2-[(8-Meth­oxy­carbonyl-4b,8-dimethyl-4b,5,6,7,8,8a,9,10-octa­hydro­phenan­thren-3-yl)amino]-3,5-dinitro­benzoic acid ethyl acetate monosolvate

Bihai Tong; Ye Zhang

doi:10.1107/S1600536812032278

. 2012 Aug 11;68(Pt 9):o2674. doi: 10.1107/S1600536812032278

2-[(8-Methoxycarbonyl-4b,8-dimethyl-4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)amino]-3,5-dinitrobenzoic acid ethyl acetate monosolvate

Bihai Tong ^a, Ye Zhang ^b,^*

PMCID: PMC3435697 PMID: 22969568

Abstract

The title compound, C₂₅H₂₇N₃O₈·C₄H₈O₂, has a diterpene skeleton in which the fused cyclohexane rings exhibit chair and half-chair conformations. An intramolecular C—H⋯O hydrogen bond occurs. In the crystal, N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds are observed.

Related literature

For the synthesis of cis-deisopropyldehydroabietate derivatives, see: Fonseca et al. (2001 ▶); Baleizao et al. (2004 ▶); Feio et al. (1999 ▶). For a related structures, see: Wang et al. (2006 ▶); Hamodrakas et al. (1978 ▶). For uses of dehydroabietic acid (DAA), see: Bhatnagar (1983 ▶, 1984 ▶). For the geometry of diterpenic compounds, see: Allen et al. (1991 ▶);

Experimental

Crystal data

C₂₅H₂₇N₃O₈·C₄H₈O₂
M _r = 585.60
Monoclinic,
a = 7.649 (4) Å
b = 13.591 (8) Å
c = 14.399 (8) Å
β = 101.371 (7)°
V = 1467.5 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.47 × 0.38 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.954, T _max = 0.988
9128 measured reflections
5885 independent reflections
4688 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.107
S = 1.03
5885 reflections
385 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032278/kp2429sup1.cif

e-68-o2674-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032278/kp2429Isup2.hkl

e-68-o2674-Isup2.hkl^{(288.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812032278/kp2429Isup3.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
N1—H1S⋯O6	0.86	2.02	2.654 (3)	129
O5—H5⋯O2S ⁱ	0.82	1.87	2.676 (3)	168
C4S—H4S3⋯O2	0.96	2.54	3.332 (4)	139
C15—H15B⋯O8	0.97	2.53	3.326 (4)	140

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the National Natural Science Foundation of China (No. 50903001) and the Guangxi Department of Education research project (200911MS281, 200911MS282) for financial support.

supplementary crystallographic information

Comment

Dehydroabietic acid (DAA) is one of the isomerides in the renewable rosin. It is widely used in the fields such as paint, adhesives, printing ink (Bhatnagar, 1983), papermaking, and rubber food (Bhatnagar, 1983). Like some natural drug, it has an aromatic diterpene structure with three rings. It also has three sterogenic centres but their absolute configuration cannot be determined by this analysis. The compound comprises a reactive carboxy group and DAA molecule might be modified to obtain some multifunctional derivatives which can be used as high added value products like novel fluorescence derivatization reagents and efficient but low toxic medicines through constructing aromatic or heteroaromatic ring on DAA' s skeleton. Methyl cis-deisopropyldehydroabietate can be easily synthesized from DAA (Fonseca et al., 2001). It provides a convenient starting material for the construction of other derivatives. Some of these derivatives lacking the isopropyl group are also antimicrobial agents (Feio et al., 1999). The molecular structure of the title compound (I) (Fig. 1), as typical of diterpenic compounds (Allen et al., 1991), shows a trans junction of rings A (defined by C16, C17, C18, C19, C20, C21) and B (defined by C11, C12, C17, C16, C15, C14) with two methyl groups in axial positions of the six membered rings. The torsion angles show a chair and a half-chair conformation for rings A and B, respectively. The overall geometry of (I) is comparable to that found for methyl dehydroabietate (Hamodrakas et al., 1978), apart from the substituted 2,4,6 - trinitrophenylamino and methylgroups at the benzene ring.

Experimental

The title compound was obtained by refluxing methyl 13-amino- cis-deisopropyldehydroabietate and 2-chloro-3, 5- dinitrobenzoic acid in ethanol in the presence of copper powder and potassium carbonate to give the title compound as a yellow precipitate in 87.7% yield. Recrystallization from ethyl acetate gave orange block-like crystals suitable for an X-ray diffraction experiment. Anal.Calcd. for C₂₉H₃₅N₃O₁₀: C, 59.48, H, 6.02, N, 7.18%. Found:C, 58.90, H, 6.56, N, 7.00%.