Cl
Ph
2
C
C
6
H
3
3
2
6
H
4-MeOC
6 4
H
b
Cy
Cy
Cy
Cy
Cy
Cy
Cy
Ph
5g
5h
5i
4-BrC
4-MeC
4-MeOC
H
6 4
Ph
6
H
4
Ph
1
1
1
1
a
0
1
2
3
6
H
4
Ph
5j
3-O
4-O
2
NC
NC
6
H
4
Ph
5k
5l
2
6
H
4
Ph
4-BrC
H
6 4
4-MeOC
6
H
4
5m
Isopropyl
b
Cyclohexyl
proceeded efficiently producing products 5 in good yields,
which were comparable with those obtained under the one-
pot protocol that employed copper(II) oxide nanoparticles.
As shown in Table 1, the transformation with substrates
possessing electron-poor aryl groups on guanidines 3,
proceeded more sluggishly (entries 4–6, 11, 12).
nucleophilic attack of the guanidinium anion 6 up on the
bis(imidoyl) chloride 4 to afford the iminoguanidine
intermediate 7, which can undergo intramolecular
cyclization to produce the 4,5-bis(arylimino)-2-(alkylim-
ino)imidazolidines 5.
In conclusion, the tandem reaction of aniline derivatives,
dialkyl carbodiimides, and bis(imidoyl) chlorides leads to
the formation of functionalized 4,5-bis(arylimino)-2-
(alkylimino)imidazolidines. The advantages of this proce-
dure are its simple workup and substrate availability, thus
providing a useful path for the synthesis of functionalized
2-iminoimidazolidines.
The structures of compounds 5a–5m were assigned by IR,
13
H and C NMR spectra, and single-crystal X-ray analyses.
1
The MS spectrum of 5a displayed the molecularion peakatm/
1
z = 423. The H NMR spectrum of 5a showed four methyl
groups which appear as two doublets at 0.79 and 1.56 ppm,
together with characteristic multiplets for the phenyl protons.
The methine protons of the two isopropyl groups have fairly
different chemical shifts (3.14 ppm for HC-Nsp3 and
4
.89 ppm for HC-N ) due to the hybridization effect of the
sp2
Experimental
1
13
nitrogen atom. The H-decoupled C NMR spectrum of 5a
exhibited 19 signals in agreement with the proposed structure.
Unequivocal evidences for the structure of 5a were
obtained from single-crystal X-ray analyses. The ORTEP
0
Aromatic amines, N,N -dialkylcarbodiimides, and diethyl
oxalate were obtained from Merck and were used without
further purification. Bis(imidoyl) chlorides 4 were synthe-
sized according to the reported procedure [27, 28]. Melting
points were measured on an Electrothermal 9100 appara-
tus. IR spectra: Shimadzu-IR-460 spectrometer; band
[
29] diagram of 5a is shown in Fig. 1. The structure was
deduced from the crystallographic data and the same were
assumed for the other derivatives on account of their NMR
spectroscopic similarities.
-
1
1
13
positions in cm . H and C NMR spectra: Bruker DRX-
500 Avance instrument at 500.1 and 125 MHz, respec-
tively; d in ppm, J in Hz. MS: Finnigan-MAT-8430 EI-MS
A plausible mechanism for the formation of compounds
5
is shown in Scheme 1. The initial event may be the
1
23

A tandem synthesis of 4,5-bis(arylimino)-2-(alkylimino)imidazolidines
monitoring), the mixture was diluted with CH Cl and aq
2
2
3
NH Cl (3 cm ) and stirred for 10 min. The layers were
4
separated, and the aqueous layer was extracted with
3
CH Cl (3 9 3 cm ). The organic layer dried over Na
2
2
2-
SO and evaporated to dryness. The residue was purified by
4
flash column chromatography (SiO2 (230–400 mesh;
Merck); AcOEt/hexane 1:6) to give the product.
(
E)-N-[(2Z,5Z)-1-Phenyl-3-isopropyl-2-(isopropylimino)-
-(phenylimino)imidazolidin-4-ylidene]benzenamine
5a, C H N )
5
(
2
7 29 5
Yellow powder; m.p.: 139–141 °C; yield: 0.30 g (72%); IR
(
KBr): mꢀ = 2966, 1660, 1595, 1359, 1205, 1079, 749,
-1 1
6
82 cm ; H NMR (500 MHz, CDCl ): d = 0.79 (6H, d,
3
J = 5.8 Hz, CHMe ), 1.56-1.65 (6H, br. m, CHMe ), 3.14
2
2
(1H, sept, J = 5.8 Hz, CHMe ), 4.89 (1H, br. m, CHMe ),
2 2
6.05–6.27 (2H, br. m, Ar), 6.60 (1H, t, J = 6.8 Hz, Ar), 6.76
(
(
(
(
2H, t, J = 7.4 Hz, Ar), 6.80–6.96 (3H, m, Ar), 7.00–7.10
1
3
4H, m, Ar), 7.11–7.22 (3H, m, Ar) ppm; C NMR
125 MHz, CDCl ): d = 19.1 (2 Me), 24.6 (2 Me), 31.7
3
CH), 45.6 (CH), 118.9 (2 CH), 120.2 (2 CH), 121.7 (CH),
121.8 (CH), 122.1 (C), 127.9 (2 CH), 128.3 (2 CH), 128.5
(
(
CH), 128.9 (2 CH), 129.6 (2 CH), 136.5 (C), 137.9 (C), 145.0
?
C), 147.1 (C), 150.3 (C) ppm; EI-MS: m/z = 423 (M , 16),
Fig. 1 X-ray crystal structure of compound 5a (thermal ellipsoids set
˚
at the 40% probability level). Selected bond lengths/A and angles/°:
380 (49), 346 (17), 217 (100), 206 (36), 160 (41), 77 (12).
C1-N5 1.227(6), C1-N2 1.407(6), C1-N1 1.456(6), C2-N3 1.261(6),
C2-N2 1.374(6), C2-C9 1.497(6), N5-C1-N2 123.6(6), N5-C1-N1
X-ray crystal structure determination of 5a: CCDC-
1506190 contains the supplementary crystallographic data
for 5a CH Cl (C H N ), F = 423.32, orthorhombic,
1
34.0(6), N2-C1-N1 102.4(5), N3-C2-N2 125.5(6)
2
2
27 29
5
w
mass spectrometer; at 70 eV; in m/z (rel. %). Elemental
analyses for C and H were performed using a Heraeus
CHN-O-Rapid analyzer. The experimental data were in
good agreement with the calculated values. Chromatogra-
phy columns were prepared from Aldrich silica gel 70–230
mesh.
space group Pbca, Z = 8, a = 11.754(2) A˚ , b = 23.515(5)
3
A˚ , c = 17.298(3) A˚ , V = 4781.1(15) A˚ , D
= 1.177 g/
calcd
3
2
cm , R = 0. 0520, wR (all data) = 0.1106, Mo
(k = 0.071 mm), T = 293 K. These data can be obtained
free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
General procedure for preparation of compounds 5
Aniline derivatives
(E)-N-[(2Z,5Z)-1-(4-Bromophenyl)-3-isopropyl-2-(iso-
propylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
zenamine (5b, C H BrN )
1
1.2 mmol), and CuO nanoparticles (10 mol%) were stirred
(1 mmol), carbodiimides
2
(
2
7
28
5
3
in 2 cm toluene at 80 °C for 8 h. After the completion of
reaction, 0.048 g NaH (2 mmol) and bis(imidoyl) chlorides
Yellow powder; m.p.: 147–149 °C; yield: 0.34 g (67%); IR
(KBr): mꢀ = 2965, 2925, 1661, 1588, 1358, 1064,
-
1
1
(
1 mmol) were added and stirred at r.t. After completion of
688 cm ; H NMR (500 MHz, CDCl ): d = 0.85 (6H,
3
the reaction (ca. 5 h; TLC (AcOEt/hexane 1:6)
d, J = 6.0 Hz, CHMe ), 1.50-1.64 (6H, br. m, CHMe ),
2
2
Scheme 1
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I. Yavari et al.
1
3
.22 (1H, sept, J = 6.0 Hz, CHMe ), 4.86 (1H, br. m,
2
H
NMR (500 MHz, CDCl3): d = 0.80 (3H, d,
CHMe ), 6.10–6.27 (2H, br. m, Ar), 6.71 (1H, t,
2
J = 5.9 Hz, CHMe ), 0.90 (3H, d, J = 5.9 Hz, CHMe ),
2 2
J = 7.3 Hz, Ar), 6.83–6.93 (4H, m, Ar), 6.94 (2H, d,
J = 7.6 Hz, Ar), 7.08 (1H, t, J = 7.3 Hz, Ar), 7.19 (4H, t,
1.60 (6H, br. m, CHMe ), 3.18 (1H, sept, J = 5.9 Hz,
2
CHMe ), 4.72-5.19 (1H, br. m, CHMe ), 6.15–6.35 (2H, br.
2
2
1
J = 7.6 Hz, Ar) ppm; C NMR (125 MHz, CDCl3):
3
m, Ar), 6.71 (1H, t, J = 7.1 Hz, Ar), 6.84 (2H, t,
J = 7.4 Hz, Ar), 6.85-7.10 (4H, br. m, Ar), 7.16 (2H, d,
J = 7.4 Hz, Ar), 7.25 (1H, s, Ar), 7.51 (1H, t, J = 7.8 Hz,
d = 19.3 (2 Me), 25.0 (2 Me), 45.9 (CH), 54.2 (CH),
1
19.1 (C), 120.4 (2 CH), 121.6 (2 CH), 122.1 (C), 122.8
1
3
(
C), 124.5 (CH), 128.3 (2 CH), 128.6 (2 CH), 128.8 (2 CH),
Ar) ppm; C NMR (125 MHz, CDCl ): d = 19.3 (2 Me),
3
1
1
31.4 (2 CH), 132.3 (CH), 137.4 (C), 141.6 (C), 149.0 (C),
?
50.1 (C) ppm; EI-MS: m/z = 501 (M , 12), 458 (36), 346
24.5 (Me), 25.0 (Me), 45.9 (CH), 54.2 (CH), 118.9 (C),
119.1 (C), 120.7 (2 CH), 121.6 (2 CH), 122.1 (C), 122.8
(C), 123.1 (CH), 124.5 (CH), 125.2 (C), 128.3 (2 CH),
(
21), 295 (100), 206 (36), 160 (31), 154 (10), 77 (17).
1
28.6 (2 CH), 128.8 (CH), 131.4 (CH), 132.3 (CH), 137.4
(
E)-N-[(2Z,5Z)-1-(4-Methoxyphenyl)-3-isopropyl-2-(iso-
?
(
C), 143.2 (C), 150.0 (C) ppm; EI-MS: m/z = 492 (M ,
5), 448 (28), 346 (33), 286 (100), 207 (41), 144 (14), 77
26).
propylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
1
zenamine (5c, C H N O)
8 31 5
2
(
Yellow powder; m.p.: 121–123 °C; yield: 0.38 g (85%); IR
(
1
-
1
;
KBr): mꢀ = 2930, 1668, 1589, 1373, 1056, 744, 688 cm
(E)-N-[(2Z,5Z)-1-(2,4-Dichlorophenyl)-3-isopropyl-2-(iso-
propylimino)-5-(4-methoxyphenylimino)imidazolidin-4-yli-
dene]-4-methoxybenzenamine (5f, C H Cl N O )
H NMR (500 MHz, CDCl ): d = 0.81 (6H, d, J = 4.8 Hz,
3
CHMe ), 1.57 (6H, br. m, CHMe ), 3.24 (1H, sept,
2
2
29 31
2 5 2
J = 4.8 Hz, CHMe ), 3.71 (3H, s, MeO), 4.62–5.12 (1H,
2
Yellow powder; m.p.: 152–155 °C; yield: 0.34 g (62%); IR
-1 1
br. m, CHMe ), 6.13–6.29 (2H, br. m, Ar), 6.53 (2H, d,
2
(KBr): mꢀ = 2964, 1655, 1502, 1365, 1239, 750 cm ; H
J = 8.1 Hz, Ar), 6.61 (1H, t, J = 7.3 Hz, Ar), 6.79 (2H, t,
J = 7.4 Hz, Ar), 6.82–6.89 (3H, m, Ar), 6.92 (2H, d,
NMR (500 MHz, CDCl ): d = 0.81 (3H, d, J = 6.5 Hz,
3
CHMe ), 0.91 (3H, d, J = 6.5 Hz, CHMe ), 1.62 (6H, br.
2
2
1
3
J = 8.1 Hz, Ar), 7.15 (2H, t, J = 7.4 Hz, Ar) ppm;
C
m, CHMe ), 3.21 (1H, br. m, CHMe ), 3.70 (3H, s, MeO),
2 2
NMR (125 MHz, CDCl ): d = 19.0 (2 Me), 24.7 (2 Me),
3.75 (3H, s, MeO), 4.80–4.90 (1H, br. m, CHMe2),
6.12–6.22 (2H, br. m, Ar), 6.41 (2H, br. m, Ar),
6.63–6.81 (2H, br. m, Ar), 6.84–7.03 (5H, m, Ar) ppm;
3
4
1
4.7 (CH), 45.6 (MeO), 55.3 (CH), 114.0 (CH), 114.1 (CH),
18.7 (C), 120.1 (2 CH), 121.3 (2 CH), 121.8 (C), 127.7 (2
1
3
CH), 128.2 (2 CH), 130.5 (4 CH), 137.7 (C), 141.7 (C), 146.9
?
C NMR (125 MHz, CDCl ): d = 24.6 (2 Me), 26.2 (Me),
3
(
C), 149.1 (C), 159.2 (C) ppm; EI-MS: m/z = 453 (M , 14),
10 (40), 346 (33), 247 (100), 206 (36), 107 (23), 77 (17).
26.5 (Me), 34.8 (CH), 52.8 (CH), 54.2 (MeO), 55.8 (MeO),
4
114.3 (CH), 120.0 (C), 120.3 (2 CH), 120.6 (2 CH), 122.4
(
(
2 CH), 126.6 (C), 126.8 (C), 128.3 (C), 128.5 (C), 129.7
CH), 130.5 (2 CH), 136.3 (C), 138.7 (C), 140.6 (CH),
(
E)-N-[(2Z,5Z)-1-(4-Nitrophenyl)-3-isopropyl-2-(isoprop-
ylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
1
42.1 (C), 149.2 (C), 153.1 (C) ppm; EI-MS: m/z = 552
zenamine (5d, C H N O )
2
7
28
6
2
?
M , 11), 508 (32), 406 (40), 286 (100), 267 (46), 144 (12),
(
Yellow powder; m.p.: 153–155 °C; yield: 0.27 g (57%); IR
(
1
07 (17).
KBr): mꢀ = 2927, 2855, 1676, 1595, 1373, 1156, 754,
-
1 1
6
94 cm ; H NMR (500 MHz, CDCl ): d = 0.88 (6H, d,
3
(
E)-N-[(2Z,5Z)-1-Phenyl-3-cyclohexyl-2-(cyclohexylim-
ino)-5-(phenylimino)imidazolidin-4-ylidene]benzenamine
5g, C H N )
J = 6.9 Hz, CHMe ), 1.44–1.46 (6H, br. m, CHMe ), 3.16
2
2
(
1H, br. m, CHMe ), 4.91(1H, br. m, CHMe ), 6.01–6.19(2H,
2 2
(
3
3 37 5
br. m, Ar), 6.64–6.88 (4H, m, Ar), 6.91 (2H, t, J = 6.5 Hz,
Ar), 7.12 (2H, d, J = 7.4 Hz, Ar), 7.40–7.49 (2H, m, Ar),
Yellow powder; m.p.: 185–187 °C; yield: 0.35 g (70%); IR
(
KBr): mꢀ = 2924, 2850, 1661, 1588, 1351, 1200, 830, 761,
1
.84–7.97 (2H, br. m, Ar)ppm; C NMR (125 MHz, CDCl ):
3
7
-1
1
3
6
88 cm ; H NMR (500 MHz, CDCl ): d = 0.69–1.82
3
d = 19.3 (2 Me), 24.6 (2 Me), 30.0 (CH), 47.1 (CH), 115.2
C), 119.1 (2 CH), 119.8 (2 CH), 120.3 (C), 120.7 (2 CH),
23.8 (CH), 124.9 (CH), 126.9 (2 CH), 128.7 (2 CH), 129.3 (2
CH), 129.6 (C), 130.5 (C), 142.3 (C), 148.9 (C), 150.1
(
20H, m, 10 CH ), 2.61 (1H, m, CH), 4.45 (1H, m, CH),
2
(
6
.10–6.22 (2H, br. m, Ar), 6.53–6.88 (6H, br. m, Ar),
.01–7.10 (4H, br. m, Ar), 7.11–7.15 (3H, br. m, Ar) ppm;
1
7
13
C NMR (125 MHz, CDCl ): d = 23.2 (2 CH ), 24.5
?
3
2
(
(
C) ppm; EI-MS:m/z = 468 (M , 14), 425 (40), 346 (53), 262
(
CH ), 25.6 (CH ), 26.3 (2 CH ), 28.3 (2 CH ), 29.3 (2
2 2 2 2
100), 206 (43), 122 (23), 77 (14).
CH ), 34.6 (CH), 52.5 (CH), 118.1 (C), 119.4 (2 CH),
2
(
E)-N-[(2Z,5Z)-1-(2,4-Dichlorophenyl)-3-isopropyl-2-(iso-
120.7 (CH), 122.3 (C), 127.0 (CH), 127.6 (CH), 127.9 (2
CH), 128.3 (2 CH), 128.9 (2 CH), 129.2 (2 CH), 130.2 (2
CH), 137.6 (C), 137.8 (C), 146.8 (C), 149.8 (C) ppm; EI-
propylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
zenamine (5e, C H Cl N )
27
2
7
2 5
?
Yellow powder; m.p.: 160–162 °C; yield: 0.30 g (60%); IR
(
MS: m/z = 503 (M , 10), 420 (70), 363 (100), 338 (16),
-
1
;
KBr): mꢀ = 2967, 1662, 1590, 1363, 1074, 748, 690 cm
194 (60), 77 (20).
1
23

A tandem synthesis of 4,5-bis(arylimino)-2-(alkylimino)imidazolidines
(
E)-N-[(2Z,5Z)-1-(4-Bromophenyl)-3-cyclohexyl-2-(cyclo-
(MeO), 114.4 (4 CH), 119.3 (C), 120.4 (CH), 121.8 (CH),
128.1 (4 CH), 128.6 (2 CH), 130.5 (C), 131.0 (2 CH), 139.4
(C), 145.6 (C), 147.1 (C), 150.0 (C), 159.6 (C) ppm; EI-
hexylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
zenamine (5h, C H BrN )
3
3
36
5
?
Yellow powder; m.p.: 174–176 °C; yield: 0.38 g (65%); IR
(
MS: m/z = 533 (M , 9), 450 (66), 426 (22), 327 (100), 206
KBr): mꢀ = 2929, 2857, 1667, 1591, 1362, 1202,
(46), 107 (23), 77 (16).
-
1
1
6
93 cm ; H NMR (500 MHz, CDCl ): d = 0.71–0.93
3
(E)-N-[(2Z,5Z)-1-(3-Nitrophenyl)-3-cyclohexyl-2-(cyclo-
(
2H, m, CH ), 0.98–1.22 (4H, m, 2 CH ), 1.23–1.42 (4H,
2 2
hexylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
m, 2 CH ), 1.52–1.59 (4H, m, 2 CH ), 1.60–1.93 (4H, m, 2
2
2
zenamine (5k, C H N O )
3
3 36 6 2
CH ), 2.43–2.71 (2H, m, CH ), 2.79 (1H, m, CH), 4.37
2
2
Yellow powder; m.p.: 185–187 °C; yield: 0.32 g (59%); IR
(
1H, m, CH), 6.13–6.18 (2H, m, Ar), 6.69 (2H, t,
(
KBr): mꢀ = 2965, 2925, 1677, 1591, 1356, 1236,
J = 6.9 Hz, Ar), 6.82 (4H, t, J = 6.9 Hz, Ar), 6.92 (2H,
1
d, J = 7.9 Hz, Ar), 7.06–7.22 (4H, m, Ar) ppm; C NMR
-
1
1
8
42 cm ; H NMR (500 MHz, CDCl ): d = 1.06–1.19
3
3
(2H, m, CH ), 1.08–1.21 (2H, m, CH ), 1.35–1.41 (4H, m,
2 2
(
125 MHz, CDCl ): d = 24.2 (2 CH ), 25.6 (CH ), 25.7
3
2
2
2
CH ), 1.57–1.75 (10H, m, 5 CH ), 1.90–2.30 (2H, m,
2 2
(
CH ), 26.4 (4 CH ), 28.4 (2 CH ), 34.6 (CH), 53.3 (CH),
2 2 2
CH ), 3.11 (1H, m, CH), 4.15 (1H, m, CH), 6.09–6.18 (2H,
2
1
18.9 (C), 119.9 (2 CH), 121.8 (CH), 122.1 (C), 122.4
m, Ar), 6.48–6.70 (2H, m, Ar), 6.73–7.11 (7H, m, Ar),
(CH), 128.0 (4 CH), 128.4 (2 CH), 131.2 (2 CH), 131.9 (2
CH), 137.1 (C), 137.3 (C), 146.9 (C), 149.1 (C), 149.3
1
.18–7.25 (2H, m, Ar), 7.45 (1H, m, Ar) ppm; C NMR
3
7
(
(
(
125 MHz, CDCl ): d = 24.6 (CH ), 25.7 (2 CH ), 26.2
?
3
2
2
(
C) ppm; EI-MS: m/z = 582 (M , 9), 489 (66), 375 (100),
08 (24), 154 (33), 83 (5), 77 (17).
CH ), 26.4 (2 CH ), 26.5 (2 CH ), 29.0 (2 CH ), 34.3
2
2
2
2
2
CH), 54.2 (CH), 115.0 (2 CH), 118.8 (2 CH), 119.3 (CH),
(
E)-N-[(2Z,5Z)-1-(p-Tolyl)-3-cyclohexyl-2-(cyclohexylim-
ino)-5-(phenylimino)imidazolidin-4-ylidene]benzenamine
5i, C H N )
120.0 (2 CH), 128.5 (2 CH), 130.0 (CH), 130.3 (CH), 130.8
(CH), 133.9 (C), 134.2 (CH), 139.8 (CH), 143.2 (C), 146.0
(C), 146.8 (C), 149.2 (C), 152.4 (C), 158.2 (C) ppm; EI-
(
3
4 39 5
?
Yellow powder; m.p.: 158–161 °C; yield: 0.41 g (79%); IR
MS: m/z = 548 (M , 11), 465 (58), 426 (46), 343 (100),
(
KBr): mꢀ = 2926, 2854, 1660, 1595, 1362, 1203, 749,
208 (27), 122 (29), 83 (5), 77 (19).
-
1
1
6
89 cm ; H NMR (500 MHz, CDCl ): d = 0.70–0.76
3
(E)-N-[(2Z,5Z)-1-(4-Nitrophenyl)-3-cyclohexyl-2-(cyclo-
(
2H, m, CH ), 1.04–1.13 (4H, m, 2 CH ), 1.21–1.35 (4H,
2 2
hexylimino)-5-(phenylimino)imidazolidin-4-ylidene]ben-
m, 2 CH ), 1.49–1.59 (4H, m, 2 CH ), 1.70–1.96 (4H, m, 2
2
2
zenamine (5l, C H N O )
3 36 6 2
3
CH ), 2.22 (3H, s, Me), 2.36–2.71 (2H, m, CH ), 2.78 (1H,
2
2
Yellow powder; m.p.: 179–181 °C; yield: 0.31 g (56%); IR
m, CH), 4.36 (1H, m, CH), 6.10–6.22 (2H, br. m, Ar),
(
KBr): mꢀ = 2924, 2855, 1677, 1595, 1511, 1339, 1280,
6
7
.48–6.53 (2H, br. m, Ar), 6.73–6.88 (8H, m, Ar),
3
-
1
1
1195, 754 cm
;
H
NMR (500 MHz, CDCl3):
1
.03–7.20 (2H, m, Ar) ppm;
C NMR (125 MHz,
d = 0.73–0.86 (2H, m, CH ), 0.98–1.21 (4H, m, 2 CH ),
2
2
CDCl ): d = 21.5 (2 CH ), 24.5 (2 CH ), 25.9 (CH ),
2
3
2
2
2
1.28–1.44 (4H, m, 2 CH ), 1.48–1.69 (4H, m, 2 CH ),
2 2
6.1 (2 CH ), 26.7 (Me), 28.5 (CH ), 28.7 (2 CH ), 35.0
2 2 2
1
.72–1.91 (4H, m, 2 CH ), 2.57–2.73 (2H, m, CH ), 2.76
2
2
(
(
CH), 53.3 (CH), 119.1 (C), 119.3 (C), 120.3 (CH), 121.6
2 CH), 128.0 (2 CH), 128.6 (2 CH), 129.6 (2 CH), 129.7 (2
(1H, m, CH), 4.35 (1H, m, CH), 6.13–6.28 (2H, m, Ar),
6
.58–6.89 (6H, m, Ar), 7.20–7.29 (4H, m, Ar), 7.74–7.92
1
CH), 135.5 (CH), 138.6 (2 CH), 141.2 (C), 143.6 (C), 146.2
?
(
3
(
(
2H, m, Ar) ppm; C NMR (125 MHz, CDCl ): d = 24.3
2 CH ), 25.6 (CH ), 25.7 (CH ), 26.6 (2 CH ), 28.6 (2
2
3
C), 147.6 (C), 150.0 (C) ppm; EI-MS: m/z = 517 (M , 8),
34 (77), 426 (38), 314 (100), 206 (13), 91 (20).
2
2
2
4
CH ), 30.8 (2 CH ), 34.7 (CH), 54.0 (CH), 119.3 (CH),
2
2
(
E)-N-[(2Z,5Z)-1-(4-Methoxyphenyl)-3-cyclohexyl-2-(cy-
119.9 (2 CH), 122.6 (CH), 123.9 (2 CH), 128.3 (2 CH),
128.6 (2 CH), 129.0 (2 CH), 129.6 (C), 130.7 (2 CH), 137.1
(C), 144.3 (C), 146.7 (C), 147.2 (C), 148.9 (C), 152.5
clohexylimino)-5-(phenylimino)imidazolidin-4-yli-
dene]benzenamine (5j, C H N O)
3
4 39 5
?
Yellow powder; m.p.: 156–158 °C; yield: 0.45 g (84%); IR
(
(C) ppm; EI-MS: m/z = 548 (M , 9), 465 (60), 426 (46),
KBr): mꢀ = 2928, 2854, 1659, 1593, 1367, 1250, 748,
343 (100), 208 (24), 122 (29), 83 (5), 77 (19).
-
1
1
6
92 cm ; H NMR (500 MHz, CDCl ): d = 0.71–0.79
3
(E)-N-[(2Z,5Z)-1-(4-Bromophenyl)-3-cyclohexyl-2-(cyclo-
(
2H, m, CH ), 1.07–1.15 (4H, m, 2 CH ), 1.25–1.34 (4H,
2 2
hexylimino)-5-(4-methoxyphenylimino)imidazolidin-4-yli-
m, 2 CH ), 1.49–1.59 (4H, m, 2 CH ), 1.70–1.80 (4H, m, 2
2
2
dene]-4-methoxybenzenamine (5m, C H BrN O )
3
5
40
5 2
CH ), 2.48–2.75 (2H, m, CH ), 2.80 (1H, m, CH), 3.70
2
2
Yellow powder; m.p.: 206–208 °C; yield: 0.42 g (66%); IR
(
3H, s, MeO), 4.45 (1H, m, CH), 6.07–6.25 (2H, br. m, Ar),
.49–6.63 (3H, m, Ar), 6.73–6.98 (7H, m, Ar), 7.01–7.23
-
1
(
KBr): mꢀ = 2964, 1653, 1507, 1365, 1239, 839, 750 cm
;
6
1
H NMR (500 MHz, CDCl ): d = 0.79–0.90 (2H, m,
1
2H, br. m, Ar) ppm; C NMR (125 MHz, CDCl3):
3
3
(
CH ), 0.96–1.39 (8H, m, 4 CH ), 1.41–1.83 (8H, m, 4
2
2
d = 24.5 (2 CH ), 25.9 (CH ), 26.1 (2 CH ), 26.7 (2 CH ),
2
2
2
2
2
CH ), 2.51–2.63 (2H, m, CH ), 2.82 (1H, m, CH), 3.67
2
2
8.7 (CH ), 35.1 (2 CH ), 37.3 (CH), 53.3 (CH), 56.0
2 2
123

I. Yavari et al.
(
3H, s, MeO), 3.71 (3H, s, MeO), 4.41 (1H, m, CH),
10. Berlinck RGS, Trindade-Silva AE, Santos MF (2012) Nat Prod
Rep 29:1382
6
6
.01–6.18 (2H, m, Ar), 6.31–6.45 (2H, br. m, Ar),
3
1
1. Nagle PS, Rodriguez F, Nguyen B, Wilson WD, Rozas I (2012) J
Med Chem 55:4397
1
.51–6.54 (4H, m, Ar), 6.78–6.99 (4H, m, Ar) ppm;
C
NMR (125 MHz, CDCl ): d = 24.2 (2 CH ), 25.5 (CH ),
12. Edelmann FT (2013) Adv Organomet Chem 61:55
13. Li D, Guang J, Zhang W-X, Wang Y, Xi Z (2010) Org Biomol
Chem 8:1816
3
2
2
2
5.7 (CH ), 26.4 (2 CH ), 28.4 (2 CH ), 31.1 (2 CH ), 34.6
2 2 2 2
(
CH), 51.2 (CH), 53.3 (MeO), 55.6 (MeO), 113.5 (4 CH),
13.7 (2 CH), 120.9 (C), 121.3 (2 CH), 122.4 (C), 124.1
C), 127.3 (C), 131.1 (2 CH), 131.9 (2 CH), 132.3 (C),
36.7 (C), 141.2 (C), 142.1 (C), 153.2 (C) ppm; EI-MS: m/
1
4. Alonso-Moreno C, Anti n˜ olo A, Carrillo-Hermosilla F, Otero A
2014) Chem Soc Rev 43:3406
1
(
(
15. Suhs T, K o¨ nig B (2006) Mini-Rev Org Chem 3:315
16. Yavari I, Sodagar E, Nematpour M (2014) Helv Chim Acta
97:420
1
?
z = 641 (M , 10), 558 (29), 475 (10), 486 (30), 375 (100),
66 (53), 154 (12), 107 (17).
1
7. Yavari I, Sodagar E, Nematpour M, Askarian-Amiri M (2015)
Synlett 26:1230
2
1
8. Ventosa-Andr e´ s P, Gonz a´ lez-Vera JA, Garc ´ı a-L o´ pez MT, Her-
ranz R (2014) Tetrahedron 70:3407
References
19. Iqbal Z, Akhtar T, Hendsbee AD, Masuda JD, Hameed S (2011)
Monatsh Chem 143:497
2
2
0. Muthusamy S, Ganesh-Kumar S (2016) Tetrahedron 72:2392
1. Kravchenkoa AN, Antonovaa MM, Baranov VV, Nelyubina YV
(2015) Synlett 26:2521
2. Beckert R (1990) J Prakt Chem 332:65
3. Yavari I, Zahedi N, Baoosi L (2016) J Iran Chem Soc 13:1847
4. Yavari I, Nematpour M, Sodagar E (2015) Monatsh Chem
1
2
3
4
5
6
7
8
9
. Chattopadhyay B, Gevorgyan V (2012) Angew Chem Int Ed
1:862
. Bhandari MR, Yousufuddin M, Lovely C (2011) Org Lett
3:1382
. Molinski TF, Ko J, Reynolds KA, Lievens SC, Skarda KR (2011)
J Nat Prod 74:882
. Ye Z, Xia S, Shao X, Cheng J, Xu X, Xu Z, Li Z, Qian X (2011) J
Agric Food Chem 59:10615
. Nishiwaki H, Kuriyama M, Nagaoka H, Kato A, Akamastu M,
Yamauchi S, Shuto Y (2012) Bioorg Med Chem 20:6305
. D o¨ ring M, G o¨ rls H, Beckert R (1994) Z Anorg Allg Chem
5
2
2
2
1
1
46:2135
2
2
2
5. Yavari I, Azad L, Sanaeishoar T (2011) Monatsh Chem 142:643
6. Langer P, D o¨ ring M (2002) Eur J Org Chem 2002:221
7. Lindauer D, Beckert R, D o¨ ring M, Fehling P, G o¨ rls H (1995) J
Prakt Chem 337:143
2
2
8. Helmholz F, Schroeder R, Langer P (2005) Z Naturforsch
6
20:551
. Lancaster KM, Gerken JB, Durrell AC, Palmer JH, Gray HB
2010) Coord Chem Rev 254:1803
6
0b:1192
9. Burnett MN, Johnson CK (1996) ORTEP-III. Report ORNL-
895. Oak Ridge National Laboratory, Tennessee
(
6
. Schaper L, Hock SJ, Herrmann WA, K u¨ hn FE (2013) Angew
Chem Int Ed 52:270
ˇ
ˇ
ˇ
. Hodnik Z, Łos JM, Zula A, Zidar N, Jakopin Z, Łos M, Dolenc
MS, Ila sˇ J, W e˛ grzyn G, Ma sˇ i cˇ LP, Kikelj D (2014) Bioorg Med
Chem Lett 24:2530
1
23