Ethyl 2-[6-(4-methyl­benzo­yl)-7-phenyl-2,3-di­hydro-1H-pyrrolizin-5-yl]-2-oxo­acetate

Jia-liang Zhong; Wen-xia Sun; Fu-li Zhang; Li-hong Liu; He Liu

doi:10.1107/S1600536813029401

. 2013 Nov 6;69(Pt 12):o1730. doi: 10.1107/S1600536813029401

Ethyl 2-[6-(4-methylbenzoyl)-7-phenyl-2,3-dihydro-1H-pyrrolizin-5-yl]-2-oxoacetate

Jia-liang Zhong ^a, Wen-xia Sun ^a, Fu-li Zhang ^a, Li-hong Liu ^b, He Liu ^b,^*

PMCID: PMC3885017 PMID: 24454192

Abstract

In the title compound, C₂₅H₂₃NO₄, the pyrrolizine ring is approximately planar with an r.m.s deviation from planarity of 0.0053 Å, while the fused dihydropyrrolizine ring adopts an envelope conformation with the C atom connected to two CH₂ as the flap. The dihedral angles between the fused ring system and the phenyl and methylbenzoyl rings are 41.65 (11) and 66.30 (8)°, respectively. In the crystal, weak C—H⋯O hydrogen bonds and C—H⋯π interactions occur. One molecule is linked to five adjacent ones through eight hydrogen bonds, forming a three-dimensional network.

Related literature

For the synthesis of the title compound, see: Itoh et al. (1984 ▶). For similar structures, see: Liu et al. (2007 ▶, 2013 ▶). graphic file with name e-69-o1730-scheme1.jpg

Experimental

Crystal data

C₂₅H₂₃NO₄
M _r = 401.44
Monoclinic,
a = 8.8949 (18) Å
b = 9.0003 (18) Å
c = 25.580 (5) Å
β = 96.75 (3)°
V = 2033.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.26 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
16259 measured reflections
3775 independent reflections
1930 reflections with I > 2σ(I)
R _int = 0.070

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.194
S = 0.97
3775 reflections
274 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813029401/zp2010sup1.cif

e-69-o1730-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813029401/zp2010Isup2.hkl

e-69-o1730-Isup2.hkl^{(185.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg4 is the centroid of the C21–C26 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20B⋯O3ⁱ	0.96	2.64	3.268 (6)	123
C12—H12B⋯O2ⁱⁱ	0.96	2.63	3.579 (5)	170
C12—H12A⋯O1ⁱⁱⁱ	0.96	2.66	3.376 (5)	132
C2—H2A⋯O4^iv	0.97	2.70	3.391 (5)	128
C19—H19⋯Cg4^v	0.93	2.96	3.769 (5)	147

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

Acknowledgments

We gratefully acknowledge financial support from the National Natural Science Foundation of China (No. 81072530).

supplementary crystallographic information

1. Comment

The title compound, (I) (Fig. 1), ethyl 2-(6-(4-methylbenzoyl)-7-phenyl -2,3-dihydro-1H-pyrrolizin-5-yl)-2-oxoacetate was synthesized from 6-(4-Methylbenzoyl)-7-phenyl-2,3-dihydro-pyrrolizine and ethyl oxalyl monochloride according to a general literature procedure of Itoh et al., (1984).

The title compound was an analogue of C₂₀H₁₉NOS (Liu, et al., 2013). The pyrrolizine ring is almost planar, while the fused dihydro-pyrrolizine ring adopts an envelope conformation. The dihedral angle between ring A (C1/C2/C3/N4/C5/C6/C7/C8) and phenyl ring B (C21—C26) is 41.65 (11)°, the dihedral angle between ring A and ring C (C13/C14/C15/C15/C17/C18/C19/C20) is 66.30 (8)°, and the dihedral angle between ring B and ring C is 74.31 (11)°. The torsion angle of O1/C9/C10/O2 was 131.5 (4)°. As a result, three side chains of ring A arranged themselves like propeller due to steric.

In the crystal, a series of weak intermolecular C—H···O (Table 1) hydrogen bonds can be found. Compared to C₂₀H₁₉NOS (Liu, et al., 2013), three O atoms of ethyloxalyl form three H-bonds, which help stablizing the crysatl packing. One molecule link to five adjacent ones through eight H-bonds to form three-dimensional infinite packing. An analysis by PLATON (Spek, 2009) shows C19—H19···π interaction with H19 to ring B centroid(Cg4) distance of 2.96 Å(Table 1, Fig2).

2. Experimental

A stirred solution of 6-(4-Methylbenzoyl)-7-phenyl-2,3-dihydro- pyrrolizine in anhydrous CH₂Cl₂ was treated with AlCl₃. A solution of ethyl oxalyl monochloride in anhydrous CH₂Cl₂ was added. The mixture was stirred for 4 h at room temperature, and cooled to 273 K, an aqueous solution of HCl(w/w10%) was then added and the resulting solution was stirred for 1 h. After addition of water to form a clear aqueous layer, the organic layer was separated and dried(anhydrous Na₂SO₄). Then the solution was evaporated under reduced pressure and purified by chromatography on silica gel column, eluting with a petroleum ether/acetone mixture (2:1) to give 65% yield of light yellow solid. The purity of the title compound was verified by elemental analysis: calculated for C₂₅H₂₃NO₄: C 74.80, H 5.77, N 3.49; found C 65.72, H 4.39, N 3.83. EI—MS m/z: 402 (M+H)⁺.

The crystal appropriate for X-ray data collection was obtained from acetone solution at room temperature after two days.