Deacetyl tenuazonic acid p-toluene­sulfonyl­hydrazone

David Siegel; Franziska Blaske; Matthias Koch; Franziska Emmerling; Irene Nehls

doi:10.1107/S1600536809048958

. 2009 Nov 21;65(Pt 12):o3136. doi: 10.1107/S1600536809048958

Deacetyl tenuazonic acid p-toluenesulfonylhydrazone

David Siegel ^a,^*, Franziska Blaske ^a, Matthias Koch ^a, Franziska Emmerling ^a, Irene Nehls ^a

PMCID: PMC2972091 PMID: 21578857

Abstract

The title compound {systematic name: 4-methyl-N′-[(3E)-2-(1-methylpropyl)-5-oxopyrrolidin-3-ylidene]benzenesulfonohydrazide}, C₁₅H₂₁N₃O₃S, is the condensation product of deacetyl tenuazonic acid (DTA) and p-toluenesulfonohydrazide. The crystal structure consists of chains along [100] linked by N—H⋯O hydrogen bonds.

Related literature

For the occurrence of tenuazonic acid (TA) in various food matrices, see: Weidenbörner (2001 ▶). For potential uses of the title compound in food analysis, see: Siegel, Rasenko et al. (2009 ▶). For the crystal structure of DTA, see: Siegel, Koch et al. (2009 ▶) and for its synthesis, see: Lebrun et al. (1988 ▶); Stickings (1959 ▶). For the structure of p-toluenesulfonylhydrazine, see: Roy & Nangia (2007 ▶). For the structures of other p-toluenesulfonyhydrazones, see, for example: Glidewell et al. (2004 ▶); Ng (1997 ▶); Yan et al. (2008 ▶). graphic file with name e-65-o3136-scheme1.jpg

Experimental

Crystal data

C₁₅H₂₁N₃O₃S
M _r = 323.41
Orthorhombic,
a = 5.1286 (16) Å
b = 8.285 (3) Å
c = 38.430 (12) Å
V = 1633.0 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 294 K
0.14 × 0.12 × 0.02 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: ψ scan (SHELXTL; Bruker, 2001 ▶) T _min = 0.970, T _max = 0.995
13112 measured reflections
4755 independent reflections
2233 reflections with I > 2σ(I)
R _int = 0.102

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.097
S = 0.77
4755 reflections
196 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ▶), 1905 Friedel pairs
Flack parameter: −0.11 (10)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048958/sj2674sup1.cif

e-65-o3136-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048958/sj2674Isup2.hkl

e-65-o3136-Isup2.hkl^{(233KB, 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
N3—H3⋯O1ⁱ	0.86	2.27	3.104 (3)	162
N1—H1⋯O3ⁱⁱ	1.03	2.10	3.063 (3)	156

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

supplementary crystallographic information

Comment

Deacetyl tenuazonic acid (DTA) is formed upon boiling the Alternaria. mycotoxin tenuazonic acid (TA) in 0.1 M HCl (Stickings, 1959). As TA is frequently encountered in various food matrices (Weidenbörner, 2001), traces of DTA are expected to occur in these matrices as well. We have recently reported a derivatization procedure for TA quantification in food, which is based on hydrazone formation with 2,4-dinitrophenylhydrazine (Siegel, Rasenko et al., 2009) and are currently evaluating a similar procedure for DTA quantification using p-toluenesulfonyl hydrazide. The title compound is the product of the latter derivatization reaction. The stucture of the title compound, (I), is shown below. Each molecule (Fig.1) is connected to three adjacent molecules via N—H···O hydrogen bonds. As a result isolated ribbons are formed along the a axis, as depicted in Fig. 2.

Experimental

DTA was supplied by the workgroup of Professor R. Faust (University of Kassel, Germany) by synthesis according to a literature procedure (Lebrun et al., 1988). Its identity was confirmed by x-ray crystallography (Siegel, Kochet al., 2009). The title compound was synthesized by dissolving 20 mg (1 eq., 0.13 mmol) of DTA and a five fold molar excess of p-toluenesulfonyl hydrazide (5 eq., 0.65 mmol, 121 mg) in 50 ml 2 M HCl. After 30 minutes of shaking the precipitate was collected, washed with water, dissolved in ethyl acetate and dried with sodium sulfate. After evaporation of the solvent, a yellow powder was obtained, which was recrystallized from ethanol twice. For single-crystal x-ray crystallography, orange crystals of the title compound were grown by solvent evaporation (methanol:water 50:50 v:v) at ambient temperature over a period of three weeks.