2-(2,4,6-Trichloro­phen­oxy)ethyl bromide

Yao, J.; Yang, W.; Zhao, X.; Shen, L.; Hu, Y.

doi:10.1107/S1600536809043256

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2850

https://doi.org/10.1107/S1600536809043256

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2-(2,4,6-Trichlorophenoxy)ethyl bromide

Jin-feng Yao,^a Wen-ge Yang,^a ^* Xiao-lei Zhao,^a Lei Shen ^a and Yong-hong Hu ^b

^aState Key Laboratory of Materials-Oriented Chemical Engineering, School of Pharmaceutical Sciences, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: chemywg@126.com

(Received 8 October 2009; accepted 20 October 2009; online 28 October 2009)

In the title compound, C₈H₆BrCl₃O, there is a weak intramolecular C—H⋯Cl hydrogen bond involving the O bound methylene group. Intermolecular Cl⋯Cl contacts [3.482 (2) Å] are present in the crystal structure.

Related literature

The title compound is used as an intermediate in the production of Prochloraz, a broad-spectrum imidazole fungicide widely used in gardening and agriculture. For the fungicidal properties of Prochloraz, see: Copping et al. (1984 ). For the preparation, see: Howard & Alfred (1982 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₆BrCl₃O
M_r = 304.39
Triclinic, $[P \overline 1]$
a = 4.0550 (8) Å
b = 8.6270 (17) Å
c = 15.183 (3) Å
α = 90.73 (3)°
β = 94.81 (3)°
γ = 90.42 (3)°
V = 529.21 (18) Å³
Z = 2
Mo Kα radiation
μ = 4.60 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.460, T_max = 0.656
2215 measured reflections
1919 independent reflections
1280 reflections with I > 2σ(I)
R_int = 0.041
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.01
1919 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.37 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
C2—H2A⋯Cl3	0.97	2.81	3.276 (6)	110

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809043256/pv2217sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043256/pv2217Isup2.hkl

checkCIF report

Comment top

Prochloraz, N-propyl-N-[2-(2,4,6-trichlorophenoxy)-ethyl] -1H-imidazole-1-carboxamide, is a broad-spectrum imidazole fungicide (Copping et al., 1984). As part of our studies in the synthesis of Prochloraz, the title compound (I), which is used as the key intermediate, has been synthesized. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). In the crystal structure, intramolecular C—H···Cl interactions (Table 1) may be effective in the stabilization of the structure.

Related literature top

The title compound is used as an intermediate in the production of Prochloraz, a broad-spectrum imidazole fungicide widely used in gardening and agriculture. For the fungicidal properties of Prochloraz, see: Copping et al. (1984). For the preparation, see: Howard & Alfred (1982). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by following a reported procedure (Howard & Alfred, 1982). 2,4,6-Trichlorophenol (15.8 g ) and sodium hydroxide (4.8 g) were dissolved in 28 ml water and added dropwise to an excess of ethylene dibromide (75.6 g). The reaction mixture was heated under reflux for ten hours. The residue was extracted with 3 x 20 ml dichlormethane, and then methylene chloride phase was washed with water, dried and evaporated to dryness under reduced pressure. Fractionation under reduced pressure yielded the title compound as a colorless oil whaich was then cooled to give 18.1 g white solid (75.2%). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution of (I).

Structure description top

The title compound is used as an intermediate in the production of Prochloraz, a broad-spectrum imidazole fungicide widely used in gardening and agriculture. For the fungicidal properties of Prochloraz, see: Copping et al. (1984). For the preparation, see: Howard & Alfred (1982). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability levels.
	Fig. 2. A packing diagram of the title compound. Intramolecular hydron bonds are shown as dashed lines.

2-(2,4,6-Trichlorophenoxy)ethyl bromide top

Crystal data top

C₈H₆BrCl₃O	Z = 2
M_r = 304.39	F(000) = 296
Triclinic, P1	D_x = 1.910 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.0550 (8) Å	Cell parameters from 25 reflections
b = 8.6270 (17) Å	θ = 10–14°
c = 15.183 (3) Å	µ = 4.60 mm⁻¹
α = 90.73 (3)°	T = 293 K
β = 94.81 (3)°	Block, colorless
γ = 90.42 (3)°	0.20 × 0.10 × 0.10 mm
V = 529.21 (18) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1280 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 25.3°, θ_min = 1.4°
ω/2θ scans	h = 0→4
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
T_min = 0.460, T_max = 0.656	l = −18→18
2215 measured reflections	3 standard reflections every 200 reflections
1919 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.066P)²] where P = (F_o² + 2F_c²)/3
1919 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₈H₆BrCl₃O	γ = 90.42 (3)°
M_r = 304.39	V = 529.21 (18) Å³
Triclinic, P1	Z = 2
a = 4.0550 (8) Å	Mo Kα radiation
b = 8.6270 (17) Å	µ = 4.60 mm⁻¹
c = 15.183 (3) Å	T = 293 K
α = 90.73 (3)°	0.20 × 0.10 × 0.10 mm
β = 94.81 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1280 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.041
T_min = 0.460, T_max = 0.656	3 standard reflections every 200 reflections
2215 measured reflections	intensity decay: 1%
1919 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.01	Δρ_max = 0.37 e Å⁻³
1919 reflections	Δρ_min = −0.42 e Å⁻³
118 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
Br	0.06298 (16)	0.24181 (8)	−0.05453 (4)	0.0696 (3)
O	0.6382 (9)	0.3089 (4)	0.1806 (2)	0.0537 (9)
Cl1	0.6363 (4)	−0.01264 (17)	0.24134 (11)	0.0689 (5)
Cl2	0.1372 (4)	0.22953 (19)	0.52835 (10)	0.0707 (5)
Cl3	0.4167 (5)	0.59982 (17)	0.26392 (11)	0.0777 (5)
C1	0.3028 (15)	0.1966 (7)	0.0606 (4)	0.0651 (16)
H1A	0.1585	0.1417	0.0977	0.078*
H1B	0.4922	0.1318	0.0521	0.078*
C2	0.4125 (15)	0.3430 (7)	0.1030 (4)	0.0609 (15)
H2A	0.2235	0.4002	0.1208	0.073*
H2B	0.5249	0.4058	0.0620	0.073*
C3	0.5043 (12)	0.2915 (6)	0.2586 (3)	0.0436 (12)
C4	0.4945 (12)	0.1458 (6)	0.2977 (4)	0.0467 (13)
C5	0.3811 (13)	0.1253 (6)	0.3795 (3)	0.0486 (13)
H5A	0.3760	0.0273	0.4042	0.058*
C6	0.2752 (13)	0.2530 (6)	0.4241 (3)	0.0476 (13)
C7	0.2808 (13)	0.3971 (6)	0.3887 (4)	0.0506 (14)
H7A	0.2071	0.4822	0.4195	0.061*
C8	0.3966 (13)	0.4152 (6)	0.3068 (4)	0.0482 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0586 (4)	0.0971 (5)	0.0522 (4)	0.0021 (3)	0.0018 (3)	−0.0099 (3)
O	0.045 (2)	0.070 (2)	0.046 (2)	0.0014 (18)	0.0040 (19)	0.0043 (18)
Cl1	0.0775 (11)	0.0580 (9)	0.0722 (10)	0.0176 (8)	0.0128 (9)	−0.0101 (7)
Cl2	0.0801 (11)	0.0855 (11)	0.0482 (9)	0.0115 (9)	0.0131 (8)	0.0051 (8)
Cl3	0.1140 (14)	0.0486 (8)	0.0695 (11)	−0.0029 (9)	0.0020 (10)	0.0059 (7)
C1	0.053 (4)	0.069 (4)	0.075 (4)	−0.002 (3)	0.018 (3)	0.002 (3)
C2	0.062 (4)	0.058 (3)	0.064 (4)	−0.001 (3)	0.016 (3)	0.004 (3)
C3	0.033 (3)	0.052 (3)	0.045 (3)	0.001 (2)	−0.001 (2)	−0.003 (2)
C4	0.044 (3)	0.045 (3)	0.051 (3)	0.008 (2)	−0.001 (3)	−0.007 (2)
C5	0.049 (3)	0.046 (3)	0.051 (3)	0.004 (2)	0.003 (3)	0.003 (3)
C6	0.041 (3)	0.059 (3)	0.042 (3)	0.005 (3)	−0.005 (2)	−0.001 (3)
C7	0.052 (3)	0.050 (3)	0.050 (3)	0.009 (3)	−0.002 (3)	−0.004 (3)
C8	0.048 (3)	0.041 (3)	0.054 (3)	0.001 (2)	−0.003 (3)	0.001 (2)

Geometric parameters (Å, º) top

Br—C1	1.973 (6)	C2—H2B	0.9700
O—C3	1.353 (6)	C3—C8	1.380 (7)
O—C2	1.464 (7)	C3—C4	1.398 (7)
Cl1—C4	1.731 (5)	C4—C5	1.373 (7)
Cl2—C6	1.737 (5)	C5—C6	1.376 (7)
Cl3—C8	1.733 (5)	C5—H5A	0.9300
C1—C2	1.459 (8)	C6—C7	1.361 (7)
C1—H1A	0.9700	C7—C8	1.375 (8)
C1—H1B	0.9700	C7—H7A	0.9300
C2—H2A	0.9700

C3—O—C2	117.4 (4)	C5—C4—C3	122.1 (5)
C2—C1—Br	108.5 (4)	C5—C4—Cl1	119.2 (4)
C2—C1—H1A	110.0	C3—C4—Cl1	118.6 (4)
Br—C1—H1A	110.0	C4—C5—C6	118.5 (5)
C2—C1—H1B	110.0	C4—C5—H5A	120.8
Br—C1—H1B	110.0	C6—C5—H5A	120.8
H1A—C1—H1B	108.4	C7—C6—C5	121.4 (5)
C1—C2—O	108.5 (5)	C7—C6—Cl2	119.5 (4)
C1—C2—H2A	110.0	C5—C6—Cl2	119.1 (4)
O—C2—H2A	110.0	C6—C7—C8	119.2 (5)
C1—C2—H2B	110.0	C6—C7—H7A	120.4
O—C2—H2B	110.0	C8—C7—H7A	120.4
H2A—C2—H2B	108.4	C7—C8—C3	122.1 (5)
O—C3—C8	122.7 (5)	C7—C8—Cl3	118.9 (4)
O—C3—C4	120.4 (4)	C3—C8—Cl3	118.9 (4)
C8—C3—C4	116.7 (5)

Br—C1—C2—O	−170.3 (3)	C4—C5—C6—C7	0.1 (8)
C3—O—C2—C1	−90.6 (6)	C4—C5—C6—Cl2	−179.0 (4)
C2—O—C3—C8	−75.1 (6)	C5—C6—C7—C8	−0.4 (8)
C2—O—C3—C4	110.3 (5)	Cl2—C6—C7—C8	178.7 (4)
O—C3—C4—C5	175.5 (5)	C6—C7—C8—C3	0.8 (8)
C8—C3—C4—C5	0.6 (7)	C6—C7—C8—Cl3	−177.7 (4)
O—C3—C4—Cl1	−3.4 (6)	O—C3—C8—C7	−175.7 (5)
C8—C3—C4—Cl1	−178.4 (4)	C4—C3—C8—C7	−0.9 (8)
C3—C4—C5—C6	−0.2 (8)	O—C3—C8—Cl3	2.8 (7)
Cl1—C4—C5—C6	178.8 (4)	C4—C3—C8—Cl3	177.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl3	0.97	2.81	3.276 (6)	110

Experimental details

Crystal data
Chemical formula	C₈H₆BrCl₃O
M_r	304.39
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.0550 (8), 8.6270 (17), 15.183 (3)
α, β, γ (°)	90.73 (3), 94.81 (3), 90.42 (3)
V (Å³)	529.21 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.60
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.460, 0.656
No. of measured, independent and observed [I > 2σ(I)] reflections	2215, 1919, 1280
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.01
No. of reflections	1919
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.42

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl3	0.97	2.81	3.276 (6)	110

Acknowledgements

This research work was financially supported by the Department of Science and Technology of Jiangsu Province (BE200830457) and the `863' project (2007 A A02Z211) of the Ministry of Science and Technology.

References

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