Ethyl 2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate

Malahat M Kurbanova; Elnur Z Huseynov; Atash V Gurbanov; Abel M Maharramov; Seik Weng Ng

doi:10.1107/S1600536812028371

. 2012 Jun 27;68(Pt 7):o2233. doi: 10.1107/S1600536812028371

Ethyl 2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

Malahat M Kurbanova ^a, Elnur Z Huseynov ^a, Atash V Gurbanov ^a, Abel M Maharramov ^a, Seik Weng Ng ^b,^c,^*

PMCID: PMC3394024 PMID: 22798889

Abstract

In the title compound, C₂₁H₂₅NO₃, the hydropyridine ring that constitutes a part of the hexahydroquinoline fused-ring system adopts a sofa conformation; the methine C atom deviates from the least-squares plane defined by the remaining five non-H atoms (r.m.s. deviation = 0.088 Å) by 0.454 (3) Å. The phenyl ring is aligned at 85.5 (1)° with respect to this mean plane. In the crystal, adjacent molecules are linked via an N—H⋯O hydrogen bond, involving the amino group and the carbonyl O atom of the fused-ring system, forming chains running along [100]. The ethyl group is disordered over two positions in a 0.609 (6):0.391 (6) ratio.

Related literature

For the synthesis, see: Safari et al. (2011 ▶). For the crystal structure of methyl 2,7,7-trimethyl-4-phenyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, see: Duque et al. (2000 ▶).

Experimental

Crystal data

C₂₁H₂₅NO₃
M _r = 339.42
Triclinic,
a = 7.3523 (4) Å
b = 9.6349 (5) Å
c = 13.9495 (7) Å
α = 98.370 (1)°
β = 91.778 (1)°
γ = 106.291 (1)°
V = 935.70 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
10191 measured reflections
4302 independent reflections
3439 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.135
S = 1.03
4302 reflections
254 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812028371/xu5576sup1.cif

e-68-o2233-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028371/xu5576Isup2.hkl

e-68-o2233-Isup2.hkl^{(210.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812028371/xu5576Isup3.cml

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⋯O1ⁱ	0.87 (1)	2.04 (1)	2.890 (1)	168 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Baku State University and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

supplementary crystallographic information

Comment

C5-Unsubstituted 1,4-dihydropyridines are readily synthesized by the reaction of dimedone, acetophenone, aromatic aldehydes, and ammonium acetate in the presence of a catalytic amount of a cobalt salt under solvent-free conditions (Safari et al. 2011). The title compound (Scheme I), was synthesized by a slightly different procedure from benzaldehyde, ethyl acetoacetate and ammonium acetate and with L-glutamine as catalyst, and in ethanol medium.

The hydropyridine ring that constitutes a part of the hexahydroquinoline fused-ring system of C₂₁H₂₅NO₃ adopts a sofa conformation; the methine C atom bearing the phenyl substituent deviates from the least-squares plane defined by the N and four double-bond C atoms by 0.454 (3) Å. The phenyl ring is nearly orthogornal to this plane (Fig. 1). The amino group is hydrogen-bond donor to the carbonyl O atom of the fused-ring of another molecule; adjacent molecules are linked by an N—H···O hydrogen bond to form a chain running along the a-axis of the triclinic cell (Table 1, Fig. 2).

Experimental

Dimedone (0.56 g, 2 mmol) was stirred with benzaldehyde (0.40 ml, 2 mmol), ethyl acetoacetate (0.5 ml, 2 mmol) and ammonium acetate (0.308 g, 2 mmol) in ethanol (50 ml) for 12 h at the room temperature. A small quantity of L-glutamine (0.05 g) was added as catalyst. Recrystallization was effected by using ethanol as solvent.