2-Isopropyl-4-meth­oxy-5-methyl­phenyl acetate

Oubabi, R.; Auhmani, A.; Ait Itto, M.Y.; Driss, M.; Soumhi, E.H.

doi:10.1107/S160053681302922X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1715

doi:10.1107/S160053681302922X

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2-Isopropyl-4-methoxy-5-methylphenyl acetate

Radouane Oubabi,^a Aziz Auhmani,^a My Youssef Ait Itto,^a Mohamed Driss ^b and El Hassane Soumhi ^c ^*

^aLaboratoire de Synthése Organique et Physico-Chimie Moléculaire, Faculté des Sciences-Semlalia, Université Cadi Ayyad, BP 2390, 40001, Marrakech, Morocco, ^bLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis ElManar, 2092 ElManar II, Tunis, Tunisia, and ^cEquipe de Chimie des Matériaux et de l'Environnement, FSTG-Marrakech, Université Cadi Ayyad, Bd Abdelkrim Khattabi, BP 549, Marrakech, Morocco
^*Correspondence e-mail: eh_soumhi@yahoo.fr

(Received 9 October 2013; accepted 23 October 2013; online 26 October 2013)

In the title compound, C₁₃H₁₈O₃, the benzene ring is almost perpendicular to the acetoxy plane, making a dihedral angle of 89.33 (11)°. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming a zigzag chain along the c-axis direction.

CCDC reference: 968255

Related literature

For background to natural monoterpenic phenols and their derivatives, see: Yuan-Lang & Erdtman (1962 ); Ündeğer et al. (2009 ); Osorio et al. (2006 ). For a related structure, see: Rajouani et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₈O₃
M_r = 222.27
Monoclinic, P 2₁ /c
a = 10.829 (2) Å
b = 9.600 (2) Å
c = 12.530 (3) Å
β = 100.34 (2)°
V = 1281.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 300 K
0.3 × 0.15 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.521, T_max = 0.992
3366 measured reflections
2780 independent reflections
1594 reflections with I > 2σ(I)
R_int = 0.018
2 standard reflections every 60 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.132
S = 1.02
2780 reflections
151 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H1⋯O2ⁱ	0.93	2.60	3.523 (3)	171
Symmetry code: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 968255

Crystal structure: contains datablocks I, hasacetf. DOI: 10.1107/S160053681302922X/is5314sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681302922X/is5314Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681302922X/is5314Isup3.cml

checkCIF report

Comment top

The p-methoxythymol is a natural phenol extracted from heartwood of tetraclinis articulate (Yuan-Lang et al., 1962). In several recent studies, natural monoterpenic phenols and their derivatives have revealed extensive biological activities, ranging from antimicrobial (Ündeğer et al., 2009) to Antileishmanial and Cytotoxic activities (Osorio et al., 2006). In the aim of preparing monoterpenic phenol derivatives, we report here, the hemisynthesis of 2-isopropyl-4-methoxy-5-methylphenyl acetate from naturally occurred p-methoxythymol. Thus, treatment of p-methoxythymol with acetic anhydride in pyridine, and provides the title compound as colorless crystals in 72.4% yield. Its structure was fully characterized by its mass and NMR spectroscopic data. Furthermore, the crystallographic study made it possible to determine the stereochemistry. The main geometric features of this group are in good agreement with those observed in a similar compound (Rajouani et al., 2008).

Related literature top

For background to natural monoterpenic phenols and their derivatives, see: Yuan-Lang & Erdtman (1962); Ündeğer et al. (2009); Osorio et al. (2006). For a related structure, see: Rajouani et al. (2008).

Experimental top

A solution of p-methoxythymol (111 mg, 0.617 mmol) in acetic anhydride (20 ml) and pyridine (20 ml) was heated under reflux for 24 h. After cooling, the mixture was acidified with 1 N HCl solution then extracted with ether (3 × 20 ml). The organic layer was washed with water, dried on anhydrous Na₂SO₄ and then evaporated under reduced pressure. The obtained residue was chromatographied on silica gel column using hexane and ethyl acetate (97/3) as eluent, to give 2-isopropyl-4-methoxy-5-methylphenyl acetate (100 mg) in 72.4% yield.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. The molecule structure of the title compound with 50% probability ellipsoids.

2-Isopropyl-4-methoxy-5-methylphenyl acetate top

Crystal data top

C₁₃H₁₈O₃	F(000) = 480
M_r = 222.27	D_x = 1.152 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.829 (2) Å	θ = 10–15°
b = 9.600 (2) Å	µ = 0.08 mm⁻¹
c = 12.530 (3) Å	T = 300 K
β = 100.34 (2)°	Prism, colourless
V = 1281.4 (5) Å³	0.3 × 0.15 × 0.1 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1594 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 27.0°, θ_min = 2.7°
ω/2θ scans	h = −13→1
Absorption correction: ψ scan (North et al., 1968)	k = −1→12
T_min = 0.521, T_max = 0.992	l = −15→15
3366 measured reflections	2 standard reflections every 60 min
2780 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.132	w = 1/[σ²(F_o²) + (0.0525P)² + 0.2201P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2780 reflections	Δρ_max = 0.16 e Å⁻³
151 parameters	Δρ_min = −0.13 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: 0.016 (3)

Crystal data top

C₁₃H₁₈O₃	V = 1281.4 (5) Å³
M_r = 222.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.829 (2) Å	µ = 0.08 mm⁻¹
b = 9.600 (2) Å	T = 300 K
c = 12.530 (3) Å	0.3 × 0.15 × 0.1 mm
β = 100.34 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1594 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.018
T_min = 0.521, T_max = 0.992	2 standard reflections every 60 min
3366 measured reflections	intensity decay: 1%
2780 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
2780 reflections	Δρ_min = −0.13 e Å⁻³
151 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
O1	0.76460 (12)	0.08305 (13)	0.33870 (9)	0.0587 (4)
O2	0.76646 (18)	−0.07552 (19)	0.46746 (13)	0.1062 (7)
O3	0.43208 (12)	−0.20942 (15)	0.03401 (10)	0.0673 (4)
C1	0.68418 (16)	−0.00154 (18)	0.26312 (13)	0.0496 (4)
C2	0.73387 (16)	−0.09160 (17)	0.19660 (13)	0.0476 (4)
C3	0.64806 (16)	−0.16266 (18)	0.11839 (14)	0.0522 (4)
H1	0.6777	−0.2242	0.0715	0.063*
C4	0.52031 (16)	−0.14316 (18)	0.10945 (13)	0.0514 (4)
C5	0.47183 (17)	−0.0533 (2)	0.17877 (14)	0.0562 (5)
C6	0.55666 (17)	0.0175 (2)	0.25510 (14)	0.0570 (5)
H2	0.5272	0.0792	0.3020	0.068*
C7	0.79534 (17)	0.0364 (2)	0.44091 (15)	0.0612 (5)
C8	0.8695 (2)	0.1412 (3)	0.51249 (17)	0.0803 (7)
H3	0.8841	0.1081	0.5860	0.096*
H4	0.8239	0.2274	0.5082	0.096*
H5	0.9485	0.1559	0.4896	0.096*
C9	0.4748 (2)	−0.2910 (2)	−0.04666 (16)	0.0742 (6)
H6	0.5283	−0.2355	−0.0830	0.089*
H7	0.4041	−0.3229	−0.0983	0.089*
H8	0.5210	−0.3697	−0.0132	0.089*
C10	0.33271 (18)	−0.0334 (3)	0.16960 (19)	0.0812 (7)
H9	0.3168	0.0323	0.2233	0.097*
H10	0.2943	−0.1210	0.1810	0.097*
H11	0.2982	0.0011	0.0986	0.097*
C11	0.87402 (16)	−0.11360 (19)	0.20594 (15)	0.0546 (5)
H12	0.9162	−0.0529	0.2641	0.066*
C12	0.9114 (2)	−0.2629 (2)	0.23722 (18)	0.0747 (6)
H13	0.8718	−0.3250	0.1813	0.090*
H14	0.8850	−0.2857	0.3043	0.090*
H15	1.0009	−0.2723	0.2458	0.090*
C13	0.9195 (2)	−0.0725 (3)	0.10231 (18)	0.0785 (6)
H16	1.0093	−0.0797	0.1133	0.094*
H17	0.8949	0.0218	0.0837	0.094*
H19	0.8830	−0.1335	0.0445	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0685 (8)	0.0536 (7)	0.0512 (7)	−0.0086 (6)	0.0036 (6)	−0.0056 (6)
O2	0.1266 (15)	0.1007 (13)	0.0758 (10)	−0.0443 (11)	−0.0236 (10)	0.0304 (10)
O3	0.0564 (7)	0.0792 (9)	0.0621 (8)	−0.0073 (7)	−0.0007 (6)	−0.0123 (7)
C1	0.0553 (10)	0.0460 (10)	0.0448 (9)	−0.0017 (8)	0.0022 (8)	0.0014 (8)
C2	0.0509 (9)	0.0444 (9)	0.0464 (9)	−0.0011 (8)	0.0054 (7)	0.0033 (8)
C3	0.0574 (11)	0.0510 (10)	0.0475 (9)	−0.0004 (8)	0.0079 (8)	−0.0034 (8)
C4	0.0508 (10)	0.0521 (10)	0.0481 (9)	−0.0037 (8)	0.0006 (8)	0.0019 (8)
C5	0.0516 (10)	0.0583 (11)	0.0562 (10)	0.0076 (9)	0.0030 (8)	0.0052 (9)
C6	0.0624 (11)	0.0543 (11)	0.0543 (11)	0.0077 (9)	0.0108 (9)	−0.0040 (9)
C7	0.0533 (11)	0.0727 (13)	0.0545 (11)	−0.0043 (10)	0.0013 (9)	0.0009 (10)
C8	0.0706 (13)	0.0957 (17)	0.0675 (13)	−0.0095 (12)	−0.0071 (11)	−0.0155 (12)
C9	0.0796 (14)	0.0819 (15)	0.0586 (11)	−0.0200 (12)	0.0054 (10)	−0.0148 (11)
C10	0.0567 (12)	0.0940 (17)	0.0900 (16)	0.0120 (12)	0.0052 (11)	−0.0100 (13)
C11	0.0504 (10)	0.0560 (11)	0.0559 (10)	−0.0048 (9)	0.0053 (8)	−0.0048 (9)
C12	0.0615 (12)	0.0719 (14)	0.0860 (15)	0.0071 (11)	0.0006 (11)	0.0076 (12)
C13	0.0652 (13)	0.0903 (16)	0.0839 (15)	−0.0030 (12)	0.0236 (11)	0.0106 (13)

Geometric parameters (Å, º) top

O1—C7	1.341 (2)	C11—C12	1.522 (3)
O1—C1	1.421 (2)	C8—H3	0.9600
O2—C7	1.183 (2)	C8—H4	0.9600
O3—C4	1.374 (2)	C8—H5	0.9600
O3—C9	1.420 (2)	C9—H6	0.9600
C1—C2	1.376 (2)	C9—H7	0.9600
C1—C6	1.379 (2)	C9—H8	0.9600
C2—C3	1.401 (2)	C10—H9	0.9600
C2—C11	1.516 (2)	C10—H10	0.9600
C3—C4	1.380 (2)	C10—H11	0.9600
C3—H1	0.9300	C11—H12	0.9800
C4—C5	1.392 (3)	C12—H13	0.9600
C5—C6	1.380 (2)	C12—H14	0.9600
C5—C10	1.502 (3)	C12—H15	0.9600
C6—H2	0.9300	C13—H16	0.9600
C7—C8	1.484 (3)	C13—H17	0.9600
C11—C13	1.521 (3)	C13—H19	0.9600

C7—O1—C1	117.57 (14)	O3—C9—H7	109.5
C4—O3—C9	118.02 (15)	H6—C9—H7	109.5
C2—C1—C6	122.33 (16)	O3—C9—H8	109.5
C2—C1—O1	120.23 (15)	H6—C9—H8	109.5
C6—C1—O1	117.31 (16)	H7—C9—H8	109.5
C1—C2—C3	116.58 (16)	C5—C10—H9	109.5
C1—C2—C11	122.40 (15)	C5—C10—H10	109.5
C3—C2—C11	121.02 (16)	H9—C10—H10	109.5
C4—C3—C2	121.33 (17)	C5—C10—H11	109.5
C4—C3—H1	119.3	H9—C10—H11	109.5
C2—C3—H1	119.3	H10—C10—H11	109.5
O3—C4—C3	123.79 (16)	C2—C11—C13	111.77 (15)
O3—C4—C5	115.01 (16)	C2—C11—C12	111.54 (15)
C3—C4—C5	121.20 (16)	C13—C11—C12	110.65 (17)
C6—C5—C4	117.32 (16)	C2—C11—H12	107.5
C6—C5—C10	121.61 (18)	C13—C11—H12	107.5
C4—C5—C10	121.07 (17)	C12—C11—H12	107.5
C1—C6—C5	121.23 (17)	C11—C12—H13	109.5
C1—C6—H2	119.4	C11—C12—H14	109.5
C5—C6—H2	119.4	H13—C12—H14	109.5
O2—C7—O1	122.63 (18)	C11—C12—H15	109.5
O2—C7—C8	125.96 (19)	H13—C12—H15	109.5
O1—C7—C8	111.41 (18)	H14—C12—H15	109.5
C7—C8—H3	109.5	C11—C13—H16	109.5
C7—C8—H4	109.5	C11—C13—H17	109.5
H3—C8—H4	109.5	H16—C13—H17	109.5
C7—C8—H5	109.5	C11—C13—H19	109.5
H3—C8—H5	109.5	H16—C13—H19	109.5
H4—C8—H5	109.5	H17—C13—H19	109.5
O3—C9—H6	109.5

C7—O1—C1—C2	−95.9 (2)	C3—C4—C5—C6	1.3 (3)
C7—O1—C1—C6	88.2 (2)	O3—C4—C5—C10	0.3 (3)
C6—C1—C2—C3	0.8 (3)	C3—C4—C5—C10	−179.34 (18)
O1—C1—C2—C3	−174.89 (14)	C2—C1—C6—C5	−0.3 (3)
C6—C1—C2—C11	−179.47 (17)	O1—C1—C6—C5	175.57 (16)
O1—C1—C2—C11	4.8 (2)	C4—C5—C6—C1	−0.8 (3)
C1—C2—C3—C4	−0.3 (2)	C10—C5—C6—C1	179.85 (19)
C11—C2—C3—C4	179.98 (16)	C1—O1—C7—O2	6.1 (3)
C9—O3—C4—C3	−7.0 (3)	C1—O1—C7—C8	−174.65 (16)
C9—O3—C4—C5	173.38 (16)	C1—C2—C11—C13	−118.73 (19)
C2—C3—C4—O3	179.64 (15)	C3—C2—C11—C13	61.0 (2)
C2—C3—C4—C5	−0.8 (3)	C1—C2—C11—C12	116.80 (19)
O3—C4—C5—C6	−179.06 (15)	C3—C2—C11—C12	−63.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H1···O2ⁱ	0.93	2.60	3.523 (3)	171

Symmetry code: (i) x, −y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H1···O2ⁱ	0.93	2.60	3.523 (3)	171

Symmetry code: (i) x, −y−1/2, z−1/2.

References

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doi:10.1107/S160053681302922X

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