1,2-Bis(bromo­meth­yl)-4,5-dimethoxy­benzene

Zhou, F.

doi:10.1107/S1600536809030001

organic compounds

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Volume 65| Part 9| September 2009| Page o2064

doi:10.1107/S1600536809030001

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1,2-Bis(bromomethyl)-4,5-dimethoxybenzene

Feng-yan Zhou ^a ^*

^aDepartment of Chemistry, Zaozhuang University, Shandong, People's Republic of China
^*Correspondence e-mail: orgzfy@163.com

(Received 24 June 2009; accepted 29 July 2009; online 8 August 2009)

Colourless crystals of the title compound, C₁₀H₁₂Br₂O₂, were synthesized from 1,2-dimethoxybenzene. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen bonds.

Related literature

For the use of the title compound in the preparation of crown ether derivatives and isoindoline compounds, see: Dalence-Guzman et al. (2008 ); Diederich et al. (1993 ); Walpole et al. (1994 ).

Experimental

Crystal data

C₁₀H₁₂Br₂O₂
M_r = 324.00
Orthorhombic, P b c a
a = 8.125 (6) Å
b = 14.689 (10) Å
c = 20.353 (13) Å
V = 2429 (3) Å³
Z = 8
Mo Kα radiation
μ = 6.65 mm⁻¹
T = 153 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.456, T_max = 0.516
12237 measured reflections
2475 independent reflections
1643 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.117
S = 1.02
2475 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O2ⁱ	0.99	2.48	3.373 (6)	150
C10—H10C⋯O2ⁱⁱ	0.98	2.48	3.392 (7)	155
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030001/jh2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030001/jh2086Isup2.hkl

checkCIF report

Comment top

Bis-bromomethylation of 1,2-dimethoxybenzene afforded the title compound(I), which was useful for the preparation of crown ether derivatives and isoindoline compounds (Diederich et al., 1993; Walpole et al., 1994; Dalence-Guzman et al., 2008). It had been believed difficult to introduce hydroxyl groups directly to the 5- and 6-positions of isoindoline. With I as an intermediate, novel isoindoline derivatives could be easily prepared. The crystal structure of I is stabilized by intermolecular C–H···O hydrogen bonds.

Related literature top

For the use of the title compound in the preparation of crown ether derivatives and isoindoline compounds, see: Dalence-Guzman et al. (2008); Diederich et al. (1993); Walpole et al. (1994).

Experimental top

Thirty-three percent HBr in AcOH (31.0 ml) was added to a solution of 1,2-dimethoxybenzene (10 g, 0.0725 mmol) and paraformaldehyde (4.35 g, 0.145 mmol) in acetic acid (100 ml), while the temperature was kept at 283 K. After stirring at room temperature for 20 h, the mixture was heated to 338 K for 1 h. The mixture was concentrated. EtOAc was added to get a white precipitate. The precipitate was filtered and washed with EtOAc to afford the title compound (9.72 g, 41.4%) as a white solid. Colourless crystals were obtained by vapor diffusion of pentane into a dichloromethane solution over a period of 3 days. ¹H NMR (400 MHz, CDCl₃, 295 K): 6.84 (2H, s), 4.63 (4H, s), 3.90 (6H, s).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing diagram of molecular, viewed down the a axis, with the C—H···O interactions shown as dashed lines.

1,2-Bis(bromomethyl)-4,5-dimethoxybenzene top

Crystal data top

C₁₀H₁₂Br₂O₂	F(000) = 1264
M_r = 324.00	D_x = 1.772 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2795 reflections
a = 8.125 (6) Å	θ = 2.8–22.0°
b = 14.689 (10) Å	µ = 6.65 mm⁻¹
c = 20.353 (13) Å	T = 153 K
V = 2429 (3) Å³	Prism, colourless
Z = 8	0.15 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2475 independent reflections
Radiation source: fine-focus sealed tube	1643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→6
T_min = 0.456, T_max = 0.516	k = −18→17
12237 measured reflections	l = −25→20

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0542P)² + 2.9265P] where P = (F_o² + 2F_c²)/3
2475 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.89 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

C₁₀H₁₂Br₂O₂	V = 2429 (3) Å³
M_r = 324.00	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.125 (6) Å	µ = 6.65 mm⁻¹
b = 14.689 (10) Å	T = 153 K
c = 20.353 (13) Å	0.15 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2475 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1643 reflections with I > 2σ(I)
T_min = 0.456, T_max = 0.516	R_int = 0.043
12237 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.02	Δρ_max = 0.89 e Å⁻³
2475 reflections	Δρ_min = −0.72 e Å⁻³
129 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
Br1	0.41088 (8)	0.58977 (4)	0.08751 (3)	0.0691 (2)
Br2	−0.16982 (8)	0.43548 (4)	0.13229 (3)	0.0720 (2)
C1	0.3186 (6)	0.2549 (3)	0.1807 (2)	0.0410 (10)
O2	0.3599 (4)	0.1778 (2)	0.21493 (15)	0.0514 (8)
C2	0.4121 (6)	0.2681 (3)	0.12203 (19)	0.0385 (10)
C3	0.1717 (6)	0.3963 (3)	0.1603 (2)	0.0443 (10)
O1	0.5203 (4)	0.1999 (2)	0.10678 (14)	0.0549 (9)
C4	0.2023 (6)	0.3175 (3)	0.1981 (2)	0.0438 (10)
H4	0.1399	0.3077	0.2370	0.053*
C5	0.3861 (6)	0.3470 (3)	0.0855 (2)	0.0428 (10)
H5	0.4500	0.3574	0.0471	0.051*
C8	0.0391 (7)	0.4600 (3)	0.1814 (2)	0.0568 (13)
H8A	0.0745	0.5235	0.1733	0.068*
H8B	0.0194	0.4529	0.2291	0.068*
C7	0.2466 (7)	0.4960 (3)	0.0628 (2)	0.0554 (12)
H7A	0.1343	0.5206	0.0689	0.067*
H7B	0.2602	0.4801	0.0158	0.067*
C6	0.2675 (6)	0.4116 (3)	0.1043 (2)	0.0441 (11)
C10	0.2760 (7)	0.1627 (4)	0.2764 (3)	0.0681 (16)
H10A	0.2901	0.2159	0.3048	0.102*
H10B	0.3222	0.1088	0.2980	0.102*
H10C	0.1585	0.1529	0.2680	0.102*
C20	0.6114 (8)	0.2081 (4)	0.0474 (3)	0.0712 (16)
H20A	0.5362	0.2043	0.0098	0.107*
H20B	0.6923	0.1588	0.0447	0.107*
H20C	0.6684	0.2669	0.0467	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0821 (5)	0.0486 (3)	0.0765 (4)	−0.0146 (3)	0.0161 (3)	0.0010 (2)
Br2	0.0562 (4)	0.0688 (4)	0.0911 (5)	0.0108 (3)	−0.0137 (3)	−0.0024 (3)
C1	0.048 (3)	0.035 (2)	0.040 (2)	0.002 (2)	−0.0024 (19)	0.0038 (18)
O2	0.051 (2)	0.0500 (18)	0.0532 (18)	0.0134 (15)	0.0079 (15)	0.0175 (14)
C2	0.034 (2)	0.040 (2)	0.042 (2)	0.0025 (19)	−0.0016 (19)	−0.0022 (18)
C3	0.046 (3)	0.036 (2)	0.051 (3)	0.002 (2)	−0.008 (2)	−0.0076 (19)
O1	0.062 (2)	0.0549 (19)	0.0474 (17)	0.0175 (18)	0.0145 (16)	0.0053 (15)
C4	0.050 (3)	0.043 (2)	0.039 (2)	0.001 (2)	0.000 (2)	−0.0005 (18)
C5	0.042 (3)	0.048 (2)	0.038 (2)	−0.003 (2)	−0.003 (2)	0.0009 (19)
C8	0.063 (3)	0.041 (3)	0.067 (3)	0.008 (2)	−0.008 (3)	−0.010 (2)
C7	0.058 (3)	0.045 (3)	0.063 (3)	−0.003 (2)	−0.013 (3)	0.011 (2)
C6	0.052 (3)	0.034 (2)	0.046 (2)	−0.003 (2)	−0.006 (2)	0.0016 (19)
C10	0.062 (4)	0.075 (3)	0.068 (3)	0.013 (3)	0.018 (3)	0.031 (3)
C20	0.077 (4)	0.075 (4)	0.062 (3)	0.019 (3)	0.029 (3)	−0.006 (3)

Geometric parameters (Å, º) top

Br1—C7	1.983 (5)	C5—C6	1.405 (6)
Br2—C8	2.002 (5)	C5—H5	0.9500
C1—C4	1.365 (6)	C8—H8A	0.9900
C1—O2	1.372 (5)	C8—H8B	0.9900
C1—C2	1.428 (6)	C7—C6	1.510 (6)
O2—C10	1.442 (6)	C7—H7A	0.9900
C2—O1	1.368 (5)	C7—H7B	0.9900
C2—C5	1.394 (6)	C10—H10A	0.9800
C3—C6	1.399 (6)	C10—H10B	0.9800
C3—C4	1.413 (6)	C10—H10C	0.9800
C3—C8	1.490 (7)	C20—H20A	0.9800
O1—C20	1.422 (6)	C20—H20B	0.9800
C4—H4	0.9500	C20—H20C	0.9800

C4—C1—O2	126.4 (4)	H8A—C8—H8B	108.1
C4—C1—C2	119.7 (4)	C6—C7—Br1	110.6 (3)
O2—C1—C2	114.0 (4)	C6—C7—H7A	109.5
C1—O2—C10	116.9 (4)	Br1—C7—H7A	109.5
O1—C2—C5	125.8 (4)	C6—C7—H7B	109.5
O1—C2—C1	115.7 (3)	Br1—C7—H7B	109.5
C5—C2—C1	118.5 (4)	H7A—C7—H7B	108.1
C6—C3—C4	118.5 (4)	C3—C6—C5	119.7 (4)
C6—C3—C8	122.5 (4)	C3—C6—C7	121.7 (4)
C4—C3—C8	119.0 (4)	C5—C6—C7	118.7 (4)
C2—O1—C20	117.7 (4)	O2—C10—H10A	109.5
C1—C4—C3	122.1 (4)	O2—C10—H10B	109.5
C1—C4—H4	118.9	H10A—C10—H10B	109.5
C3—C4—H4	118.9	O2—C10—H10C	109.5
C2—C5—C6	121.4 (4)	H10A—C10—H10C	109.5
C2—C5—H5	119.3	H10B—C10—H10C	109.5
C6—C5—H5	119.3	O1—C20—H20A	109.5
C3—C8—Br2	110.9 (3)	O1—C20—H20B	109.5
C3—C8—H8A	109.5	H20A—C20—H20B	109.5
Br2—C8—H8A	109.5	O1—C20—H20C	109.5
C3—C8—H8B	109.5	H20A—C20—H20C	109.5
Br2—C8—H8B	109.5	H20B—C20—H20C	109.5

C4—C1—O2—C10	−2.0 (7)	O1—C2—C5—C6	177.7 (4)
C2—C1—O2—C10	177.1 (4)	C1—C2—C5—C6	−2.0 (6)
C4—C1—C2—O1	−177.0 (4)	C6—C3—C8—Br2	82.9 (5)
O2—C1—C2—O1	3.8 (6)	C4—C3—C8—Br2	−97.1 (4)
C4—C1—C2—C5	2.7 (6)	C4—C3—C6—C5	2.6 (6)
O2—C1—C2—C5	−176.5 (4)	C8—C3—C6—C5	−177.4 (4)
C5—C2—O1—C20	−2.2 (7)	C4—C3—C6—C7	−177.6 (4)
C1—C2—O1—C20	177.5 (4)	C8—C3—C6—C7	2.3 (7)
O2—C1—C4—C3	178.3 (4)	C2—C5—C6—C3	−0.7 (7)
C2—C1—C4—C3	−0.8 (7)	C2—C5—C6—C7	179.6 (4)
C6—C3—C4—C1	−1.9 (7)	Br1—C7—C6—C3	96.8 (5)
C8—C3—C4—C1	178.1 (4)	Br1—C7—C6—C5	−83.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱ	0.99	2.48	3.373 (6)	150
C10—H10C···O2ⁱⁱ	0.98	2.48	3.392 (7)	155

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂Br₂O₂
M_r	324.00
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	153
a, b, c (Å)	8.125 (6), 14.689 (10), 20.353 (13)
V (Å³)	2429 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.65
Crystal size (mm)	0.15 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.456, 0.516
No. of measured, independent and observed [I > 2σ(I)] reflections	12237, 2475, 1643
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.117, 1.02
No. of reflections	2475
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.72

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Br1—C7	1.983 (5)	C2—C5	1.394 (6)
Br2—C8	2.002 (5)	C3—C6	1.399 (6)
C1—C4	1.365 (6)	C3—C4	1.413 (6)
C1—O2	1.372 (5)	C3—C8	1.490 (7)
C1—C2	1.428 (6)	O1—C20	1.422 (6)
O2—C10	1.442 (6)	C5—C6	1.405 (6)
C2—O1	1.368 (5)	C7—C6	1.510 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱ	0.99	2.48	3.373 (6)	150.2
C10—H10C···O2ⁱⁱ	0.98	2.48	3.392 (7)	155.2

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, y, −z+1/2.

Acknowledgements

The author is grateful to the Sciences Foundation of Shandong Provincial Education Department (No. J06D61) as well as the Doctoral Science Foundation of Zaozhuang University.

References

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