4-Allyl-2-meth­oxy­phenyl 2-acet­oxy­benzoate

Liu, X.-W.; Li, J.-Y.; Yang, Y.-J.; Zhang, J.-Y.

doi:10.1107/S1600536811021416

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1621

doi:10.1107/S1600536811021416

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4-Allyl-2-methoxyphenyl 2-acetoxybenzoate

Xi-Wang Liu,^a Jian-Yong Li,^a ^* Ya-Jun Yang ^a and Ji-Yu Zhang ^a

^aKey Laboratory of New Animal Drug Project, Gansu Province Key Laboratory of Veterinary Drug Discovery, Ministry of Agriculture, Lanzhou Institute of Animal Science and Veterinary Pharmaceutics, Chinese Academy of Agricultural Sciences, Lanzhou 730050, People's Republic of China
^*Correspondence e-mail: lijy1971@163.com

(Received 19 April 2011; accepted 3 June 2011; online 11 June 2011)

In the title compound, C₁₉H₁₈O₅, the ester group is twisted with respect to the acetylsalicylic acid and eugenol rings at dihedral angles of 22.48 (2) and 81.07 (1)°, respectively. The dihedral angle between the two benzene rings is 60.72 (1)°. The crystal packing exhibits no significantly short intermolecular contacts.

Related literature

For background regarding the medicinal properties of eugenol, see: Feng & Lipton (1987 ); Dohi et al. (1989 ). For the synthesis of the aspirin eugenol ester and its biological activity, see: Li et al. (2011 ).

Experimental

Crystal data

C₁₉H₁₈O₅
M_r = 326.33
Monoclinic, P 2₁ /n
a = 10.60 (2) Å
b = 12.58 (2) Å
c = 13.23 (2) Å
β = 109.020 (17)°
V = 1667 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.26 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.976, T_max = 0.980
8695 measured reflections
3089 independent reflections
1786 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.142
S = 1.01
3089 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021416/ez2244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021416/ez2244Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021416/ez2244Isup3.cml

checkCIF report

Comment top

Aspirin has been widely used as an analgesic and anti-inflammatory drug. As the major constituent of clove oil, eugenol also shows antipyretic activity (Feng & Lipton, 1987) and anti-inflammatory activity (Dohi et al., 1989). In this paper, we report the structure of the title compound, which was synthesized from the reaction of aspirin and eugenol in sodium hydroxide solution.

Related literature top

For background regarding the medicinal properties of eugenol, see: Feng & Lipton (1987); Dohi et al. (1989). For the synthesis of the aspirin eugenol ester and its biological activity, see: Li et al. (2011).

Experimental top

The title compound was obtained according to the literature method (Li et al., 2011). Acetylsalicylic acid (0.025 mol) and thionyl chloride (2.5 ml) were mixed in 10 ml tetrahydrofuran (THF), and refluxed at 343 K for 2 h. The surplus thionyl chloride and THF were removed under reduced pressure. The target O-Acetylsalicylyl chloride was dissolved in 5 ml THF, added dropwise to an iced solution of eugenol (0.025 mol) and sodium hydroxide (0.04 mol) in 40 ml water. After stirring at room temprature for 3 h, the crude product was obtained by filtration. The crystals were obtained by recrystalization from methanol. Elemental analysis: calculated for C₁₉ H₁₈O₅: C 69.93%, H 5.56%, O 24.51%; found: C 69.93%, H 5.53%, O 24.54%.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and displacement ellipsoids drawn at the 30% probability level.

4-Allyl-2-methoxyphenyl 2-acetoxybenzoate top

Crystal data top

C₁₉H₁₈O₅	F(000) = 688
M_r = 326.33	D_x = 1.300 Mg m⁻³
Monoclinic, P2₁/n	Melting point = 344–345 K
Hall symbol: P 21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.60 (2) Å	Cell parameters from 2334 reflections
b = 12.58 (2) Å	θ = 2.3–23.9°
c = 13.23 (2) Å	µ = 0.09 mm⁻¹
β = 109.020 (17)°	T = 296 K
V = 1667 (5) Å³	Block, colorless
Z = 4	0.26 × 0.24 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	3089 independent reflections
Radiation source: fine-focus sealed tube	1786 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
T_min = 0.976, T_max = 0.980	k = −15→15
8695 measured reflections	l = −16→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0532P)² + 0.6544P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3089 reflections	Δρ_max = 0.49 e Å⁻³
220 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (3)

Crystal data top

C₁₉H₁₈O₅	V = 1667 (5) Å³
M_r = 326.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.60 (2) Å	µ = 0.09 mm⁻¹
b = 12.58 (2) Å	T = 296 K
c = 13.23 (2) Å	0.26 × 0.24 × 0.22 mm
β = 109.020 (17)°

Data collection top

Bruker APEXII CCD diffractometer	3089 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1786 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.980	R_int = 0.054
8695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.01	Δρ_max = 0.49 e Å⁻³
3089 reflections	Δρ_min = −0.25 e Å⁻³
220 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.

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

	x	y	z	U_iso*/U_eq
C1	0.5429 (3)	0.8815 (2)	1.1109 (2)	0.0552 (7)
H1	0.5154	0.9490	1.0842	0.066*
C2	0.6740 (3)	0.8662 (3)	1.1758 (3)	0.0651 (9)
H2	0.7329	0.9233	1.1933	0.078*
C3	0.7161 (3)	0.7671 (3)	1.2139 (2)	0.0667 (9)
H3	0.8038	0.7566	1.2575	0.080*
C4	0.6290 (3)	0.6826 (3)	1.1880 (2)	0.0589 (8)
H4	0.6582	0.6150	1.2135	0.071*
C5	0.4980 (2)	0.6979 (2)	1.1242 (2)	0.0454 (6)
C6	0.4519 (2)	0.7981 (2)	1.0850 (2)	0.0445 (6)
C7	0.3121 (3)	0.8251 (2)	1.0192 (2)	0.0460 (6)
C8	0.0856 (2)	0.7755 (2)	0.9839 (2)	0.0457 (7)
C9	0.0242 (2)	0.8431 (2)	1.0363 (2)	0.0451 (6)
C10	−0.1134 (3)	0.8549 (2)	0.9951 (2)	0.0522 (7)
H10	−0.1563	0.8996	1.0295	0.063*
C11	−0.1880 (3)	0.8015 (2)	0.9038 (2)	0.0563 (7)
C12	−0.1244 (3)	0.7362 (2)	0.8531 (2)	0.0619 (8)
H12	−0.1735	0.7007	0.7911	0.074*
C13	0.0134 (3)	0.7226 (2)	0.8936 (2)	0.0563 (8)
H13	0.0560	0.6776	0.8593	0.068*
C14	0.3662 (3)	0.5694 (2)	1.0060 (3)	0.0523 (7)
C15	0.2725 (3)	0.4813 (3)	1.0018 (3)	0.0784 (10)
H15A	0.2235	0.4650	0.9286	0.118*
H15B	0.2114	0.5019	1.0382	0.118*
H15C	0.3216	0.4197	1.0359	0.118*
C16	0.0468 (3)	0.9576 (2)	1.1848 (2)	0.0664 (8)
H16A	−0.0043	1.0124	1.1391	0.100*
H16B	0.1152	0.9894	1.2436	0.100*
H16C	−0.0109	0.9156	1.2118	0.100*
C17	−0.3382 (3)	0.8185 (3)	0.8597 (3)	0.0794 (10)
H17A	−0.3803	0.7545	0.8231	0.095*
H17B	−0.3719	0.8312	0.9186	0.095*
C18	−0.3746 (4)	0.9083 (4)	0.7853 (5)	0.1113 (15)
H18	−0.3360	0.9723	0.8151	0.134*
C19	−0.4456 (4)	0.9161 (4)	0.6917 (4)	0.1173 (16)
H19A	−0.4886	0.8564	0.6548	0.141*
H19B	−0.4565	0.9817	0.6575	0.141*
O1	0.41425 (17)	0.60944 (14)	1.10660 (15)	0.0517 (5)
O4	0.22313 (15)	0.75382 (14)	1.03094 (14)	0.0512 (5)
O2	0.3986 (2)	0.60219 (17)	0.93385 (16)	0.0684 (6)
O3	0.28083 (19)	0.90274 (16)	0.96467 (17)	0.0681 (6)
O5	0.10653 (18)	0.89150 (15)	1.12579 (15)	0.0582 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0542 (17)	0.0533 (16)	0.0632 (19)	−0.0034 (13)	0.0263 (16)	−0.0015 (15)
C2	0.0491 (18)	0.076 (2)	0.073 (2)	−0.0145 (16)	0.0245 (17)	−0.0128 (18)
C3	0.0390 (16)	0.095 (3)	0.063 (2)	0.0017 (17)	0.0112 (15)	−0.0091 (19)
C4	0.0483 (17)	0.0676 (19)	0.0568 (19)	0.0101 (15)	0.0115 (15)	0.0017 (16)
C5	0.0426 (15)	0.0516 (16)	0.0420 (15)	0.0016 (12)	0.0139 (13)	−0.0015 (13)
C6	0.0431 (14)	0.0494 (15)	0.0435 (15)	0.0003 (12)	0.0177 (13)	−0.0015 (13)
C7	0.0468 (15)	0.0433 (15)	0.0506 (16)	−0.0001 (12)	0.0197 (13)	0.0004 (14)
C8	0.0382 (14)	0.0477 (15)	0.0518 (17)	0.0038 (12)	0.0153 (13)	0.0055 (13)
C9	0.0424 (15)	0.0473 (14)	0.0446 (16)	0.0017 (12)	0.0127 (13)	0.0014 (13)
C10	0.0426 (15)	0.0616 (17)	0.0552 (18)	0.0108 (13)	0.0196 (14)	0.0042 (15)
C11	0.0407 (15)	0.076 (2)	0.0493 (17)	−0.0026 (14)	0.0110 (14)	0.0006 (17)
C12	0.0541 (18)	0.075 (2)	0.0530 (18)	−0.0113 (15)	0.0126 (15)	−0.0093 (16)
C13	0.0573 (18)	0.0576 (17)	0.0596 (19)	−0.0026 (14)	0.0268 (16)	−0.0067 (15)
C14	0.0411 (15)	0.0520 (16)	0.0586 (19)	0.0105 (12)	0.0090 (15)	−0.0025 (16)
C15	0.064 (2)	0.072 (2)	0.093 (3)	−0.0104 (17)	0.0180 (19)	−0.015 (2)
C16	0.073 (2)	0.071 (2)	0.0570 (19)	0.0082 (17)	0.0236 (17)	−0.0100 (16)
C17	0.0428 (17)	0.115 (3)	0.074 (2)	−0.0002 (19)	0.0107 (17)	0.005 (2)
C18	0.048 (2)	0.131 (4)	0.138 (4)	0.020 (2)	0.009 (3)	0.003 (4)
C19	0.080 (3)	0.128 (4)	0.121 (4)	0.026 (3)	0.001 (3)	0.012 (3)
O1	0.0531 (11)	0.0474 (11)	0.0527 (12)	0.0001 (9)	0.0146 (10)	0.0027 (9)
O4	0.0372 (9)	0.0490 (10)	0.0684 (13)	0.0070 (8)	0.0188 (9)	0.0113 (9)
O2	0.0699 (14)	0.0784 (15)	0.0533 (13)	0.0034 (11)	0.0150 (12)	−0.0029 (11)
O3	0.0577 (12)	0.0600 (13)	0.0808 (15)	0.0010 (10)	0.0144 (11)	0.0244 (12)
O5	0.0482 (11)	0.0671 (13)	0.0543 (12)	0.0069 (10)	0.0097 (10)	−0.0124 (10)

Geometric parameters (Å, º) top

C1—C6	1.390 (4)	C11—C17	1.521 (5)
C1—C2	1.387 (4)	C12—C13	1.392 (5)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.364 (5)	C13—H13	0.9300
C2—H2	0.9300	C14—O2	1.189 (4)
C3—C4	1.376 (5)	C14—O1	1.357 (4)
C3—H3	0.9300	C14—C15	1.477 (4)
C4—C5	1.383 (4)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.390 (4)	C15—H15C	0.9600
C5—O1	1.394 (4)	C16—O5	1.423 (3)
C6—C7	1.492 (4)	C16—H16A	0.9600
C7—O3	1.195 (3)	C16—H16B	0.9600
C7—O4	1.346 (3)	C16—H16C	0.9600
C8—C13	1.363 (4)	C17—C18	1.465 (6)
C8—C9	1.386 (4)	C17—H17A	0.9700
C8—O4	1.412 (4)	C17—H17B	0.9700
C9—O5	1.364 (3)	C18—C19	1.226 (6)
C9—C10	1.389 (4)	C18—H18	0.9300
C10—C11	1.382 (4)	C19—H19A	0.9300
C10—H10	0.9300	C19—H19B	0.9300
C11—C12	1.368 (4)

C6—C1—C2	121.5 (3)	C13—C12—H12	119.7
C6—C1—H1	119.3	C8—C13—C12	119.7 (3)
C2—C1—H1	119.3	C8—C13—H13	120.1
C3—C2—C1	119.8 (3)	C12—C13—H13	120.1
C3—C2—H2	120.1	O2—C14—O1	123.0 (3)
C1—C2—H2	120.1	O2—C14—C15	126.7 (3)
C2—C3—C4	120.1 (3)	O1—C14—C15	110.4 (3)
C2—C3—H3	119.9	C14—C15—H15A	109.5
C4—C3—H3	119.9	C14—C15—H15B	109.5
C3—C4—C5	120.2 (3)	H15A—C15—H15B	109.5
C3—C4—H4	119.9	C14—C15—H15C	109.5
C5—C4—H4	119.9	H15A—C15—H15C	109.5
C4—C5—C6	121.0 (3)	H15B—C15—H15C	109.5
C4—C5—O1	116.6 (3)	O5—C16—H16A	109.5
C6—C5—O1	122.3 (3)	O5—C16—H16B	109.5
C1—C6—C5	117.5 (3)	H16A—C16—H16B	109.5
C1—C6—C7	116.7 (3)	O5—C16—H16C	109.5
C5—C6—C7	125.8 (2)	H16A—C16—H16C	109.5
O3—C7—O4	123.2 (3)	H16B—C16—H16C	109.5
O3—C7—C6	124.4 (2)	C18—C17—C11	112.3 (3)
O4—C7—C6	112.4 (2)	C18—C17—H17A	109.1
C13—C8—C9	121.1 (3)	C11—C17—H17A	109.1
C13—C8—O4	119.7 (2)	C18—C17—H17B	109.1
C9—C8—O4	118.9 (3)	C11—C17—H17B	109.1
O5—C9—C8	115.9 (3)	H17A—C17—H17B	107.9
O5—C9—C10	125.9 (2)	C19—C18—C17	132.9 (5)
C8—C9—C10	118.3 (3)	C19—C18—H18	113.5
C11—C10—C9	121.3 (2)	C17—C18—H18	113.5
C11—C10—H10	119.4	C18—C19—H19A	120.0
C9—C10—H10	119.4	C18—C19—H19B	120.0
C12—C11—C10	119.1 (3)	H19A—C19—H19B	120.0
C12—C11—C17	121.2 (3)	C14—O1—C5	118.3 (2)
C10—C11—C17	119.7 (3)	C7—O4—C8	118.8 (2)
C11—C12—C13	120.5 (3)	C9—O5—C16	117.7 (2)
C11—C12—H12	119.7

C6—C1—C2—C3	1.2 (4)	C9—C10—C11—C12	−0.4 (4)
C1—C2—C3—C4	0.1 (4)	C9—C10—C11—C17	−178.6 (3)
C2—C3—C4—C5	−0.7 (4)	C10—C11—C12—C13	0.9 (4)
C3—C4—C5—C6	0.1 (4)	C17—C11—C12—C13	179.1 (3)
C3—C4—C5—O1	−176.5 (2)	C9—C8—C13—C12	−0.1 (4)
C2—C1—C6—C5	−1.7 (4)	O4—C8—C13—C12	173.8 (2)
C2—C1—C6—C7	176.9 (2)	C11—C12—C13—C8	−0.6 (4)
C4—C5—C6—C1	1.0 (4)	C12—C11—C17—C18	−90.0 (5)
O1—C5—C6—C1	177.5 (2)	C10—C11—C17—C18	88.1 (4)
C4—C5—C6—C7	−177.5 (2)	C11—C17—C18—C19	122.2 (5)
O1—C5—C6—C7	−1.0 (4)	O2—C14—O1—C5	4.8 (4)
C1—C6—C7—O3	21.1 (4)	C15—C14—O1—C5	−176.0 (2)
C5—C6—C7—O3	−160.4 (3)	C4—C5—O1—C14	−113.6 (3)
C1—C6—C7—O4	−156.7 (2)	C6—C5—O1—C14	69.8 (3)
C5—C6—C7—O4	21.8 (3)	O3—C7—O4—C8	−5.3 (4)
C13—C8—C9—O5	179.9 (2)	C6—C7—O4—C8	172.4 (2)
O4—C8—C9—O5	6.0 (3)	C13—C8—O4—C7	105.2 (3)
C13—C8—C9—C10	0.6 (4)	C9—C8—O4—C7	−80.8 (3)
O4—C8—C9—C10	−173.3 (2)	C8—C9—O5—C16	−177.1 (2)
O5—C9—C10—C11	−179.6 (2)	C10—C9—O5—C16	2.2 (4)
C8—C9—C10—C11	−0.4 (4)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈O₅
M_r	326.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.60 (2), 12.58 (2), 13.23 (2)
β (°)	109.020 (17)
V (Å³)	1667 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.24 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.976, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	8695, 3089, 1786
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.142, 1.01
No. of reflections	3089
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.25

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the earmarked fund for China Agriculture Research System (cars-38).

References

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