Methyl 4-but­oxy-3-methoxy­benzoate

Zhang, M.; Lu, R.-Z.; Han, L.-N.; Wei, W.-B.; Wang, H.-B.

doi:10.1107/S1600536809003080

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o434

doi:10.1107/S1600536809003080

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Methyl 4-butoxy-3-methoxybenzoate

Min Zhang,^a Ran-Zhe Lu,^a Lu-Na Han,^a Wen-Bin Wei ^a and Hai-Bo Wang ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 13 January 2009; accepted 24 January 2009; online 31 January 2009)

The title compound, C₁₃H₁₈O₄, is an intermediate product in the synthesis of quinazoline derivatives. Crystal structure analysis shows that the benzene–butoxy C_ar—O—C—C torsion angle is 175.3 (2)° and that the benzene–methoxycarbonyl C_ar—C—O—C torsion angle is 175.2 (2)°. Torsion angles close to 180° indicate that the molecule is almost planar.

Related literature

For general background, see: Knesl et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₁₈O₄
M_r = 238.27
Triclinic, $[P \overline 1]$
a = 7.9660 (16) Å
b = 9.1630 (18) Å
c = 10.143 (2) Å
α = 64.80 (2)°
β = 70.96 (3)°
γ = 79.26 (3)°
V = 632.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.991
2474 measured reflections
2294 independent reflections
1567 reflections with I > 2σ(I)
R_int = 0.067
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.168
S = 1.00
2294 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809003080/wk2098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003080/wk2098Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies on quinazoline derivatives (Knesl et al., 2006), we report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C4–C9) is, of course, planar.

Related literature top

For general background, see: Knesl et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, methyl 3-methoxy-4-hydroxybenzoate (55 mmol), 1-bromobutane (110 mmol) and potassium carbonate (165 mmol) were mixed with DMF (60 ml), and then the mixture was heated to reflux for 2 h. Reaction progress was monitored by TLC. After cooling and filtration, the title compound was obtained (yield 92%, m.p. 317 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: PLATON (Spek, 2003).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.

Methyl 4-butoxy-3-methoxybenzoate top

Crystal data top

C₁₃H₁₈O₄	Z = 2
M_r = 238.27	F(000) = 256
Triclinic, P1	D_x = 1.252 Mg m⁻³
Hall symbol: -P 1	Melting point: 317 K
a = 7.9660 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1630 (18) Å	Cell parameters from 25 reflections
c = 10.143 (2) Å	θ = 9–12°
α = 64.80 (2)°	µ = 0.09 mm⁻¹
β = 70.96 (3)°	T = 293 K
γ = 79.26 (3)°	Block, colourless
V = 632.3 (2) Å³	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1567 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.067
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −10→11
T_min = 0.973, T_max = 0.991	l = −11→12
2474 measured reflections	3 standard reflections every 200 reflections
2294 independent reflections	intensity decay: 1%

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.07P)² + 0.43P] where P = (F_o² + 2F_c²)/3
2294 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₈O₄	γ = 79.26 (3)°
M_r = 238.27	V = 632.3 (2) Å³
Triclinic, P1	Z = 2
a = 7.9660 (16) Å	Mo Kα radiation
b = 9.1630 (18) Å	µ = 0.09 mm⁻¹
c = 10.143 (2) Å	T = 293 K
α = 64.80 (2)°	0.30 × 0.20 × 0.10 mm
β = 70.96 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1567 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.067
T_min = 0.973, T_max = 0.991	3 standard reflections every 200 reflections
2474 measured reflections	intensity decay: 1%
2294 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
2294 reflections	Δρ_min = −0.21 e Å⁻³
154 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.3147 (2)	0.6241 (2)	0.05115 (19)	0.0488 (5)
O2	0.0656 (2)	0.4271 (2)	0.15700 (19)	0.0516 (5)
O3	0.0117 (3)	0.1304 (3)	0.7289 (2)	0.0733 (7)
O4	0.1887 (2)	0.2708 (2)	0.75552 (19)	0.0570 (5)
C1	0.6296 (5)	1.0667 (4)	−0.4050 (3)	0.0749 (10)
H1A	0.7158	1.1438	−0.4358	0.112*
H1B	0.5201	1.1226	−0.4245	0.112*
H1C	0.6732	0.9990	−0.4612	0.112*
C2	0.5977 (4)	0.9645 (4)	−0.2387 (3)	0.0606 (8)
H2A	0.5569	1.0348	−0.1838	0.073*
H2B	0.7101	0.9117	−0.2204	0.073*
C3	0.4645 (3)	0.8369 (3)	−0.1746 (3)	0.0473 (6)
H3A	0.3493	0.8884	−0.1865	0.057*
H3B	0.5016	0.7675	−0.2305	0.057*
C4	0.4487 (4)	0.7377 (3)	−0.0111 (3)	0.0493 (7)
H4A	0.5619	0.6806	0.0002	0.059*
H4B	0.4189	0.8078	0.0438	0.059*
C5	0.2767 (3)	0.5331 (3)	0.2032 (3)	0.0410 (6)
C6	0.3595 (3)	0.5399 (3)	0.3000 (3)	0.0495 (7)
H6A	0.4504	0.6098	0.2622	0.059*
C7	0.3085 (3)	0.4438 (3)	0.4524 (3)	0.0477 (6)
H7A	0.3639	0.4505	0.5172	0.057*
C8	0.1752 (3)	0.3373 (3)	0.5099 (3)	0.0443 (6)
C9	0.0934 (3)	0.3285 (3)	0.4133 (3)	0.0438 (6)
H9A	0.0051	0.2559	0.4516	0.053*
C10	0.1400 (3)	0.4256 (3)	0.2606 (3)	0.0401 (6)
C11	−0.0929 (4)	0.3439 (4)	0.2120 (3)	0.0564 (8)
H11A	−0.1314	0.3542	0.1278	0.085*
H11B	−0.1841	0.3895	0.2749	0.085*
H11C	−0.0703	0.2317	0.2702	0.085*
C12	0.1161 (3)	0.2332 (3)	0.6753 (3)	0.0468 (6)
C13	0.1295 (4)	0.1866 (4)	0.9164 (3)	0.0661 (8)
H13A	0.1890	0.2239	0.9638	0.099*
H13B	0.1562	0.0729	0.9425	0.099*
H13C	0.0034	0.2066	0.9511	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0478 (10)	0.0490 (11)	0.0479 (10)	−0.0110 (8)	−0.0085 (8)	−0.0176 (8)
O2	0.0480 (10)	0.0598 (12)	0.0497 (10)	−0.0140 (9)	−0.0114 (8)	−0.0211 (9)
O3	0.0858 (16)	0.0749 (15)	0.0559 (12)	−0.0289 (13)	−0.0188 (11)	−0.0135 (11)
O4	0.0592 (12)	0.0667 (13)	0.0460 (10)	−0.0054 (10)	−0.0141 (9)	−0.0226 (9)
C1	0.076 (2)	0.065 (2)	0.066 (2)	−0.0173 (18)	−0.0084 (16)	−0.0119 (16)
C2	0.0603 (18)	0.0566 (18)	0.0607 (17)	−0.0145 (15)	−0.0097 (14)	−0.0198 (14)
C3	0.0466 (15)	0.0402 (15)	0.0547 (15)	0.0003 (12)	−0.0074 (11)	−0.0241 (12)
C4	0.0486 (15)	0.0425 (15)	0.0589 (16)	−0.0092 (12)	−0.0099 (12)	−0.0228 (12)
C5	0.0390 (13)	0.0368 (13)	0.0485 (13)	0.0017 (11)	−0.0093 (10)	−0.0215 (11)
C6	0.0443 (15)	0.0510 (16)	0.0575 (16)	−0.0088 (12)	−0.0119 (12)	−0.0245 (13)
C7	0.0444 (15)	0.0497 (16)	0.0563 (15)	0.0033 (12)	−0.0201 (12)	−0.0254 (12)
C8	0.0394 (13)	0.0425 (14)	0.0528 (15)	0.0072 (11)	−0.0137 (11)	−0.0236 (12)
C9	0.0403 (14)	0.0397 (14)	0.0536 (15)	0.0013 (11)	−0.0115 (11)	−0.0228 (11)
C10	0.0361 (13)	0.0417 (14)	0.0498 (14)	0.0055 (11)	−0.0125 (10)	−0.0274 (11)
C11	0.0539 (17)	0.0673 (19)	0.0517 (15)	−0.0164 (15)	−0.0143 (12)	−0.0217 (14)
C12	0.0418 (14)	0.0487 (16)	0.0534 (15)	0.0075 (12)	−0.0184 (12)	−0.0235 (12)
C13	0.0680 (19)	0.079 (2)	0.0490 (16)	−0.0016 (17)	−0.0149 (14)	−0.0253 (15)

Geometric parameters (Å, º) top

O1—C5	1.364 (3)	C4—H4B	0.9700
O1—C4	1.427 (3)	C5—C6	1.375 (3)
O2—C10	1.359 (3)	C5—C10	1.411 (3)
O2—C11	1.423 (3)	C6—C7	1.376 (4)
O3—C12	1.198 (3)	C6—H6A	0.9300
O4—C12	1.317 (3)	C7—C8	1.385 (3)
O4—C13	1.429 (3)	C7—H7A	0.9300
C1—C2	1.501 (4)	C8—C9	1.376 (3)
C1—H1A	0.9600	C8—C12	1.495 (4)
C1—H1B	0.9600	C9—C10	1.379 (3)
C1—H1C	0.9600	C9—H9A	0.9300
C2—C3	1.510 (4)	C11—H11A	0.9600
C2—H2A	0.9700	C11—H11B	0.9600
C2—H2B	0.9700	C11—H11C	0.9600
C3—C4	1.488 (4)	C13—H13A	0.9600
C3—H3A	0.9700	C13—H13B	0.9600
C3—H3B	0.9700	C13—H13C	0.9600
C4—H4A	0.9700

C5—O1—C4	116.99 (19)	C5—C6—C7	120.4 (2)
C10—O2—C11	117.84 (19)	C5—C6—H6A	119.8
C12—O4—C13	116.2 (2)	C7—C6—H6A	119.8
C2—C1—H1A	109.5	C6—C7—C8	120.5 (2)
C2—C1—H1B	109.5	C6—C7—H7A	119.8
H1A—C1—H1B	109.5	C8—C7—H7A	119.8
C2—C1—H1C	109.5	C9—C8—C7	119.4 (2)
H1A—C1—H1C	109.5	C9—C8—C12	119.2 (2)
H1B—C1—H1C	109.5	C7—C8—C12	121.4 (2)
C1—C2—C3	115.2 (3)	C8—C9—C10	121.2 (2)
C1—C2—H2A	108.5	C8—C9—H9A	119.4
C3—C2—H2A	108.5	C10—C9—H9A	119.4
C1—C2—H2B	108.5	O2—C10—C9	125.5 (2)
C3—C2—H2B	108.5	O2—C10—C5	115.7 (2)
H2A—C2—H2B	107.5	C9—C10—C5	118.9 (2)
C4—C3—C2	111.0 (2)	O2—C11—H11A	109.5
C4—C3—H3A	109.4	O2—C11—H11B	109.5
C2—C3—H3A	109.4	H11A—C11—H11B	109.5
C4—C3—H3B	109.4	O2—C11—H11C	109.5
C2—C3—H3B	109.4	H11A—C11—H11C	109.5
H3A—C3—H3B	108.0	H11B—C11—H11C	109.5
O1—C4—C3	110.7 (2)	O3—C12—O4	124.0 (2)
O1—C4—H4A	109.5	O3—C12—C8	123.9 (2)
C3—C4—H4A	109.5	O4—C12—C8	112.0 (2)
O1—C4—H4B	109.5	O4—C13—H13A	109.5
C3—C4—H4B	109.5	O4—C13—H13B	109.5
H4A—C4—H4B	108.1	H13A—C13—H13B	109.5
O1—C5—C6	125.3 (2)	O4—C13—H13C	109.5
O1—C5—C10	115.1 (2)	H13A—C13—H13C	109.5
C6—C5—C10	119.7 (2)	H13B—C13—H13C	109.5

C1—C2—C3—C4	177.4 (3)	C11—O2—C10—C5	−168.8 (2)
C5—O1—C4—C3	−175.3 (2)	C8—C9—C10—O2	−179.1 (2)
C2—C3—C4—O1	176.4 (2)	C8—C9—C10—C5	1.3 (4)
C4—O1—C5—C6	−1.4 (4)	O1—C5—C10—O2	0.2 (3)
C4—O1—C5—C10	178.3 (2)	C6—C5—C10—O2	179.9 (2)
O1—C5—C6—C7	179.0 (2)	O1—C5—C10—C9	179.8 (2)
C10—C5—C6—C7	−0.7 (4)	C6—C5—C10—C9	−0.4 (4)
C5—C6—C7—C8	1.0 (4)	C13—O4—C12—O3	−3.1 (4)
C6—C7—C8—C9	−0.2 (4)	C13—O4—C12—C8	175.2 (2)
C6—C7—C8—C12	−179.3 (2)	C9—C8—C12—O3	7.1 (4)
C7—C8—C9—C10	−0.9 (4)	C7—C8—C12—O3	−173.9 (3)
C12—C8—C9—C10	178.1 (2)	C9—C8—C12—O4	−171.2 (2)
C11—O2—C10—C9	11.6 (4)	C7—C8—C12—O4	7.8 (4)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈O₄
M_r	238.27
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.9660 (16), 9.1630 (18), 10.143 (2)
α, β, γ (°)	64.80 (2), 70.96 (3), 79.26 (3)
V (Å³)	632.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2474, 2294, 1567
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.168, 1.00
No. of reflections	2294
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Knesl, P., Roeseling, D. & Jordis, U. (2006). Molecules, 11, 286–297. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar