Methyl 4-methyl-2-oxo-1,2,5,6-tetra­hydro-4H-pyrrolo[3,2,1-ij]quinoline-6-carboxyl­ate

Yulia A Zhuravleva; Anatolij V Zimichev; Margarita N Zemtsova; Victor B Rybakov; Yurij N Klimochkin

doi:10.1107/S1600536809029948

. 2009 Jul 31;65(Pt 8):o2059. doi: 10.1107/S1600536809029948

Methyl 4-methyl-2-oxo-1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinoline-6-carboxylate

Yulia A Zhuravleva ^a, Anatolij V Zimichev ^a, Margarita N Zemtsova ^a, Victor B Rybakov ^b,^*, Yurij N Klimochkin ^a

PMCID: PMC2977288 PMID: 21583721

Abstract

In the title molecule, C₁₄H₁₅NO₃, the six-membered heterocyclic ring exhibits an envelope conformation. In the crystal, C—H⋯π interactions link the molecules into centrosymmetric dimers, and weak intermolecular C—H⋯O hydrogen bonds link these dimers into columns propagated along [100].

Related literature

For details of the synthesis, see: Zhuravleva et al. (2009 ▶). For a related structure, see: Bond et al. (1979 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₄H₁₅NO₃
M _r = 245.27
Monoclinic,
a = 8.309 (3) Å
b = 18.524 (5) Å
c = 8.730 (3) Å
β = 112.30 (3)°
V = 1243.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.20 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2699 measured reflections
2445 independent reflections
1974 reflections with I > 2σ(I)
R _int = 0.030
1 standard reflections frequency: 60 min intensity decay: 2%

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.174
S = 1.09
2445 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 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: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029948/cv2589sup1.cif

e-65-o2059-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029948/cv2589Isup2.hkl

e-65-o2059-Isup2.hkl^{(120.1KB, 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
C3—H3A⋯Cgⁱ	0.97	2.55	3.514 (3)	174
C4—H4⋯O12ⁱⁱ	0.98	2.40	3.274 (3)	149
C11—H11A⋯O12ⁱⁱⁱ	0.97	2.56	3.394 (3)	145

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg is the centroid of the C5–C10 ring.

Acknowledgments

The authors are indebted to the Russian Foundation for Basic Research for covering the licence fee for use of the Cambridge Structural Database.

supplementary crystallographic information

Comment

Alkaloids have diverse and impotant physiological activity but it is impossible to fill alkaloids demand from natural source. This causes an attention to new synthetic methods and investigation of similar compounds. Methyl 2-oxo-1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinoline-6-carboxylate (II) was prepared from the previously synthesized substituted 1,2,3,4-tetrahydroquinoline-4-carboxylic acid (I) - Fig. 1. The configuration of substituents cannot be resolved unambiguously by NMR. In accordance with the ¹H NMR and GC-MS data starting I was pure cis-isomer (Zhuravleva et al., 2009). Only one entry (Bond et al., 1979) with the same heterothricycllic moiety was found in CSDB (ver. 5.30; Allen, 2002). All geometric parameters - the same bonds and angles are identical in s.u. intervals.

In the crystal, the C–H···π (centroid of C5-10) interactions (Table 1) link the molecules into centrosymmetric dimers. Weak intermolecular C–H···O hydrogen bonds (Table 1) link further these dimers into columns propagated in direction [100] .

Experimental

To a stirred solution of cis-methyl 1-(chloroacetyl)-2-methyl-1,2,3,4-tetrahydroquinoline-4-carboxylate (3.6 mmol) in 1,2-dichlorobenzene (20 ml) aluminium chloride (36 mmol) was added dropwise at 378 K. The resulting mixture was stirred for 5 h at 378 K. To the cooled reaction mixture was added ice-water and adjusted to pH 10 with solution of sodium hydrocarbonate. The mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate and concentrated under reduced pressure. Recrystallization of the crude product from ethanol gave 0.73 g of colourless crystals. Yield 73%, mp 398-341 K.

IR, ν, cm^-1: 1731 (CO), 1701 (NCO). MS, m/z: 245 (100) [M]+, 230 (40), 187 (7), 186 (84), 170 (66), 158 (91), 142 (46). ¹H NMR, δ: 1.15 d (3H, CH₃), 2.09-2.20 m (1H, 3-CH₂), 2.30-2.40 m (1H, 3-CH), 3.50 s (1H, CH₂), 3.55 s (1H, CH₂), 3.65 s (3H, OCH₃), 3.96-4.01 m (1H, 2-CH), 4.17-4.27 m (1H, 4-CH), 6.95 t (1H, 6-H), 7.13 pt (2H, 7-H, 5-H). Anal. calc. for C₁₄H₁₅NO₃, %: C 69.21; H 6.37; N 5.53. Found, %: C 68.57; H 6.12; N 5.71.

Single crystals for X-ray analysis were obtained by slow evaporation of an methylene chloride - hexane (2: 3) solution. IR spectrum was recorded (in KBr) on Shimadzu FTIR-8400S. Mass spectrum was measured on Finnigan Trance DSQ spectrometer. ¹H NMR spectrum was obtained in DMSO-d₆ on Bruker AM 300 (300 MHz), using TMS as internal standard. Elemental composition was determined on Euro Vector EA-3000 elemental analyzer.