Ethyl 2-acetyl-3-(4-chloro­anilino)butanoate

K Rajesh; V Vijayakumar; T Narasimhamurthy; J Suresh; P L Nilantha Lakshman

doi:10.1107/S1600536809030876

. 2009 Aug 8;65(Pt 9):o2125. doi: 10.1107/S1600536809030876

Ethyl 2-acetyl-3-(4-chloroanilino)butanoate

K Rajesh ^a, V Vijayakumar ^a, T Narasimhamurthy ^b, J Suresh ^c, P L Nilantha Lakshman ^d,^*

PMCID: PMC2970076 PMID: 21577538

Abstract

The title compound, C₁₄H₁₈ClNO₃, adopts an extended conformation, with all of the main chain torsion angles associated with the ester and amino groups trans. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds are observed.

Related literature

For the crystal structure of ethyl 2-acetyl-3-anilinobutanoate, see: Priya et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₈ClNO₃
M _r = 283.74
Triclinic,
a = 6.9161 (2) Å
b = 10.1319 (3) Å
c = 11.4063 (3) Å
α = 87.511 (10)°
β = 80.873 (10)°
γ = 73.367 (2)°
V = 756.14 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.17 × 0.14 × 0.11 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.958, T _max = 0.972
14994 measured reflections
4229 independent reflections
3037 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.132
S = 1.04
4229 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030876/ci2874sup1.cif

e-65-o2125-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030876/ci2874Isup2.hkl

e-65-o2125-Isup2.hkl^{(203KB, 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
N7—H7⋯O12ⁱ	0.85 (2)	2.185 (19)	3.0282 (17)	170 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the use of the CCD facility at the Indian Institute of Science, Bangalore, set up under the IRHPA–DST programme.

supplementary crystallographic information

Comment

Ethyl butanoate is commonly used as an artificial flavoring agent in alcoholic beverages, perfumery products and as a plasticizer for cellulose. The crystal structure of ethyl 2-acetyl-3-anilinobutanoate has been reported (Priya et al., 2006).

In the title molecule (Fig. 1), there are three planar subunits viz. the chlorophenyl amine (C1-C6/N7/Cl1), acetyl (C10/C11/O12/C13) and ethyl acetate (C10/C14/O15/O16/C17/C18) groups. The chlorophenyl amino ring is inclined at angles of 76.28 (9) and 3.48 (7)° to the acetyl and ethyl acetate groups, respectively, with the acetyl group at an angle of 72.9 (1)° to the ethyl acetate group. The molecule adopts an extended conformation, with all of the main chain torsion angles associated with the ester and amino groups, i.e. from C18—C17—O16—C14 to C10—C8—N7—C1 lie in the range 157.20 (14)-178.59 (15)°.

In the crystal structure, molecules associate into dimers through intermolecular N—H···O hydrogen bonds (Table 1). The hydrogen-bonded centrosymmetric dimers are characterized by an R₂²(12) ring motif (Fig. 2) (Bernstein et al., 1995).

Experimental

A mixture of acetaldehyde (22.5 ml), ethyl acetoacetate (6.3 ml) and aniline (6.5 ml) was placed in a round bottomed flask. The contents were stirred at 273 K to 278 K for about 5 h under nitrogen atmosphere. A paste-like solid was formed, which was initially washed with benzene, then chloroform and then extracted with diethyl ether. The extract allowed to evaporate at room temperature yielded the product with crystalline nature. The resulting compound was recrystallized from diethyl ether (yield 88%, m. p. 357 K).