2,2-Diethyl 3,4-dimethyl 5-(4-cyano­phen­yl)pyrrolidine-2,2,3,4-tetra­carboxyl­ate

Long He

doi:10.1107/S1600536812029625

. 2012 Jul 7;68(Pt 8):o2363. doi: 10.1107/S1600536812029625

2,2-Diethyl 3,4-dimethyl 5-(4-cyanophenyl)pyrrolidine-2,2,3,4-tetracarboxylate

Long He ^a,^*

PMCID: PMC3414296 PMID: 22904829

Abstract

The title compound, C₂₁H₂₄N₂O₈, was synthesized by a 1,3-dipolar cycloaddition reaction of dimethyl fumarate, diethyl 2-aminomalonate and 4-cyanobenzaldehyde. Both methyl ester groups display a trans configuration and the pyrrolidine ring possesses an envelope conformation, with the C atom in the 3-position as the flap. In the crystal, N—H⋯N hydrogen bonds and weak C—H⋯O interactions occur.

Related literature

For the biological activity of pyrrolidine derivatives, see: Coldham & Hufton (2005 ▶); Pandey et al. (2006 ▶); Schreiber et al. (2000 ▶). For a related structure, see: He et al. (2010 ▶).

Experimental

Crystal data

C₂₁H₂₄N₂O₈
M _r = 432.42
Orthorhombic,
a = 8.4720 (2) Å
b = 10.3043 (2) Å
c = 25.8774 (5) Å
V = 2259.05 (8) Å³
Z = 4
Cu Kα radiation
μ = 0.83 mm⁻¹
T = 291 K
0.38 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T _min = 0.744, T _max = 0.789
26556 measured reflections
2565 independent reflections
2050 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.141
S = 1.03
2565 reflections
288 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812029625/xu5557sup1.cif

e-68-o2363-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029625/xu5557Isup2.hkl

e-68-o2363-Isup2.hkl^{(123.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812029625/xu5557Isup3.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
N2—H1⋯N1ⁱ	0.86 (4)	2.47 (4)	3.240 (5)	148 (4)
C8—H8⋯O1ⁱⁱ	0.98	2.39	3.333 (4)	161 (1)
C13—H13C⋯O7ⁱⁱ	0.96	2.46	3.388 (6)	163
C18—H18C⋯O5ⁱⁱⁱ	0.96	2.55	3.453 (9)	157

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

Acknowledgments

The author acknowledges financial support from China West Normal University (11B004).

supplementary crystallographic information

Comment

Facile synthesis of structurally diverse heterocycles is important in chemical biology. Five-membered pyrrolidines compounds is an important class of heterocyclic compounds with wide spread applications to the synthesis of biologically active compounds and natural alkaloids (Coldham & Hufton, 2005; Pandey et al., 2006; Schreiber et al., 2000). Its crystal structure is reported here.

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The pyrrolidine ring possesses an envelope conformation. The crystal packing is stabilized by C—H···O and N—H···N hydrogen bonds (Table 1).

Experimental

To a solution of 4-cyanobenzaldehyde (0.065 g, 0.5 mmol), sodium sulflate (0.1 g) and diethyl 2-aminomalonate (0.070 g, 0.4 mmol) in chloroform (4 ml) was added dimethyl fumarate (0.145 g, 1 mmol). The mixture was stirred at 323 K for 2 d and then cooled to room temperature, the solvent was evaporated under reduced pressure and the residues was purified by flash chromatograghy on silica gel. The colourless powder was obtained. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution.