(Z)-3-Anilino-1,3-diphenylprop-2-en-1-one

Li-Ping Zhang; Lin-Juan Wei; Ming-Qing Chen; Zhan-Hui Zhang

doi:10.1107/S1600536808016711

. 2008 Jun 21;64(Pt 7):o1327. doi: 10.1107/S1600536808016711

(Z)-3-Anilino-1,3-diphenylprop-2-en-1-one

Li-Ping Zhang ^a,^*, Lin-Juan Wei ^a, Ming-Qing Chen ^a, Zhan-Hui Zhang ^b

PMCID: PMC2961639 PMID: 21202951

Abstract

In the title compound, C₂₁H₁₇NO, the phenyl ring directly linked to the carbonyl group is oriented at an angle of 7.3 (2)° with respect to the aniline ring, and at an angle of 55.6 (2)° with respect to the other phenyl ring. There is an intramolecular hydrogen bond involving the NH group and the carbonyl O atom. The crystal structure is stabilized by weak C—H⋯π interactions, which link the molecules into a herringbone arrangement.

Related literature

For related literature see: Dondoni & Perrone (1993 ▶); Ferraz et al. (1995 ▶); Michael et al. (2001 ▶); Azzaro et al. (1981 ▶); Alberola et al. (1999 ▶); Chaaban et al. (1979 ▶); Augusti & Kascheres (1993 ▶); Bejan et al. (1998 ▶); Eberlin & Kascheres (1988 ▶); Greenhill (1977 ▶); Michael et al. (1999 ▶); Elassar & El-Khair (2003 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

C₂₁H₁₇NO
M _r = 299.36
Monoclinic,
a = 15.880 (7) Å
b = 6.034 (3) Å
c = 18.401 (8) Å
β = 114.433 (7)°
V = 1605.4 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 294 (2) K
0.24 × 0.20 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.96, T _max = 0.98
7511 measured reflections
2774 independent reflections
1580 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.079
wR(F ²) = 0.249
S = 1.04
2774 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016711/su2060sup1.cif

e-64-o1327-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016711/su2060Isup2.hkl

e-64-o1327-Isup2.hkl^{(136.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.94	2.643 (5)	138
C18—H18⋯Cgⁱ	0.93	2.84	3.627 (1)	142

Open in a new tab

Symmetry code: (i) Inline graphic . Cg is the centroid of the C16–C21 ring.

Acknowledgments

This work was supported financially by Jiangnan University.

supplementary crystallographic information

Comment

β-enamino ketones are a highly versatile class of intermediates for the synthesis of natural therapeutic and biologically active analogues (Dondoni & Perrone, 1993; Ferraz et al., 1995; Michael et al., 2001; Azzaro et al., 1981). Pyrroles, oxazoles, pyridinones, quinolines, dibenzodiazepines have also been prepared from enaminones (Alberola et al., 1999; Chaaban et al., 1979; Augusti & Kascheres, 1993; Bejan et al., 1998; Eberlin & Kascheres, 1988). It is therefore not surprising that many synthetic methods have been developed for the preparation of these compounds (Greenhill, 1977; Michael et al., 1999; Elassar & El-Khair, 2003). During our development of new environmentally friendly methodologies for the preparation of β-enamino ketones (Zhang et al., 2006), we synthesized the title compound, (I), the structure of which is reported here.

The molecular structure of compound (I) is illustrated in Fig. 1. The geometry of the enamine double bond is Z, with hydrogen bonding of the enamine N—H to the carbonyl oxygen atom (Table 1). Phenyl ring A (C1-C6) forms dihedral angles of 7.3 (2)° and 55.6 (2)° with the aniline ring C (C16-C21) and the phenyl ring B (C10-C15), respectively. As in other β-enamino ketones compound (I) displays electron delocalization, as shown by the comparison of the N1—C9 [1.347 (6)°] and N1—C16 [1.417 (6) Å] bond lengths.

The crystal structure of compound (I) is stabilized by weak C—H···π interactions, which link the molecules into a herringbone chain (Fig. 2). The distance of the H atom to the centroid of the benzene ring is 2.834 (10) Å.

Experimental

A mixture of the 1,3-diphenylpropane-1,3-dione (5 mmol), aniline (5 mmol) and InBr₃ (0.05 mmol) was stirred at room temperature for 6 h. After completion of the reaction, the reaction mixture was diluted with H₂O (10 ml) and extracted with EtOAc(210 ml). The combined organic layers were dried, concentrated, and then purified by column chromatography on SiO₂ with ethyl acetate-cyclohexane (1: 8), giving a yellow-orange solid (yield 68%). Mp 96–97°C; IR (neat, cm^-1): ν 3053, 1592, 1568, 1475, 1441, 1323, 1212, 1079, 1053, 1022, 904, 841, 697 ¹H NMR (CDCl₃, 300 MHz): δ 6.09 (s, 1H), 6.78 (d, 2H), 6.96–7.00 (m, 1H), 7.09–7.14 (m, 2H), 7.26–7.50 (m, 8H), 7.96 (d, 2H), 12.90 (br s, 1H, NH). ¹³C NMR (CDCl₃, 75 MHz): δ 97.0, 123.1, 124.2, 127.2, 128.2, 128.5, 128.7, 129.6, 131.3, 135.8, 139.4, 139.8, 161.4, 189.6. ESI-MS: 300 (M+1)⁺ Elemental Anal. Calcd. for C₂₁H₁₇NO: C, 84.25; H, 5.72; N, 4.68. Found: C, 84.48; H, 5.82; N, 4.45. Single crystals of (I), suitable for X-ray diffraction analysis, were obtained from ethyl acetate-cyclohexane by slow evaporation at room temperature.