Ethyl 2-[1,3-dioxo-6-(piperidin-1-yl)-2,3-dihydro-1H-benz[de]isoquinolin-2-yl]acetate

Song Xia; Chun-Ling Zheng; Fei-Fei He; Ya-Bin Shi; Hai-Bo Wang

doi:10.1107/S1600536811022707

. 2011 Jun 18;67(Pt 7):o1717. doi: 10.1107/S1600536811022707

Ethyl 2-[1,3-dioxo-6-(piperidin-1-yl)-2,3-dihydro-1H-benz[de]isoquinolin-2-yl]acetate

Song Xia ^a,^b, Chun-Ling Zheng ^a, Fei-Fei He ^a,^b, Ya-Bin Shi ^a,^b, Hai-Bo Wang ^a,^*

PMCID: PMC3152026 PMID: 21837109

Abstract

In the title compound, C₂₁H₂₂N₂O₄, the naphthalimide unit is almost planar (r.m.s. deviation = 0.081Å). The carboximide N atom and the five C atoms of the ethoxycarbonylmethyl substituent also lie close to a common plane (r.m.s. deviation = 0.119Å), which subtends an angle of 71.06 (8)° to the naphthalamide plane. The piperidine ring adopts a chair conformation. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into zigzag chains along the a axis.

Related literature

For general background to applications of 1,8-naphthalimides, see: McAdam et al. (2003 ▶); Fülöp et al. (2009 ▶). For a related structure, see: Hanton et al. (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₂₂N₂O₄
M _r = 366.41
Orthorhombic,
a = 10.959 (2) Å
b = 18.037 (4) Å
c = 9.3330 (19) Å
V = 1844.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.973, T _max = 0.991
3547 measured reflections
1808 independent reflections
1280 reflections with I > 2σ(I)
R _int = 0.039
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.115
S = 1.00
1808 reflections
244 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811022707/sj5150sup1.cif

e-67-o1717-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022707/sj5150Isup2.hkl

e-67-o1717-Isup2.hkl^{(89KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811022707/sj5150Isup3.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
C1—H1A⋯O2ⁱ	0.97	2.60	3.455 (6)	147
C1—H1B⋯O1ⁱⁱ	0.97	2.51	3.373 (5)	149
C5—H5A⋯O2ⁱⁱⁱ	0.97	2.44	3.219 (6)	138
C18—H18B⋯O4^iv	0.97	2.56	3.315 (5)	135

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

This work was supported by the Higher Education Institutions Natural Science Foundation of the Jiangsu Educational Commission (grant No. 09KJB540001) and the General Program of the National Natural Science Foundation of China (grant No. 51003047).

supplementary crystallographic information

Comment

1,8-naphthalimide derivatives are recognized to have an importance in dye and medicinal chemistry. They can be used as intermediates in the synthesis of organic pigments, in biological fluorescent labeling and as optical brighteners, pH-dependent sensors, laser and electroluminscent dyes and liquid crystals (McAdam et al., 2003). We have selected 4-substituted 1,8-naphthalimides to use in the synthesis of fluorophore groups, since they are highly photostable, cheap and their chemical modification is straightforward. Moreover, these dyes exhibit large Stoke's shifts due to the formation of an intramolecular charge transfer (ICT) state upon absorption of light. (Fülöp et al. 2009).

We report here the crystal structure of the title compound, N-[(2-Ethoxy)-2-oxo-ethyl]-4-piperidino-1,8-naphthalimide. In the structure of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges (Hanton et al., 2010). In the crystal structure, intermolecular C-H···O hydrogen bonds link the molecules into zig-zag chains along the a axis, to form a stable structure (Fig. 2).

Experimental

The title compound, 1H-Benz[de]isoquinoline- 2(3H)-acetic acid, 6-(piperidin-1-yl)-1,3-dioxo-, ethyl ester was prepared by a method similar to that reported in the literature (Fülöp et al. 2009). 1H-Benz [de]isoquinoline- 2(3H)-acetic acid, 6-bromo-1,3-dioxo-, ethyl ester(3.82 g, 10.5 mmol) was dissolved in N-methylpyrrolidone (NMP, 58.5 mL) and piperidine (4.5 mL, 52.5 mmol) together with triethylamine (TEA, 14.8 mL, 105 mmol) were added. The mixture was stirred for 4 h at 383K. Then water (200 mL) was added, which induced formation of yellow precipitate. The precipitate was filtered, washed with water (150 mL), dried and re-crystallized from ethanol. Yield 3.34 g (86%). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.