Dehydro­abietic acid

Xiao-Ping Rao; Zhan-Qian Song; Shi-Bin Shang

doi:10.1107/S1600536809035600

. 2009 Sep 9;65(Pt 10):o2402. doi: 10.1107/S1600536809035600

Dehydroabietic acid

Xiao-Ping Rao ^a,^*, Zhan-Qian Song ^a, Shi-Bin Shang ^a

PMCID: PMC2970241 PMID: 21577865

Abstract

The title compound [systematic name: (1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylic acid], C₂₀H₂₈O₂, has been isolated from disproportionated rosin which is obtained by isomerizing gum rosin with a Pd-C catalyst.. Two crystallographically independent molecules exist in the asymmetric unit. In each molecule, there are three six-membered rings, which adopt planar, half-chair and chair conformations. The two cyclohexane rings form a trans ring junction with the two methyl groups in axial positions. The crystal structure is stabilized by intermolecular O—H⋯O hydrogen bonds.

Related literature

For the synthesis and uses of dehydroabietic acid, see: Halbrook & Lawrence (1966 ▶); Jia et al. (2009 ▶); Piispanen et al. (2001 ▶); Rao et al. (2006 ▶); Rao, Song & He (2008 ▶); Rao, Song, He & Jia (2008 ▶); Sepulveda et al. (2005 ▶); Wada et al. (1985 ▶).

Experimental

Crystal data

C₂₀H₂₈O₂
M _r = 300.42
Monoclinic,
a = 11.738 (2) Å
b = 11.875 (2) Å
c = 13.654 (3) Å
β = 107.50 (3)°
V = 1815.1 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995 ▶) T _min = 0.973, T _max = 0.986
3592 measured reflections
3417 independent reflections
2173 reflections with I > 2σ(I)
R _int = 0.086
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.077
wR(F ²) = 0.182
S = 1.00
3417 reflections
361 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035600/at2868sup1.cif

e-65-o2402-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035600/at2868Isup2.hkl

e-65-o2402-Isup2.hkl^{(167.6KB, 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
O2—H2D⋯O3ⁱ	0.82	1.82	2.621 (8)	165
O4—H4A⋯O1ⁱⁱ	0.82	1.79	2.598 (8)	168

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 30800871) and the Fundamental Research Foundation of the Central Commonwealth Institute of the Chinese Academy of Forestry (grant No. CAFYBB2008021),

supplementary crystallographic information

Comment

Dehydroabietic acid is an abietane diterpenic resin acid which can be easily obtained from Pinus resin or commercial disproportionated rosin (Halbrook & Lawrence, 1966). The tri-cyclic hydrophenanthrene structure of dehydroabietic acid has strong hydrophobicity, so it can be used as raw material for the synthesis of surfactants (Piispanen et al., 2001; Jia et al., 2009). Dehydroabietic acid is also widely used as starting material for design and synthesis of biological compounds (Sepulveda et al., 2005; Rao, Song & He, 2008; Rao, Song He & Jia, 2008; Wada et al., 1985). In this work, we describe the crystal structure of the title compound.

The overall geometry of the title compound (Fig. 1) is comparable to that found for dehydroabietic N-methyl anilide (Rao et al., 2006) Two crystallorgraphic independent molecules exist in the asymmetric unit. In each molecule there are three six-membered rings, in which they form plannar, half-chair and chair conformations, respectively. The tricyclo phenanthrene structure of the title compound exhibited the same conformation with dehydroabietic N-methyl anilide. The two cyclohexane rings form a trans ring junction with two methyl groups in the same side of tricyclo phenanthrene structure. There are three chiral centers in each molecule, they exhibited R–, S– and R– configurations, respectively.

The crystal structure is stabilized by intermolecular O—H···O hydrogen bonds.

Experimental

The title compound wasere isolated from disproportionated rosin by recrystallization 5 times from acetone. Single crystals were grown from acetone.