4-Benz­yl­oxy-2-bromo-1-meth­­oxy­benzene

In the title compound, C₁₄H₁₃BrO₂, the phenyl ring is oriented at a dihedral angle of 72.6 (3)° with respect to the bromo­meth­oxy­phenyl ring. The crystal structure is stabilized by weak inter­molecular C—H⋯O inter­actions.

Related literature

For the synthesis of analogues of the title compound, see: Shi et al. (2004). The title compound could be converted to aromatic boric acid derivatives, which are significant inter­mediates of various novel bioactive compounds through Suzuki–Miyaura Coupling, see: Suzuki (2011).

Experimental

Crystal data

• C₁₄H₁₃BrO₂

• M_r = 293.15

• Monoclinic, P 2₁ /c

• a = 6.1415 (7) Å

• b = 8.2635 (7) Å

• c = 25.287 (2) Å

• β = 94.401 (10)°

• V = 1279.5 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 3.20 mm⁻¹

• T = 293 K

• 0.32 × 0.28 × 0.22 mm

Data collection

• Oxford Diffraction Xcalibur Eos diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) T_min = 0.859, T_max = 1.0

• 3982 measured reflections

• 3982 independent reflections

• 2610 reflections with I > 2σ(I)

Refinement

• R[F² > 2σ(F²)] = 0.055

• wR(F²) = 0.164

• S = 1.00

• 3982 reflections

• 156 parameters

• H-atom parameters constrained

• Δρ_max = 0.45 e Å⁻³

• Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2^i	0.93	2.54	3.453 (7)	169
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO CCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Supporting information

S1. Comment

The title compound, 4-(benzyloxy)-2-bromo-1-methoxybenzene was synthesize from 4-methoxyphenol through 4 steps reactions. The hydroxyl group of 4-methoxyphenol was protected by acetyl to give 4-methoxyphenyl acetate. Then ortho-position aromatic hydrogen atom of methoxy was substituted by bromidum to abtain 3-bromo-4-methoxyphenyl acetate when NBS (N-bromosuccinimide) was added in CH₃CN. After hydrolysis of acetyl group and re-protection by benzyl group with benzyl bromide, the title compound was prerarated almost quantitatively.

4-(Benzyloxy)-2-bromo-1-methoxybenzene could be converted to aromatic boric acid derivates, which are significant intermediate to form various novel bioactive compounds throngh Suzuki–Miyaura Coupling. Herein, we report the crystal structure of the important compound.

The title compound have two armatic rings, which are nearly orthogonal to each other [dihedral angle 72.58°]. The central oxygen atom (O₂) and carbon atom (C₈) are nearly coplanar with the bromobenzoyl ring and the benzoyl rings [O₂—C₄—C₅—C₆ torsion angles = 178.5 (6)° and C₈—C₉—C₁₀—C₁₁ torsion angles = 176.5 (6)°], respectively. The crystal structure is stabilized by weak intermolecular C—H···O interactions (Table 1).

Related literature

For the synthesis of analogues of the title compound, see: Shi et al. (2004). The title compound could be converted to aromatic boric acid derivates, which are significant intermediates of various novel bioactive compounds through Suzuki–Miyaura Coupling, see: Suzuki (2011).

S2. Experimental

Single crystals of 4-(benzyloxy)-2-bromo-1-methoxybenzene, C₁₄H₁₃BrO₂ were recrystallized from acetone mounted in inert oil and transferred to the cold gas stream of the diffractometer.

S3. Refinement

All the H-atoms were placed in calculated positions and treated as riding atoms [C—H = 0.93 - 0.96 Å], with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others.

Computing details

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO CCD (Oxford Diffraction, 2010); data reduction: CrysAlis PRO CCD (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Molecular structre showing 30% probability displacement ellipsoids.
	Fig. 2. The packing viewed along c axis with C—H···O interactions, indicating the dimer.

4-Benzyloxy-2-bromo-1-methoxybenzene

Crystal data

C14H13BrO2	F(000) = 592
Mr = 293.15	Dx = 1.522 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 1416 reflections
a = 6.1415 (7) Å	θ = 2.9–26.3°
b = 8.2635 (7) Å	µ = 3.20 mm^−1
c = 25.287 (2) Å	T = 293 K
β = 94.401 (10)°	Block, colourless
V = 1279.5 (2) Å^3	0.32 × 0.28 × 0.22 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur Eos diffractometer	3982 independent reflections
Radiation source: fine-focus sealed tube	2610 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 16.0874 pixels mm^-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −10→10
Tmin = 0.859, Tmax = 1.0	l = −30→31
3982 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1035P)^2] where P = (Fo^2 + 2Fc^2)/3
3982 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.52954 (11)	0.35775 (8)	0.77207 (3)	0.0720 (3)
O1	0.1613 (7)	0.1331 (5)	0.78343 (15)	0.0634 (11)
O2	0.6766 (7)	0.1821 (5)	0.97133 (16)	0.0691 (13)
C1	0.2856 (9)	0.1387 (7)	0.8308 (2)	0.0509 (14)
C2	0.4647 (9)	0.2388 (6)	0.8329 (2)	0.0478 (14)
C3	0.6002 (10)	0.2562 (6)	0.8784 (2)	0.0535 (16)
H3	0.7197	0.3254	0.8788	0.064*
C4	0.5592 (11)	0.1714 (6)	0.9233 (2)	0.0547 (16)
C5	0.3786 (10)	0.0679 (7)	0.9211 (2)	0.0605 (16)
H5	0.3478	0.0097	0.9511	0.073*
C6	0.2472 (10)	0.0511 (6)	0.8754 (2)	0.0548 (16)
H6	0.1301	−0.0204	0.8744	0.066*
C7	−0.0252 (9)	0.0291 (9)	0.7806 (2)	0.080 (2)
H7A	−0.1048	0.0410	0.7467	0.120*
H7C	−0.1177	0.0575	0.8081	0.120*
H7B	0.0217	−0.0812	0.7852	0.120*
C8	0.8485 (11)	0.2936 (8)	0.9758 (3)	0.0695 (19)
H8B	0.7976	0.3985	0.9628	0.083*
H8A	0.9648	0.2583	0.9546	0.083*
C9	0.9321 (11)	0.3061 (7)	1.0329 (2)	0.0573 (16)
C10	1.1363 (11)	0.2430 (7)	1.0508 (3)	0.0678 (19)
H10	1.2196	0.1869	1.0276	0.081*
C11	1.2111 (11)	0.2643 (8)	1.1021 (3)	0.072 (2)
H11	1.3478	0.2234	1.1135	0.087*
C12	1.0936 (13)	0.3434 (8)	1.1375 (3)	0.0714 (19)
H12	1.1467	0.3536	1.1728	0.086*
C13	0.8960 (13)	0.4075 (7)	1.1202 (3)	0.075 (2)
H13	0.8154	0.4652	1.1435	0.091*
C14	0.8152 (12)	0.3870 (7)	1.0678 (3)	0.0700 (19)
H14	0.6792	0.4292	1.0566	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0649 (4)	0.0851 (4)	0.0653 (4)	−0.0096 (4)	0.0005 (4)	0.0306 (4)
O1	0.058 (3)	0.078 (3)	0.051 (2)	−0.019 (2)	−0.015 (2)	0.005 (2)
O2	0.085 (3)	0.067 (3)	0.052 (3)	−0.034 (2)	−0.016 (2)	0.009 (2)
C1	0.052 (4)	0.045 (3)	0.056 (4)	−0.002 (3)	0.003 (3)	−0.008 (3)
C2	0.050 (4)	0.043 (3)	0.050 (4)	0.001 (3)	0.003 (3)	0.003 (3)
C3	0.056 (4)	0.045 (3)	0.059 (4)	−0.007 (3)	0.002 (3)	0.006 (3)
C4	0.070 (4)	0.047 (3)	0.047 (4)	−0.007 (3)	0.001 (3)	0.000 (3)
C5	0.081 (5)	0.052 (3)	0.049 (4)	−0.021 (4)	0.009 (4)	0.000 (3)
C6	0.060 (4)	0.050 (3)	0.054 (4)	−0.018 (3)	0.001 (3)	−0.003 (3)
C7	0.071 (5)	0.102 (5)	0.067 (5)	−0.024 (4)	0.004 (4)	−0.010 (4)
C8	0.071 (5)	0.073 (4)	0.065 (5)	−0.023 (4)	0.005 (4)	0.003 (4)
C9	0.064 (4)	0.053 (3)	0.055 (4)	−0.021 (3)	0.006 (4)	−0.002 (3)
C10	0.059 (4)	0.070 (4)	0.075 (5)	0.000 (4)	0.008 (4)	−0.017 (4)
C11	0.056 (4)	0.079 (5)	0.079 (5)	0.003 (4)	−0.014 (4)	−0.007 (4)
C12	0.093 (6)	0.065 (4)	0.054 (4)	−0.018 (5)	−0.006 (4)	−0.004 (4)
C13	0.083 (6)	0.070 (4)	0.075 (5)	−0.008 (4)	0.015 (4)	−0.018 (4)
C14	0.059 (4)	0.074 (4)	0.076 (5)	0.009 (4)	−0.003 (4)	0.003 (4)

Geometric parameters (Å, º)

Br1—C2	1.893 (5)	C7—H7B	0.9600
O1—C1	1.370 (6)	C8—H8B	0.9700
O1—C7	1.430 (7)	C8—H8A	0.9700
O2—C4	1.367 (7)	C8—C9	1.499 (8)
O2—C8	1.399 (7)	C9—C10	1.401 (9)
C1—C2	1.374 (7)	C9—C14	1.356 (9)
C1—C6	1.377 (8)	C10—H10	0.9300
C2—C3	1.375 (8)	C10—C11	1.354 (9)
C3—H3	0.9300	C11—H11	0.9300
C3—C4	1.374 (8)	C11—C12	1.360 (9)
C4—C5	1.398 (8)	C12—H12	0.9300
C5—H5	0.9300	C12—C13	1.365 (9)
C5—C6	1.364 (8)	C13—H13	0.9300
C6—H6	0.9300	C13—C14	1.387 (9)
C7—H7A	0.9600	C14—H14	0.9300
C7—H7C	0.9600
O1—C1—C2	116.4 (5)	C6—C5—H5	119.6
O1—C1—C6	125.4 (5)	H7A—C7—H7C	109.5
O1—C7—H7A	109.5	H7A—C7—H7B	109.5
O1—C7—H7C	109.5	H7C—C7—H7B	109.5
O1—C7—H7B	109.5	H8B—C8—H8A	108.3
O2—C4—C3	125.7 (6)	C9—C8—H8B	109.9
O2—C4—C5	116.0 (5)	C9—C8—H8A	109.9
O2—C8—H8B	109.9	C9—C10—H10	120.3
O2—C8—H8A	109.9	C9—C14—C13	120.9 (7)
O2—C8—C9	108.9 (5)	C9—C14—H14	119.6
C1—O1—C7	117.0 (4)	C10—C9—C8	121.1 (6)
C1—C2—Br1	119.9 (4)	C10—C11—H11	118.8
C1—C2—C3	121.8 (5)	C10—C11—C12	122.4 (6)
C1—C6—H6	119.6	C11—C10—C9	119.3 (6)
C2—C1—C6	118.1 (5)	C11—C10—H10	120.3
C2—C3—H3	120.0	C11—C12—H12	120.7
C3—C2—Br1	118.3 (4)	C11—C12—C13	118.6 (7)
C3—C4—C5	118.3 (6)	C12—C11—H11	118.8
C4—O2—C8	117.2 (5)	C12—C13—H13	119.9
C4—C3—C2	120.1 (6)	C12—C13—C14	120.2 (7)
C4—C3—H3	120.0	C13—C12—H12	120.7
C4—C5—H5	119.6	C13—C14—H14	119.6
C5—C6—C1	120.9 (5)	C14—C9—C8	120.2 (6)
C5—C6—H6	119.6	C14—C9—C10	118.6 (6)
C6—C5—C4	120.8 (5)	C14—C13—H13	119.9
Br1—C2—C3—C4	−179.7 (4)	C6—C1—C2—Br1	178.4 (4)
O1—C1—C2—Br1	−0.7 (7)	C6—C1—C2—C3	−1.8 (8)
O1—C1—C2—C3	179.1 (5)	C7—O1—C1—C2	179.8 (5)
O1—C1—C6—C5	−178.6 (5)	C7—O1—C1—C6	0.9 (8)
O2—C4—C5—C6	178.5 (6)	C8—O2—C4—C3	2.6 (9)
O2—C8—C9—C10	109.0 (7)	C8—O2—C4—C5	−175.4 (5)
O2—C8—C9—C14	−74.4 (7)	C8—C9—C10—C11	176.5 (6)
C1—C2—C3—C4	0.5 (9)	C8—C9—C14—C13	−176.3 (6)
C2—C1—C6—C5	2.4 (9)	C9—C10—C11—C12	1.0 (11)
C2—C3—C4—O2	−177.7 (5)	C10—C9—C14—C13	0.2 (9)
C2—C3—C4—C5	0.3 (9)	C10—C11—C12—C13	−2.0 (11)
C3—C4—C5—C6	0.3 (9)	C11—C12—C13—C14	2.1 (10)
C4—O2—C8—C9	170.9 (5)	C12—C13—C14—C9	−1.3 (10)
C4—C5—C6—C1	−1.7 (9)	C14—C9—C10—C11	−0.1 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^i	0.93	2.54	3.453 (7)	169

Symmetry code: (i) −x+1, −y, −z+2.