13-Ethoxy­carbonyl-16-(1-methyl­ethyl)-17,19-dinoratis-15-ene-4,14-dicarboxylic acid monohydrate: a new derivative of maleopimaric acid

Meng Zhang; Xiao-xin Guo; Yong-hong Zhou; Hong-jun Liu

doi:10.1107/S1600536809028141

. 2009 Jul 22;65(Pt 8):o1959. doi: 10.1107/S1600536809028141

13-Ethoxycarbonyl-16-(1-methylethyl)-17,19-dinoratis-15-ene-4,14-dicarboxylic acid monohydrate: a new derivative of maleopimaric acid

Meng Zhang ^a, Xiao-xin Guo ^a, Yong-hong Zhou ^a,^*, Hong-jun Liu ^a

PMCID: PMC2977153 PMID: 21583637

Abstract

The title compound, C₂₆H₃₈O₆·H₂O, is a mono-ester of a derivative of maleopimaric acid, an abietic-type acid. The two fused and unbridged cyclohexane rings adopt approximate chair conformations while the three other three six-membered rings have boat conformations.

Related literature

Abietic type resin acid, the major component of gum rosin, is a high quality biomass resource for the development of new chiral drugs, see: McCoy (2000 ▶); Schweizer et al. (2003 ▶). For the use of abietic acid and its derivatives in the design and synthesis of industrially and physiologically important products, see: Savluchinske-Feio et al. (2007 ▶). For the structures of other maleopimaric acid derivatives, see: Li et al. (2005 ▶); Pan et al. (2006 ▶); Rao et al. (2006 ▶).

Experimental

Crystal data

C₂₆H₃₈O₆·H₂O
M _r = 464.58
Orthorhombic,
a = 7.3406 (14) Å
b = 17.901 (4) Å
c = 19.681 (4) Å
V = 2586.2 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.98, T _max = 0.98
14084 measured reflections
2892 independent reflections
2318 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.113
S = 1.08
2892 reflections
303 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028141/bh2234sup1.cif

e-65-o1959-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028141/bh2234Isup2.hkl

e-65-o1959-Isup2.hkl^{(142KB, hkl)}

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

Acknowledgments

This work was supported by the President of the Chinese Academy of Forestry Foundation (CAFYBB2008009).

supplementary crystallographic information

Comment

Rosin, a versatile natural resin, possesses a rare combination of many desirable properties and has consequently found innumerable industrial uses in a modified form or in conjunction with other natural or synthetic resins. Abietic type resin acid is the major component of gum rosin, including abietic acid, neoabietic acid, levo-pimaric acid, palustric acid, and is a high quality biomass resource in developing chiral new drug (McCoy, 2000; Schweizer et al., 2003).

Abietic acid and its derivatives are readily available hydrophenanthrene compounds which become useful starting materials for the design and synthesis of industrially and physiologically important productions (Savluchinske-Feio et al., 2007). The crystal structures of other derivatives of maleopimaric acid have already been published (Rao et al., 2006; Li et al., 2005; Pan et al., 2006).

The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit consists of two molecules, viz. maleopimaric ester derivative and one lattice water molecule. The cyclohexane rings C2···C5/C10/C11 and C1/C2/C11···C14 have typical chair forms. The cyclohexane ring C5···C10 has a slightly distorted boat conformation; the other two six-membered rings adopt boat conformations. The configuration about the C17C18 bond is Z (Fig. 1), with the H atom and the isopropyl group cis with respect to each other. The bond lengths and angles have normal values.

In the crystal structure, the molecules are linked (Fig. 2) by O—H···O and C—H···O intermolecular hydrogen bonds.

Experimental

Abietic acid (30.2 g), acetic acid (20 ml), and maleic acid ethyl ester (14.4 g) were put into a 100-ml three-necked flask and magnetically stirred; the mixture was stirred for 25 min. The solution was then put into 5 ml of glacial acetic acid and cooled, washed with hot water (10 ml), dried (MgSO₄), and concentrated to dryness. Recrystallization from ethanol (95%) afforded the adduct (33.9 g, 73%).