A facile synthesis and characterization of the novel 2,2-dichloro-1-[3-(2,2-dichloro-acetyl)-2-(4-methoxy-phenyl)-imidazolidin -1-yl]-ethanone

Article abstract of DOI:10.1081/SCC-120014029

The synthesis of (2,2-dichloro-1-[3-(2,2-dichloro-acetyl)-2-(4-methoxy-phenyl)-imidazolidin -1-yl]-ethanone by a facile one-pot reaction between N,N′-bis(4-methoxy-benzylidene)-ethane-1,2-diamine and dichloroacetyl chloride is described. The structure was

Full text of DOI:10.1081/SCC-120014029

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A FACILE SYNTHESIS AND CHARACTERIZATION OF THE
NOVEL 2,2-DICHLORO-1-[3-(2,2-DICHLORO-ACETYL)-2-
(
4-METHOXY-PHENYL)-IMIDAZOLIDIN-1-YL]-ETHANONE
a a b
Canan Ünaleroğlu , Barış Temelli & Tuncer Hökelek
a
Department of Chemistry , Hacettepe University , Beytepe-Ankara, 06532, Turkey
Department of Physics , Hacettepe University , Beytepe-Ankara, 06532, Turkey
b
Published online: 16 Aug 2006.
To cite this article: Canan Ünaleroğlu , Barış Temelli & Tuncer Hökelek (2002) A FACILE SYNTHESIS AND CHARACTERIZATION
OF THE NOVEL 2,2-DICHLORO-1-[3-(2,2-DICHLORO-ACETYL)-2-(4-METHOXY-PHENYL)-IMIDAZOLIDIN-1-YL]-ETHANONE, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:21, 3255-3261, DOI:
10.1081/SCC-120014029
To link to this article: http://dx.doi.org/10.1081/SCC-120014029
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 21, pp. 3255–3261, 2002
A FACILE SYNTHESIS AND
CHARACTERIZATION OF THE NOVEL
2
,2-DICHLORO-1-[3-(2,2-DICHLORO-
ACETYL)-2-(4-METHOXY-PHENYL)-
IMIDAZOLIDIN-1-YL]-ETHANONE
1,*
1
¨
Canan Unalerog
˘
and Tuncer Ho
lu,
Bar|sꢀ Temelli,
2
¨
kelek
1
2
Department of Chemistry, and Department of Physics,
Hacettepe University, 06532 Beytepe-Ankara, Turkey
ABSTRACT
The synthesis of (2,2-dichloro-1-[3-(2,2-dichloro-acetyl)-2-
(4-methoxy-phenyl)-imidazolidin-1-yl]-ethanone by a facile
0
one-pot reaction between N,N -bis(4-methoxy-benzylidene)-
ethane-1,2-diamine and dichloroacetyl chloride is described.
1
The structure was confirmed by H NMR, MS and FTIR
techniques and X-ray crystallography.
Key Words: Imidazolidin; Imine; Intramolecular cyclization
The reaction of imines with ketenes in the presence of tertiary amines
to produce b-lactams (2-azetidiones) is known as the Staudinger reaction,
[
1,2]
which is very useful in synthetic organic chemistry.
The cycloaddition
*
Corresponding author. E-mail: canan@hacettepe.edu.tr
255
3
DOI: 10.1081/SCC-120014029
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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¨
˘ ¨
UNALEROGLU, TEMELLI, AND HOKELEK
3
256
of various types of imines with ketenes derived from acid chlorides
[
3–7]
yields [2 þ 2] cycloaddition products.
part of a conjugated system both [2 þ 2] and [4 þ 2] cycloadducts form.
Recently, bis-b-lactams have been prepared by Bhawal et al. via reaction of
When the imine function is a
[
8,9]
0
0
0
bisimines, R CH¼NCH CH N¼CHR (R ¼C H OCH , Ph, –CH¼CHPh),
2
2
6
4
3
with ketenes derived from acid chlorides, ROCH COCl (R¼Ph, Bn, Ac), in
2
[
10]
the presence of triethylamine in dichloromethane.
In the present work, we have extended the above methodology to the
0
synthesis of a bis-b-lactam starting with N,N -bis(4-methoxy-benzylidene)-
ethane-1,2-diamine (I), dichloroacetyl chloride and triethylamine in CH Cl .
2
2
We obtained 2,2-dichloro-1-[3-(2,2-dichloro-acetyl)-2-(4-methoxy-phenyl)-
imidazolidin-1-yl]-ethanone (II) as a novel product (Eq. 1). Agafonov et al.
performed similar reactions between bisimines and benzoyl chloride in the
presence of triethylamine and obtained a number of products including
[
11,12]
mono- and bis-acylated imidazolidine derivatives.
ð1Þ
We conducted several experiments to show the effect of the addition
order of reactants (dropwise adding the acid chloride onto I and triethyl-
amine or adding the amine onto the acid chloride and I), and solvent effect
using a nonpolar solvent (benzene) on the product. II was formed as the
only product regardless of the order of addition and solvent type. The
expected [2 þ 2] addition product was not formed. The structure of II was
1
confirmed by MS, H NMR, FTIR techniques and single crystal X-ray
analysis for which the ORTEP diagram is given in Fig. 1.
To establish the role of triethylamine, the reaction was repeated in the
absence of the amine in CH Cl . Compound II was formed again in high
2
2
yield. Thus, the exclusive formation of imidazolidine (II) indicates that
2 þ 2] cycloaddition reaction through a ketene pathway is disfavored in
this system.
We suggest two possible mechanisms for the formation of imidazoli-
dine (II): i. the reaction of I with dichloroacetyl chloride gives B via
[

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NOVEL 2,2-DICHLORO-1-ETHANONE
3257
[
14]
Figure 1. An ORTEP
thermal ellipsoids are drawn at the 50% probability level.
diagram of II with the atom-numbering scheme. The
ð2Þ
formation of A. Elimination of RCHCl2 following the intramolecular
cyclization through C can furnish the desired product II (Eq. 2), or ii. the
reaction of dichloroacetyl chloride with I gives D which is followed by the
intramolecular cyclization to E. Then the reaction of E with dichloroacetyl
chloride yields the product II (Eq. 3). These proposed mechanisms agree
[
11–13]
with the related reports available in the literature.

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¨
˘
UNALEROGLU, TEMELLI, AND HOKELEK
¨
3
258
ð3Þ
The method described here provides a facile one-pot route for the high
yield synthesis of 2-substituted imidazolidines that can be isolated easily.
The formation of a bis-acylated product in higher selectivity is another
advantage of this system.
EXPERIMENTAL
Ethylenediamine and dichloroacetyl chloride were obtained from
Aldrich. All reagents were dried prior to use. NMR spectra were recorded
in CDCl solution using TMS as internal standard on a DPX-400 instru-
3
ment (Bruker). FTIR spectra were obtained on a SHIMADZU FTIR-8101
spectrophotometer as KBr discs. MS data were measured with a GC-MS
Thermoquest Trace 2000 instrument. Melting point was measured on a
Gallenkamp apparatus.
X-Ray Analysis
Data of II were measured on an Enraf-Nonius CAD-4 diffractometer
˚
using graphite monochromated Cu-K (l ¼ 1.54184 A) radiation. Crystals
a
belongs to orthorhombic space group P2 ab with a ¼ 9.883(2), b ¼ 11.527(1),
1
3
ꢁ3
ꢁ1
˚
˚
c ¼ 15,384(2) A; V ¼ 1752.6(4) A ; Z ¼ 4, D ¼ 1.516 Mg ꢀ m , ꢀ ¼ 6.273 mm
.
Out of 1363 reflections measured, 076 were treated observed with
x
[
15]
[
I ꢂ 2.0 ꢁ(I )]. The structure was solved by direct methods, SHELXS97.
Least square refinement of scale factor, positional and anisotropic thermal
parameters for non hydrogen atoms converged to R ¼ 0.0648, wR ¼ 0.1528.
The H atoms were positioned geometrically, and a riding model was used

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NOVEL 2,2-DICHLORO-1-ETHANONE
3259
during the refinement. Refinements were carried out by using
SHELXL97.
[16]
0
N,N -bis(4-Methoxy-benzylidene)-ethane-1,2-diamine:
4.57 g, 33.60 mmol) was dissolved in ethanol (20 mL). Ethylenediamine
Anisaldehyde
(
(
ꢃ
0.88 g, 14.66 mmol) was then added and the solution was heated at 60 C.
After 1 h, the reaction was completed. The product was filtered and recrys-
ꢃ
ꢃ
ꢁ1
tallized in methanol. Yield: 90%, m.p.: 110 –111 C, IR (cm ): 3080
(
ꢂC-H aromatic); 2840–2900 (ꢂC-H aliphatic); 1641 (ꢂ
); 1109 (ꢂC-O). The crys-
tal structure of N,N -bis(4-methoxy-benzylidene)-ethane-1,2-diamine (I) was
C¼O
0
[17]
described.
,2-Dichloro-1-[3-(2,2-dichloro-acetyl)-2-(4-methoxy-phenyl)-imidazoli-
din-1-yl]-ethanone: Asolution of dichloroacetyl chloride (2.98 g,
0.24 mmol) in dry CH Cl (15 mL) was slowly added to a solution contain-
2
2
2
2
ing imine I (1.5 g, 5.06 mmol) and triethylamine (2.05 g, 20.24 mmol) in
ꢃ
CH Cl (15 mL) at 0 C, under nitrogen. The reaction mixture was then
2
2
allowed to warm to r.t. and stirred further for 24 h. It was then washed
with satd. NaHCO3 (2 ꢄ 20 mL), brine and dried (CaCl ). Crude
2
product was separated through addition of EtOAc and recrystallized in
ꢃ
ꢃ
þ
EtOAc. Yield: 78%, m.p.: 188 –189 C, MS (EI): m/z 398 (M ) and the
isotopic patterns of M þ 2, M þ 4, M þ 6 and M þ 8, m/z 363 [m/z 398–35
(
Cl)], m/z 328 [m/z 398–70 (2Cl)], m/z 291 [m/z 398–107 (C H OCH )], m/z
6 4 3
87 [m/z 398–111 (COCHCl )]; H NMR (DMSO-d ) d: 3.83 (s, 3H,
OCH ), 4.01 and 4.19 (2s (br), 4H, NCH CH N), 6.58 (s, 1H, NCHN),
.85–6.93 (m, 4H, 2(–CHCl ) and Haromatic), 7.28–7.35 (m, 2H, Haromatic);
IR (cm ): 3025 (ꢂC-H aromatic); 2825–2900 (ꢂC-H aliphatic); 1680 (ꢂCO-N);
1
2
–
6
2
6
3
2
2
2
ꢁ
1
1090 (ꢂC-O).
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1
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2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
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NOVEL 2,2-DICHLORO-1-ETHANONE
3261
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Received in the UK August 15, 2001

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