Crystal structure of (E)-N′-{[(1R,3R)-3-isopropyl-1-methyl-2-oxo­cyclo­pent­yl]methyl­idene}-4-methyl­benzene­sulfono­hydrazide

David Tymann; Dina Christina Dragon; Christopher Golz; Hans Preut; Carsten Strohmann; Martin Hiersemann

doi:10.1107/S2056989014026747

. 2015 Jan 10;71(Pt 2):o99–o100. doi: 10.1107/S2056989014026747

Crystal structure of (E)-N′-{[(1R,3R)-3-isopropyl-1-methyl-2-oxocyclopentyl]methylidene}-4-methylbenzenesulfonohydrazide

David Tymann ^a, Dina Christina Dragon ^a, Christopher Golz ^a, Hans Preut ^a,^*, Carsten Strohmann ^a, Martin Hiersemann ^a

PMCID: PMC4384629 PMID: 25878892

Abstract

The title compound, C₁₇H₂₄N₂O₃S, was synthesized in order to determine the relative configuration of the corresponding β-keto aldehyde. In the U-shaped molecule, the five-membered ring approximates an envelope with the methylene atom adjacent to the quaternary C atom being the flap. The dihedral angles between the four nearly coplanar atoms of the five-membered ring and the flap and the aromatic ring are 38.8 (4) and 22.9 (2)°, respectively. The bond angles around the S atom are in the range 104.11 (16)–119.95 (16)°. In the crystal, molecules are linked via N—H⋯O by hydrogen bonds, forming a chain along the a-axis direction.

Keywords: crystal structure, benzenesulfonohydrazide, terpenoid-related building blocks, hydrogen bonding, cyclopentanoids

Related literature

For the synthesis of terpenoid-related building blocks, in particular cyclopentanoids, see: Becker et al. (2013 ▸); Gille et al. (2011 ▸); Helmboldt et al. (2006 ▸); Nelson et al. (2011 ▸); Tymann et al.(2014 ▸). For a review on cyclopentanoids by ring contraction see: Silva (2002 ▸). For a solid–acid catalysed rearrangement of cyclic α,β-epoxy ketones see: Elings et al. (2000 ▸).

Experimental

Crystal data

C₁₇H₂₄N₂O₃S
M _r = 336.44
Monoclinic,
a = 6.6198 (8) Å
b = 16.8318 (18) Å
c = 7.9506 (9) Å
β = 97.141 (11)°
V = 879.00 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 173 K
0.23 × 0.10 × 0.03 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2008 ▸) T _min = 0.98, T _max = 1.00
6620 measured reflections
3684 independent reflections
3185 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.091
S = 1.01
3684 reflections
216 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack x determined using 1307 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons & Flack,2004 ▸)
Absolute structure parameter: 0.02 (5)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▸); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008 ▸); data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, 2864. DOI: 10.1107/S2056989014026747/tk5349sup1.cif

e-71-00o99-sup1.cif^{(248.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026747/tk5349Isup2.hkl

e-71-00o99-Isup2.hkl^{(205.8KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014026747/tk5349Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989014026747/tk5349fig1.tif

The molecular structure of the title compound, showing the labelling of all non-H atoms. Displacement ellipsoids are shown at the 30% probability level.

CCDC reference: 1037859

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1NO3ⁱ	0.91(4)	2.03(4)	2.889(4)	158(3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support obtained from the Beilstein Institut is gratefully acknowledged

supplementary crystallographic information

S1. Comment

Prompted by our efforts in natural product synthesis, we seek access to cyclopentyl units. Herein, we chosed a ring contraction strategy of a cyclic epoxy ketone. A Brønsted-acid promoted [1,2]-sigmatropic rearrangement of cis-piperitone oxide delivered trans-3-Isopropyl-1-methyl-2-oxocyclopentane-1-carbaldehyde (II). A subsequent condensation of (II) with p-toulenesulfonyl hydrazide afforded the title compound (I).

S2. Experimental

A sealable glass pressure tube was charged with a solution of trans-3-Isopropyl-1-methyl-2-oxocyclopentane-1-carbaldehyde (II) (C₁₀H₁₆O₂, M = 168.23 g/mol, [α]_D²⁰ = +248.3 (c 0.059 mol/L, CHCl₃), 150 mg, 0.89 mmol, 1.0 eq) and p-toluenesulfonyl hydrazide (C₇H₁₀N₂O₂S, M = 186.23 g/mol, 232 mg, 1.24 mmol, 1.4 eq) in methanol (9 ml, 10.1 ml/mmol). The tube was sealed with a Teflon screw cap and placed in a pre-heated oil bath (353 K). After being stirred for 2.5 h at 353 K, the reaction mixture was cooled to ambient temperature and stirred for additional 16 h at room temperature. Next, the volatiles were removed under reduced pressure. Purification of the residue by flash chromatography (cyclohexane/ethyl acetate 50/1 to 5/1) delivered the title compound (I) (C₁₇H₂₄N₂O₃S, M = 336.45 g/mol, 161 mg, 0.48 mmol, 54%) as a white solid and as an apparent mixture of double bond isomers (ratio = 68:32). Subsequent recrystallization of (I) from n-pentane provided colourless plates of the E-configured double bond isomer of (I). The ratio of isomers was determined by integration of the ¹H NMR signals at 6.66 p.p.m. (s, 1H) and 7.12 p.p.m. (s, 1H). Characterization data are reported for the mixture of isomers. R_f 0.44 (cyclohexane/ethyl acetate 2/1); m.p. 361–363 K; ¹H NMR (CDCl₃, 500 MHz, ratio of double bond isomers = 68:32) δ 0.81 (d, J = 6.7 Hz, 3H^major), 0.93 (d, J = 6.9 Hz, 3H^minor), 0.97 (d, J = 6.7 Hz, 3H^major), 1.08–1.09 (m, 3H^major+3H^minor), 1.12 (s, 3H^minor), 1.52–1.59 (m, 1H^minor), 1.62–1.81 (m, 2H^major+3H^minor), 1.93–2.02 (m, 1H^major), 2.05–2.23 (m, 3H^major+1H^minor), 2.42 (s, 3H^minor), 2.43 (s, 3H^major), 2.53–2.56 (m, 1H^minor), 6.66 (s, 1H^minor), 7.12 (s 1H^minor), 7.29–7.32 (m, 2H^major+2H^minor), 7.58 (br. s, 1H), 7.70 (br. s, 1H), 7.79 (d, J = 8.2 Hz, 2H^major), 7.84 (d, J = 8.2 Hz, 2H^minor); ¹³C NMR (CDCl₃, 126 MHz) δ 16.9 (CH₃^minor), 18.5 (CH₃^major), 19.3 (CH₃^minor), 20.1 (CH₃^major), 20.5 (CH₂^major), 20.9 (CH₃^major), 21.57 (CH₃^minor), 21.59 (CH₃^major), 23.7 (CH₃^minor), 24.3 (CH₂^minor), 26.2 (CH^major), 27.3 (CH^minor), 31.4 (CH₂^major), 35.8 (CH₂^minor), 53.1 (C^major), 55.2 (CH^minor), 55.3 (CH^major), 61.9 (C^minor), 127.8 (CH^minor), 127.9 (CH^major), 129.4 (CH^minor), 129.5 (CH^major), 135.1 (C^major), 136.6 (C^minor), 134.8 (C^minor), 144.2 (C^major), 152.8 (CH^major), 154.0 (CH^minor), 218.9 (C^major+C^minor); IR ν 3445 (m), 3175 (m), 2960 (m), 2360 (w), 1730 (s), 1595 (m), 1470 (m), 1355 (s), 1320 (m), 1185 (s), 1165 (s), 1093 (m), 815 (s); Anal. Calcd. for C₁₇H₂₄N₂O₃S: C, 60.7; H, 7.2; N, 8.3; Found: C, 60.9; H, 7.2; N, 8.1.