6-Formyl-2-naphthyl cis-1,5,7-trimethyl-2,4-dioxo-3-aza­bicyclo­[3.3.1]nonane-7-carboxyl­ate

Sheng-guang Xu; Chun-hua Wang; Jun-shen Liu; Xi-guang Liu; Long Li

doi:10.1107/S1600536809054786

. 2009 Dec 24;66(Pt 1):o245. doi: 10.1107/S1600536809054786

6-Formyl-2-naphthyl cis-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonane-7-carboxylate

Sheng-guang Xu ^a,^*, Chun-hua Wang ^a, Jun-shen Liu ^a, Xi-guang Liu ^a, Long Li ^a

PMCID: PMC2980281 PMID: 21580126

Abstract

In the title compound, C₂₃H₂₃NO₅, the C₅N ring adopts an envelope conformation with a C atom as the flap, whilst the saturated C₆ ring fused to it adopts a chair conformation. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R ₂ ²(8) loops.

Related literature

For further information on the title compound as a building block in a dynamic combinatorial library, see: Xu & Giuseppone (2008 ▶). For further synthetic details, see: Askew et al. (1989 ▶); Rebek et al. (1987 ▶); Steglich & Höfle (1969 ▶); Williams et al. (1989 ▶); Chamontin et al. (1999 ▶).

Experimental

Crystal data

C₂₃H₂₃NO₅
M _r = 393.42
Monoclinic,
a = 11.896 (2) Å
b = 11.692 (2) Å
c = 16.636 (2) Å
β = 121.124 (9)°
V = 1980.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.28 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.974, T _max = 0.982
10443 measured reflections
3897 independent reflections
3217 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.105
S = 1.03
3897 reflections
265 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809054786/hb5273sup1.cif

e-66-0o245-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054786/hb5273Isup2.hkl

e-66-0o245-Isup2.hkl^{(191KB, 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—H22⋯O5ⁱ	0.87	2.02	2.8776 (14)	166

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Foundation of Ludong University and the Students Research Fund of Ludong University.

supplementary crystallographic information

Comment

The title compound (6-formylnaphthalen-2-yl cis-1,5,7-trimethyl-2,4-dioxo-3-aza-bicyclo[3.3.1]nonane-7-carboxylate), reported by Xu and Giuseppone (Xu et al., 2008) as a key building block in a dynamic combinatorial library in which one product was self-amplified via self-complementary process, contains a steric bulk and a imide functional group which is a good receptor for adenine through the hydrogen bonding interaction like a base pairing. Herein we report the molecular and crystal structure of the title compound.

The unit structure of the title compound is illustrated in Fig. 1. The asymmetry of the title compound contains two ten-member rings: a naphthalene ring and a V conformation ring, which are connected each other via the carboxylate (O₂—C₁₂—O₃). The naphth ring is approximately planar. In addition, the molecures are linked by the N₁—H···O₅ hrdrogen bond, forming inversion dimers.

Experimental

As delineated in Scheme 1, the product was synthesized (Rebek et al., 1987; Askew et al., 1989; Williams et al., 1989) from the starting material Kemp's triacid (01) which is commercially available. Firstly, anhydride acid (02) was prepared after dehydration of Kemp Triacid (01) under reflux 17 h in xylenes under N₂. After anhydride acid (02) was treated with concentrated aqueous ammonium hydroxide (NH₄OH) and 4-(dimthylamino)pyridine (DMAP) (Steglich et al., 1969) at 383 K overnight, Imide Acid (03) was gained. Then we got Imide Acid Chloride (04) after the solution of Imide Acid (03) in fresh thionylchloride was reflux under nitrogen atmosphere for 3 h. At the end the target Materiel Al₁ was prepared from Imide Acid Chloride (04) reacted with 6-hydroxy-2-naphthaldehyde (Chamontin et al., 1999) catalyzed by sodium hydride (NaH).

Product, yielding 60%. ¹H NMR (400MH_z,CDCl₃, TMS) δ 10.069 (s, 1H), δ 8.244 (s, 1H), δ 7.930–7.818 (m, 3H), δ 7.589 (s, 1H), δ 7.589 (s, 1H), δ 7.540–7.535 (d, 1H), δ 7.234–7.206 (m, 1H), δ 2.822–2.787 (d, 2H), δ 2.029–1.996 (d, 1H), δ 1.488–1.267 (m, 12H); ¹³C NMR (CDCl₃) δ 191.97, 176.06, 173.75,150.71, 137.03, 134.04, 133.97, 131.06, 130.68, 128.88, 123.60, 122.10, 118.76,44.329, 43.799, 42.625, 40.178, 30.529, 24.313; ESI-TOF Eaxct Mass for C₂₃H₂₃NO₅[M+Li]⁺: calcd 399.1722, 400.1731, 401.1764, 402.1791, found 399.1740, 400.1769, 401.1801, 402.1832.