Synthesis and structural study of N-isopropenylbenzimidazolone

Article abstract of DOI:10.1134/S0036024415050271

The synthesis and the crystal structure of the N-isopropenylbenzimidazolone (C₁₀H₁₀N₂O) are presented. The synthesis was performed by Meth-Cohen method by reaction of o-phenylenediamine with ethyl acetoacetate in refluxed xylene. The single crystal structure was determined at room temperature by means of X-rays diffraction. The crystal system is monoclinic, with space group C2/c and eight molecules per unit cell. The unit cell dimensions are: a = 15.978(1) ?, b = 6.100(2) ?, c = 18.222(2) ?, β = 90.16(1)° and V = 1776.0(6) ?³.

Full text of DOI:10.1134/S0036024415050271

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2015, Vol. 89, No. 5, pp. 807–811. © Pleiades Publishing, Ltd., 2015.
STRUCTURE OF MATTER
AND QUANTUM CHEMISTRY
Synthesis and Structural Study of N-Isopropenylbenzimidazolone1
D. Mondieiga, Ph. Negriera, J. M. Legerb, L. Lakhrissic,d, A. El Assyry*,e,
B. Lakhrissic, E. M. Essassid, B. Benalie, and A. Boucettae
a Centre de Physique Moléculaire Optique et Hertzienne, Université Bordeaux1, 351 cours de la Libération Talence, France
b Laboratoire de Pharmacochimie, EA4138 Université Victor Segalen Bordeaux2, 146 rue Léo Saignat, Bordeaux, France
c Laboratoire d’Agroressources et Génie des procédés, Université Ibn Tofail, Département de Chimie, B.P. 133, Kénitra, Maroc
d Laboratoire de Chimie Organique Hétérocyclique, Faculté des Sciences, Rabat, Maroc
e Laboratoire d’Opto-électronique et de Physico-Chimie des Matériaux, (Unité associée au CNRST), Université Ibn Tofail,
Département de Physique, B.P. 133, Kénitra, Maroc
* e-mail: abdeslam_elassyry@yahoo.fr
Received May 7, 2014
Abstract—The synthesis and the crystal structure of the N-isopropenylbenzimidazolone (C10H10N2O) are
presented. The synthesis was performed by Meth-Cohen method by reaction of o-phenylenediamine with
ethyl acetoacetate in refluxed xylene. The single crystal structure was determined at room temperature by
means of X-rays diffraction. The crystal system is monoclinic, with space group C2/c and eight molecules per
unit cell. The unit cell dimensions are: a = 15.978(1) Å, b = 6.100(2) Å, c = 18.222(2) Å, β = 90.16(1)° and
V = 1776.0(6) Å3.
Keywords: N-isopropenybenzimidazolone, synthesis, single crystal structure.
DOI: 10.1134/S0036024415050271
Table 1. Crystal data and structure refinement for N-iso-
propenylbenzimidazolone
1. INTRODUCTION
Benzimidazolone is an interesting heterocycle. It is
present in various natural compounds [1]. Its deriva-
tives are known to have various pharmaceutical appli-
cations as novel NOP receptor agonists [2], progester-
one receptor antagonists [3], they are also potential
therapeutics for cystic fibrosis, chronic obstructive
pulmonary disease, and have gastroprokinetic proper-
ties [4]. They can also be used as pigments [5]. Else-
where, the benzimidazolone derivatives have biologi-
cal activity [6–10] as well as complexant and surfac-
tant properties [11–16].
Empirical formula: C10H10N2O
Formula weight = 174.2
Crystal system: Monoclinic
Space group: C2/c, Z = 8
Cell dimensions: a = 15.978(1) Å, b = 6.100(2) Å,
c = 18.222 (2) Å, β = 90.16(1)°
V = 1776.0(6) Å3
T = 296(2) K
Dcal = 1.303 g/cm3
It is known that the condensation of o-phenylene-
diamine 1 with ethyl acetoacetate 2, in refluxed xylene
during 1 h, gives 4-methyl-1,5-benzodiazepin-1-one
but by prolonging the reaction time for 6 h, the authors
have obtained N-isopropenylbenzimidazol-2-one-3
resulting from a sigmatropic rearrangement [1, 3] of
the diazepinic ring [17].
Studies on thermal, structural, spectral and confor-
mational properties of the benzimidazolone molecule
were recently reported by our group [18–21]. In this
paper, we describe the synthesis of N-isopropenylben-
zimidazolone by the Meth-Cohen method [9], by the
reaction of o-phenylenediamine with ethyl acetoacetate
in refluxing xylene (Scheme 1). Then we present the
X-rays crystal structure analysis of this compound.
No. reflections used = 1514
μ(CuKα) = 0.886 mm–1, λ = 1.5418 Å
2θmax = 64.95°
Crystal size = 0.25 × 0.10 × 0.10 mm
F(000) = 736
R[I > 2σ(F2)] = 0.0344 and wR(F 2) = 0.0851
Max. and min. transmission 0.9332 and 0.8443
No. of parameters = 159
Goodness-of-fit on F 2 = 1.067
Extinction coefficient = 0.0064(4)
Measurement Enraf-Nonius CAD4
Program system: Enraf-Nonius SDP
Structure determination: SHELXL-97
Refinement: full-matrix least-squares
1
The article is published in the original.
807

808
MONDIEIG et al.
CH3
H
N
NH2
NH2
O
O
Xylene
+
O
CH2
Δ, 6 h
N
OC2H5
H3C
CH2
1
2
3
Scheme 1. N-Isopropenylbenzimidazolone synthesis.
2. EXPERIMENTAL SECTION
2.1. Synthesis Control Methods
Melting point was determined with an electrother-
mal IA 9200 digital melting point apparatus in capil-
lary tubes and are uncorrected.
treated with acetic acid (25 mL) to give the second
portion of N-isopropenylbenzimidazolone (5 g). The
precipitate was then filtered, washed several times with
water and diethyl ether and dried in the oven. (Total
yield ~70%). The compound structure was confirmed
1
by H and 13C NMR spectroscopy, m.p. 120–122°C,
1H NMR (CDCl3): δ 2.10 (3H, s, CH3), δ 5.10 (1H, s,
H2a), δ 5.30 (1H, s, H2b), δ 6.95–7.05 (4H, m, Harom),
NMR spectra were recorded on a BRUKER AM
1
300 spectrometer operating at 300 MHz for H and
75 MHz for 13C in CDCl3. Chemical shifts are
reported in δ units (ppm) relative to internal SiMe4
standard.
δ 10.70 (1H,s, NH); 13C NMR (CDCl3): δ 19.6;19.7
(CH3), δ 112.0 (=CH2), δ 137.6 (NC), δ 108.5 (C-4),
δ 108.9 (C-7), δ 120.6 (C-5), δ 121.2 (C-6), δ 128.5
(C-8), δ 129.4 (C-9), δ 152.7 (C=O).
2.2. X-rays Diffraction
A colorless single crystal (0.25 × 0.10 × 0.10 mm)
was selected and mounted on an ENRAF-NONIUS
CAD4 diffractometer equipped with a charge coupled
3.2. Crystal Data
N-isopropenylbenzimidazolone structure was
determined at room temperature. The details of struc-
ture analysis are given in Table1 and an ORTEP plot of
the molecule is shown in Fig. 1. The compound crys-
tallizes in monoclinic C2/c group and contains 8 mol-
ecules per unit cell. The atomic coordinates and equiv-
alent isotropic displacement parameters of the atoms
are given in Table 2. Bond lengths and angles are given
in Table 3. The two rings of the N-isopropenylbenzim-
idazolone are nearly planar as found for various ben-
zimidazole derivatives structures [24, 25]. The highest
deviation (–0.017(2) Å) to the mean plane is for N6.
device (CCD) detector using the CuK radiation (λ =
α
1.5418 Å). 1514 reflexions were collected in the 4.85 to
64.95° θ range. The details of data collection are given
in Table 1. The structure was solved by direct methods.
The non-hydrogen atoms were located from the dif-
ference Fourier maps and further refined anisotropi-
cally by full-matrix least-squares to final reliability
values of 0.0344. All hydrogen atoms were refined iso-
tropically. Refinements were carried out using
SHELXL-97 [22]. Molecular structures were drawn
using ORTEP and Material studio software [23].
This plane is nearly parallel to the [1 0] direction,
1
the angle between the plane and the diagonal is about
8°. The projection of the crystal structure along the
a‒c plane is shown in Fig. 2. The benzene ring pres-
3. RESULTS AND DISCUSSION
3.1. Synthesis
To a mixture of o-phenylenediamine 1 (51.0 g, ents standard C–C bond lengths. These parameters
0.47 mol) with xylene (200 mL), an ethyl acetoacetate are in agreement with previous theoretical studies of
(69.0 g, 0.53 mol) solution in xylene (30 mL) was some heterocyclic derivatives [26] and experimental
added dropwise within 10 min. The reaction mixture studies on benzodiazepine derivatives [27, 28]. The
was refluxed for 6 h. The water and ethanol formed short N(3)–C(2) distance (1.359 Å) indicates a slight
were removed progressively by an azeotropic distilla- resonance with the O(1) and the long N(6)–C(2)
tion. The mixture was then cooled and the precipitated (1.385 Å) distance shows an increase of this resonance
white solid was collected by filtration, washed two due essentially to the isopropenyl group effect. Fur-
times with ether, dried in the oven to give the first por- thermore, the molecules are stacked with some hydro-
tion of N-isopropenylbenzimidazolone (55.0 g). The gen bonds. The most important is N(3)–H(3)···O(1)
filtrate was then treated with 20% NaOH (400 mL), hydrogen bond with N(3)···O(1) distance of 2.827 Å
the N-isopropenylbenzimidazolone salt was filtered, and angle of 171.7°. Other intramolecular hydrogen
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Table 2. Atomic coordinates (Å) and equivalent isotropic Table 3. Bond lengths [Å] and angles [deg]
displacement parameters (Å2) for the non-hydrogen atoms
Bond lengths
(Ueq is defined as one third of the trace of the orthogonal-
ized Uij tensor) and isotropic displacement parameters (Å2)
N3
O1
N3
N6
N6
N6
N3
C4
C4
C5
C7
C8
C2
C2
C4
C2
C5
C11
H3
C5
C7
C10
C8
C9
1.359(5) C9
1.231(2) C11
1.386(2) C11
1.385(2) C7
1.406(2) C8
1.433(2) C9
0.889(18) C10
1.394(2) C12
1.380(5) C12
1.379(2) C12
1.387(2) C13
1.382(2) C13
C10
C12
C13
H7
H8
H9
H10
H12A
H12B
H12C
H13A
H13B
1.389(3)
for hydrogen atoms
1.488(3)
1.315(3)
1.001(19)
0.96(2)
0.963(18)
0.975(17)
1.00(3)
0.99(2)
1.00(2)
1.02(2)
Ueq or Uiso
Atom
x
y
z
O1
N3
N6
C2
C4
C5
C7
C8
C9
0.08611(7) 0.08697(18) 0.43663(6) 0.0549(4)
–0.04621(8) 0.2330(2)
0.03799(7) 0.4075(2)
0.03140(9) 0.2259(2)
–0.08974(9) 0.4157(3)
–0.03668(8) 0.5288(3)
–0.16984(10) 0.4890(3)
–0.19541(11) 0.6806(3)
0.45683(7) 0.0480(4)
0.38140(7) 0.0437(4)
0.42661(8) 0.0436(5)
0.43241(8) 0.0427(5)
0.38502(7) 0.0410(4)
0.44630(9) 0.0534(6)
0.41192(10) 0.0577(6)
1.03(2)
Bond angles
C2 N3 C4 110.68(12) C12
C2 N6 C5 109.10(12) N6
C2 N6 C11 124.39(12) C4
C5 N6 C11 126.37(13) C8
C2 N3 H3 123.7(12) C7
C4 N3 H3 125.4(12) C9
O1 C2 N3 127.62(13) C8
C11 C13
C11 C13
C7 H7
C7 H7
C8 H8
C8 H8
C9 H9
125.30(16)
119.37(16)
119.8(10)
122.7(10)
117.9(11)
121.2(11)
119.2(11)
119.0(11)
–0.14237(11) 0.7930(3) 0.36544(10) 0.0574(6)
0.35138(9) 0.0505(5)
C10 –0.06161(11) 0.7205(3)
C11
C12
C13
H3
0.10821(9) 0.4524(3) 0.33499(8) 0.0466(5)
0.12855(14) 0.2777(4) 0.28090(11) 0.0645(7)
0.14668(12) 0.6423(3) 0.34043(12) 0.0643(7)
N3 C2 N6 106.65(11) C10 C9 H9
–0.0643(11) 0.138(3)
–0.2070(11) 0.404(3)
–0.2504(13) 0.734(3)
–0.1617(12) 0.926(3)
0.4902(10) 0.056(5)
0.4801(11) 0.068(5)
0.4223(10) 0.067(5)
0.3425(10) 0.069(5)
O1 C2 N6 125.73(13) C5
N3 C4 C7 131.79(15) C9
C5 C4 C7 121.27(16) C11
N3 C4 C5 106.92(13) C11
C4 C5 C10 121.30(14) C11
C10 H10 120.3(10)
C10 H10 122.6(10)
C12 H12A 115.2(15)
C12 H12B 111.1(14)
C12 H12C 109.4(14)
H7
H8
H9
H10 –0.0236(10) 0.798(3)
H12A 0.0813(17) 0.234(4)
H12B 0.1464(15) 0.142(4)
H12C 0.1752(15) 0.329(4)
H13A 0.1943(13) 0.678(4)
H13B 0.1308(13) 0.758(4)
0.3186(9)
0.056(5)
N6 C5 C4 106.63(14) H12A C12 H12B 106(2)
N6 C5 C10 132.06(14) H12A C12 H12C 106(2)
C4 C7 C8 117.54(16) H12B C12 H12C 109(2)
0.2476(13) 0.111(9)
0.3058(13) 0.102(8)
0.2483(13) 0.099(7)
0.3055(11) 0.081(6)
0.3794(12) 0.086(7)
C7 C8 C9 120.96(16) C11
C8 C9 C10 121.79(17) C11
C13 H13A 119.5(13)
C13 H13B 122.5(13)
C5 C10 C9 117.11(15) H13A C13 H13B 118.0(18)
Table 4. Hydrogen bonding geometry (Å)
D–HΛA
D–H (Å)
HΛA (Å)
DΛA (Å)
D–HΛA (deg)
Symmetry code
N(3)–H(3)LO(1)S1
C(12)–H(12B)LO(1)S2
C(13)–H(12C)LO(1)S3
0.889(18)
0.99(2)
1.946(19)
2.60(3)
2.827(2)
3.142(3)
3.373(2)
171.1(17)
115.1(17)
162.7(18)
–x, –y, –z + 1
x, y, z
1.03(2)
2.37(2)
x, y + 1, z
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MONDIEIG et al.
C7
N3
C8
O1
C4
C2
C5
C9
N6
C10
C11
C13
C12
Fig. 1. ORTEP plot of N-isopropenylbenzimidazolone with the ellipsoids drawn at the 50% probability level.
c
z
x
a
b
Fig. 2. Projection of the N-isopropenylbenzimidazolone crystal structure along the a,c-plane. The dashed lines indicate the
hydrogen bonds.
bonding chelate withdrawals appear involving try. Intra- and intermolecular hydrogen bonds are
C(12B)–H(12B)···O(1) and C(13)–H(13C)···O(1). participating in crystal cohesion. The strongest hydro-
The shortest bond lengths are given in Table 4 along gen bonds are N–H···O bonds.
with the angles. In Fig. 2, the hydrogen bonds are
marked with dashed lines.
ACKNOWLEDGMENTS
This work has been supported in part by the
CONCLUSIONS
Morocco-French (CNRST-CNRS) Convention and
The synthesis and the single-crystal stucture of the by the Hassan II Academy of Science and Technology.
N-isopropenylbenzimidazolone molecule is pre-
sented. The compound was prepared according to
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