trans-Ethyl­enedi-p-phenyl­ene diacetate

Ritter, S.; Neudörfl, J.-M.; Velder, J.; Schmalz, H.-G.

doi:10.1107/S1600536809032620

organic compounds

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Volume 65| Part 9| September 2009| Page o2229

doi:10.1107/S1600536809032620

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trans-Ethylenedi-p-phenylene diacetate

Stefanie Ritter,^a Jörg-M. Neudörfl,^a Janna Velder ^a and Hans-Günther Schmalz ^a ^*

^aDepartment für Chemie der Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany
^*Correspondence e-mail: schmalz@uni-koeln.de

(Received 12 August 2009; accepted 17 August 2009; online 26 August 2009)

The centrosymmetric title compound, C₁₈H₂₆O₄, was prepared in high yield from 4-acetoxystyrene via Ru-catalysed homo-olefin metathesis. Exclusive formation of the E-configurated isomer was observed. In the crystal, a strong C—H⋯π intermolecular interaction links the molecules together.

Related literature

For the preparation of differently substituted stilbenes using a Ru-catalysed metathesis strategy, see: Velder et al. (2006 ). For alternative methodologies for the synthesis of oxy-functionalized stilbenes using Wittig-type olefinations or Heck-couplings, see: Kim et al. (2002 ); Lion et al. (2005 ); Botella et al. (2004 ); Reetz et al. (1998 ). For the bioactivity of various stilbenes with a focus on their anticancer activity, see: Aggarwal et al. (2004 ); Wolter et al. (2002 ); Fremont (2000 ); Jang et al. (1997 ); Wieder et al. (2001 ). For related structures see: Malone et al. (1997 ). For a previous synthesis of the title compound see: Johnson et al. (1952 ).

Experimental

Crystal data

C₁₈H₁₆O₄
M_r = 296.31
Monoclinic, P 2₁ /c
a = 9.7430 (4) Å
b = 7.2839 (4) Å
c = 11.2723 (6) Å
β = 113.649 (3)°
V = 732.78 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.52 × 0.36 × 0.34 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
3533 measured reflections
1595 independent reflections
1119 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.106
S = 1.03
1595 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Geometry the C—H⋯π interaction (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cg1ⁱ	0.95	2.81	3.539 (2)	135
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of the C2–C7 ring.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SCHAKAL99 (Keller, 1999 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and enCIFer (Allen et al., 2004 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032620/hg2554sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032620/hg2554Isup2.hkl

checkCIF report

Comment top

Resveratrol-related stilbenes exhibit promising anticancer activity (Aggarwal et al., 2004; Wolter et al., 2002; Fremont et al., 2000; Jang et al., 1997). Based on our own research in the field of bioactive stilbenes (Wieder et al., 2001) we decided to reinvestigate the possibility of using a cross-metathesis strategy for the synthesis of compounds of type 1 (Velder et al., 2006) which turned out to be a highly efficient route towards symmetrically as well as unsymmetrically substituted E-stilbenes. Alternative strategies for the synthesis of stilbenes are based on Wittig-type olefinations or Heck couplings (Kim et al. (2002), Lion et al. (2005), Botella et al. (2004), Reetz et al. (1998)). One of the compounds prepared is the title compound trans-1,2-bis-(4-acetoxyphenyl)ethene. Within each molecule the two planes defined by the arene moieties are co-planar but slightly stepped (by 0.324 (2) Å) due to the fact that the plane defined by the central double bond is twisted by a torsion angle of -13.8 (2)° (C1a—C1—C2—C7) and 165.7 (15)° (C1a—C1—C2—C3), respectively (figure 1). The molecules form layers which are intermolecularly linked through a C—H···π interaction of type III (Malone et al. 1997). This interaction occurs between the H atom of one phenyl group and the π-system of the other phenyl moiety (figure 2). With a H···π distance of only 2.77 Å these interactions are rather strong.

Related literature top

For the preparation of differently substituted stilbenes using a Ru-catalysed metathesis strategy, see: Velder et al. (2006). For alternative methodologies for the synthesis of oxy-functionalized stilbenes using Wittig-type olefinations or Heck-couplings, see: Kim et al. (2002); Lion et al. (2005); Botella et al. (2004); Reetz et al. (1998). For the bioactivity of various stilbenes with a focus on their anticancer activity, see: Aggarwal et al. (2004); Wolter et al. (2002); Fremont (2000); Jang et al. (1997); Wieder et al. (2001). For related structures see: Malone et al. (1997). For a previous synthesis of the title compound see: Johnson et al. (1952). Cg1 is the centroid of the C2–C7 ring.

Experimental top

In a glove-box (Labmaster 130, mBraun), the catalyst (Grubbs-II, 2 mol %) was weighted into a 25 ml Schlenk tube, which was sealed with a rubber septum. This was then taken out of the box, connected to an Ar-vacuum double manifold and equipped with a reflux condenser under argon. A solution of 3-acetoxy-styrene (1.0 g, 6.17 mmol) in CH₂Cl₂ (20 ml) was added via syringe and the resulting solution was refluxed for 1.5 h under argon. After allowing the reaction mixture to cool to room temperature, the solvent was evaporated in vacuo and the crude product was purified by recrystallization from EtOAc/cyclohexane 5:1 to give 0.8 g (88%) of the homo-metathesis product 1. mp. 214 °C (Johnson et al. (1952) 215–218°C). ¹H NMR (300 MHz, CDCl₃): δ = 2.29 (s, 3H, CH₃), 7.04 (s, 1H, CH=), 7.08 (d, 2H, J = 8.7 Hz, H-3, H-5), 7.49 (d, 2H, J = 8.7 Hz, H-2, H-6); ¹³C NMR (300 MHz, CDCl₃): δ = 21.2 (CH₃), 121.8 (C-3, C-5), 127.4 (C-2, C-6), 127.9 (C-7), 135.0 (C-1), 150.1 (C-4), 169.5 (C=O); HRMS, calcd for C₁₈H₁₆O₄ (M⁺) 296.1048, found 296.105.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SCHAKAL99 (Keller, 1999); software used to prepare material for publication: PLATON (Spek, 2009) and enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. A top view of 1. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Intramolecular C—H···π interactions.

trans-Ethylenedi-p-phenylene diacetate top

Crystal data top

C₁₈H₁₆O₄	F(000) = 312
M_r = 296.31	D_x = 1.343 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 214 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.7430 (4) Å	Cell parameters from 3533 reflections
b = 7.2839 (4) Å	θ = 2.3–27.0°
c = 11.2723 (6) Å	µ = 0.10 mm⁻¹
β = 113.649 (3)°	T = 100 K
V = 732.78 (7) Å³	Needle, colourless
Z = 2	0.52 × 0.36 × 0.34 mm

Data collection top

Nonius KappaCCD diffractometer	1119 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
ϕ and ω scans	h = −12→12
3533 measured reflections	k = −8→9
1595 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0486P)² + 0.0561P] where P = (F_o² + 2F_c²)/3
1595 reflections	(Δ/σ)_max = 0.002
101 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₈H₁₆O₄	V = 732.78 (7) Å³
M_r = 296.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7430 (4) Å	µ = 0.10 mm⁻¹
b = 7.2839 (4) Å	T = 100 K
c = 11.2723 (6) Å	0.52 × 0.36 × 0.34 mm
β = 113.649 (3)°

Data collection top

Nonius KappaCCD diffractometer	1119 reflections with I > 2σ(I)
3533 measured reflections	R_int = 0.038
1595 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
1595 reflections	Δρ_min = −0.21 e Å⁻³
101 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The coordinates of the hydrogen atoms are constrained, and the U values of the H atoms are constrained relative to the U_eq of the atom the hydrogen binds to (1.2 for CH and CH₂, 1.5 for CH₃).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.26496 (12)	0.47976 (14)	0.58904 (9)	0.0210 (3)
O2	0.37476 (12)	0.75603 (15)	0.60504 (10)	0.0249 (3)
C1	0.06877 (16)	0.48067 (19)	0.04361 (14)	0.0165 (3)
H1	0.1412	0.4466	0.0111	0.020*
C2	0.11855 (16)	0.48580 (19)	0.18473 (14)	0.0151 (3)
C3	0.25433 (16)	0.4033 (2)	0.26319 (14)	0.0171 (3)
H3	0.3134	0.3468	0.2238	0.020*
C4	0.30488 (16)	0.4019 (2)	0.39715 (14)	0.0176 (3)
H4	0.3971	0.3446	0.4492	0.021*
C5	0.21842 (17)	0.4853 (2)	0.45310 (13)	0.0165 (4)
C6	0.08410 (17)	0.5691 (2)	0.37923 (14)	0.0189 (4)
H6	0.0261	0.6259	0.4195	0.023*
C7	0.03502 (17)	0.5694 (2)	0.24605 (14)	0.0179 (4)
H7	−0.0572	0.6274	0.1950	0.021*
C8	0.34023 (17)	0.6307 (2)	0.65644 (15)	0.0187 (4)
C9	0.37163 (18)	0.6128 (2)	0.79670 (14)	0.0245 (4)
H9A	0.4210	0.7245	0.8424	0.037*
H9B	0.4373	0.5070	0.8330	0.037*
H9C	0.2773	0.5951	0.8069	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0304 (7)	0.0177 (6)	0.0123 (6)	−0.0031 (5)	0.0058 (5)	−0.0012 (4)
O2	0.0264 (7)	0.0227 (6)	0.0258 (6)	−0.0058 (5)	0.0106 (5)	−0.0025 (5)
C1	0.0191 (8)	0.0139 (8)	0.0174 (8)	−0.0008 (6)	0.0083 (6)	−0.0011 (6)
C2	0.0168 (8)	0.0117 (7)	0.0154 (8)	−0.0031 (6)	0.0051 (6)	0.0008 (6)
C3	0.0184 (8)	0.0156 (8)	0.0175 (8)	−0.0012 (6)	0.0076 (7)	−0.0019 (6)
C4	0.0156 (8)	0.0154 (8)	0.0181 (8)	−0.0004 (6)	0.0027 (6)	0.0013 (6)
C5	0.0239 (9)	0.0132 (8)	0.0106 (8)	−0.0049 (6)	0.0049 (7)	−0.0005 (6)
C6	0.0245 (9)	0.0145 (8)	0.0192 (8)	0.0008 (6)	0.0102 (7)	−0.0023 (6)
C7	0.0198 (9)	0.0152 (8)	0.0169 (8)	0.0018 (6)	0.0055 (7)	0.0010 (6)
C8	0.0146 (8)	0.0187 (9)	0.0212 (8)	0.0035 (6)	0.0056 (7)	−0.0039 (7)
C9	0.0275 (9)	0.0245 (9)	0.0174 (9)	0.0029 (7)	0.0046 (7)	−0.0037 (7)

Geometric parameters (Å, º) top

O1—C8	1.3700 (18)	C4—C5	1.380 (2)
O1—C5	1.4135 (16)	C4—H4	0.9500
O2—C8	1.1994 (17)	C5—C6	1.380 (2)
C1—C1ⁱ	1.336 (3)	C6—C7	1.381 (2)
C1—C2	1.466 (2)	C6—H6	0.9500
C1—H1	0.9500	C7—H7	0.9500
C2—C3	1.398 (2)	C8—C9	1.491 (2)
C2—C7	1.401 (2)	C9—H9A	0.9800
C3—C4	1.388 (2)	C9—H9B	0.9800
C3—H3	0.9500	C9—H9C	0.9800

C8—O1—C5	116.48 (11)	C5—C6—C7	119.19 (14)
C1ⁱ—C1—C2	126.23 (17)	C5—C6—H6	120.4
C1ⁱ—C1—H1	116.9	C7—C6—H6	120.4
C2—C1—H1	116.9	C6—C7—C2	121.30 (14)
C3—C2—C7	117.66 (14)	C6—C7—H7	119.3
C3—C2—C1	119.52 (13)	C2—C7—H7	119.3
C7—C2—C1	122.81 (13)	O2—C8—O1	122.30 (14)
C4—C3—C2	121.62 (14)	O2—C8—C9	126.94 (14)
C4—C3—H3	119.2	O1—C8—C9	110.76 (13)
C2—C3—H3	119.2	C8—C9—H9A	109.5
C5—C4—C3	118.61 (14)	C8—C9—H9B	109.5
C5—C4—H4	120.7	H9A—C9—H9B	109.5
C3—C4—H4	120.7	C8—C9—H9C	109.5
C4—C5—C6	121.62 (13)	H9A—C9—H9C	109.5
C4—C5—O1	119.59 (13)	H9B—C9—H9C	109.5
C6—C5—O1	118.75 (13)

C1ⁱ—C1—C2—C3	165.70 (18)	C8—O1—C5—C6	−85.05 (16)
C1ⁱ—C1—C2—C7	−13.8 (3)	C4—C5—C6—C7	0.0 (2)
C7—C2—C3—C4	0.6 (2)	O1—C5—C6—C7	−177.66 (13)
C1—C2—C3—C4	−178.87 (13)	C5—C6—C7—C2	0.3 (2)
C2—C3—C4—C5	−0.4 (2)	C3—C2—C7—C6	−0.6 (2)
C3—C4—C5—C6	0.1 (2)	C1—C2—C7—C6	178.93 (13)
C3—C4—C5—O1	177.71 (12)	C5—O1—C8—O2	−5.1 (2)
C8—O1—C5—C4	97.22 (15)	C5—O1—C8—C9	175.46 (12)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cg1ⁱⁱ	0.95	2.81	3.539 (2)	135

Symmetry code: (ii) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆O₄
M_r	296.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.7430 (4), 7.2839 (4), 11.2723 (6)
β (°)	113.649 (3)
V (Å³)	732.78 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.52 × 0.36 × 0.34

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3533, 1595, 1119
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.106, 1.03
No. of reflections	1595
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SCHAKAL99 (Keller, 1999), PLATON (Spek, 2009) and enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cg1ⁱ	0.95	2.81	3.539 (2)	135

Symmetry code: (i) −x, y+1/2, −z+1/2.

References

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doi:10.1107/S1600536809032620

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