Pseudoaglycone of Spinosyn A

Hongxin Chai; Mingxing Liu; Qi Zhang; Daxin Shi; Jiarong Li

doi:10.1107/S1600536812028851

. 2012 Jul 18;68(Pt 8):o2488. doi: 10.1107/S1600536812028851

Pseudoaglycone of Spinosyn A

Hongxin Chai ^a, Mingxing Liu ^a, Qi Zhang ^a,^*, Daxin Shi ^a, Jiarong Li ^a,^*

PMCID: PMC3414943 PMID: 22904930

Abstract

The title compound [systematic name: 9-ethyl-13-hydroxy-14-methyl-2-(3,4,5-trimethoxy-6-methyltetrahydro-2H-pyran-2-yloxy)-3,3a,5b,6,9,10,11,12,13,14,16a,16b-dodecahydro-1H-as-indaceno[3,2-d][1]oxacyclododecine-7,15(2H,5aH)-dione], C₃₃H₅₀O₉, was obtained by hydrolysis of Spinosyn A. The fused cyclopentene ring adopts a twisted conformation, while the fused cyclohexene and cyclopentane rings are in envelope conformations with the same C atom at the flaps. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds into a layer parallel to the ab plane.

Related literature

For the insecticidal activity and research background of Spinosyn, see: Sparks et al. (2008 ▶); Thompson et al. (2000 ▶); Salgado et al. (1998 ▶). For the structure of Spinosyn A, see: Evans & Black (1993 ▶).

Experimental

Crystal data

C₃₃H₅₀O₉
M _r = 590.73
Orthorhombic,
a = 8.7776 (15) Å
b = 8.7959 (15) Å
c = 41.737 (7) Å
V = 3222.4 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 K
0.34 × 0.27 × 0.08 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
25322 measured reflections
4876 independent reflections
4194 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.134
S = 1.00
4876 reflections
389 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku/MSC, 2009 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028851/is5144sup1.cif

e-68-o2488-sup1.cif^{(40.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028851/is5144Isup2.hkl

e-68-o2488-Isup2.hkl^{(238.9KB, 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
O16—H16O⋯O18ⁱ	0.92 (4)	1.96 (3)	2.840 (3)	160 (3)
C3—H3B⋯O10ⁱⁱ	0.99	2.47	3.310 (3)	142

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

Acknowledgments

The authors thank Beijing Institute of Technology for the X-ray diffraction analysis.

supplementary crystallographic information

Comment

Spinosyns, a novel class of green pesticides, were characterized with high efficiency, fast degradation (Sparks et al., 2008), low toxicity (Thompson et al., 2000) and safety to environment (Salgado et al., 1998). Inspired by the high and broad insecticidal activity of Spinosyns and continuing our interest in its structure modification, we obtained pseudoaglycone of Spinosyn A from hydrolysis of the amino sugar forosamine. Here, we report the crystal structure of the title compound (Fig. 1).

Experimental

A solution of 2.0 g Spinosyn A (purchased from SHANGHAI HOHANCE GROUP, 98%) and 5eq H₂SO₄ was heated to 80 °C in ethanol (20 ml) for 2 h. The reaction mixture was cooled to room temperature and then filtered to give the title compound. The product was recrystallizated from ethanol to give colourless crystalline powder (m.p. 441–443 K).