Methyl 3,5-dibromo-2-diacetyl­amino­benzoate

Jerry P Jasinski; James A Golen; A S Praveen; H S Yathirajan; B Narayana

doi:10.1107/S1600536811034568

. 2011 Aug 27;67(Pt 9):o2503. doi: 10.1107/S1600536811034568

Methyl 3,5-dibromo-2-diacetylaminobenzoate

Jerry P Jasinski ^a,^*, James A Golen ^a, A S Praveen ^b, H S Yathirajan ^b, B Narayana ^c

PMCID: PMC3200936 PMID: 22059049

Abstract

The title methyl benzoate compound, C₁₂H₁₁Br₂NO₄, consists of an ortho-substituted diacetylamino group and meta-substituted Br atoms. The crystal packing is stabilized by weak intermolecular C—H⋯O interactions.

Related literature

For the use of halogenated benzoates to stimulate the microbial dechlorination of polychlorinated biphenyls, see: Deweerd & Bedard (1999 ▶). For related structures, see: Gowda et al. (2008 ▶); Saeed et al. (2010 ▶); Yathirajan et al. (2007 ▶). For bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₁Br₂NO₄
M _r = 393.04
Triclinic,
a = 7.6386 (8) Å
b = 8.8870 (6) Å
c = 10.8691 (8) Å
α = 78.186 (6)°
β = 76.155 (7)°
γ = 82.750 (7)°
V = 698.91 (10) Å³
Z = 2
Mo Kα radiation
μ = 5.81 mm⁻¹
T = 173 K
0.24 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.336, T _max = 0.421
5598 measured reflections
2864 independent reflections
2186 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.070
S = 1.00
2864 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034568/dn2715sup1.cif

e-67-o2503-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034568/dn2715Isup2.hkl

e-67-o2503-Isup2.hkl^{(140.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811034568/dn2715Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱ	0.98	2.44	3.404 (4)	168
C6—H6A⋯O4ⁱⁱ	0.95	2.46	3.237 (4)	140

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

ASP thanks University of Mysore and R. L. Fine Chem, Bangalore for access to their research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

The title compound, (I), was obtained as an unexpected product in the present synthetic reaction (Fig. 1). Benzoates have wide importance in the plastics, food and pharmaceutical industries. The use of halogenated benzoates to stimulate the microbial dechlorination of poly chlorinated biphenyls is discussed (Deweerd & Bedard, 1999). The crystal structures of 4-bromophenyl benzoate (Gowda et al., 2008), methyl 4-(bromomethyl)benzoate (Yathirajan et al., 2007) and methyl 3,5-dibromo-4-methylbenzoate (Saeed et al., 2010) have been reported. In view of the importance of benzoates, the crystal structure of title compound, (I), C₁₂H₁₁Br₂NO₄, is reported.

The title methyl benzoate compound, (I), consists of an ortho substituted N, N diacetyl group and meta substituted dibromine atoms (Fig. 2). Crystal packing is stabilized by weak C—H···O intermolecular interactions (Table 1).

Experimental

Preparation of 2-amino-3, 5-dibromobenzoic acid: A mixture of 2-aminobenzoic acid (25 g, 0.1822 mol) in acetic acid (50 mL) was cooled at 273 –278 K. A mixture of bromine (32.79 g, 10.5 mL, 0.1822 mol) in acetic acid (1:1 by Vol.) was added drop wise over 30 min. After addition, the mixture was stirred at 273-278 K for one hour and at room temperature for 3-4 hours. To the mixture, water (100ml) was added at 288-293 K. The solid was filtered, washed with water (50 mL x 2), and dried at 353 K for 5 hrs (Yield - 93 %).

Preparation of methyl 2-(N-acetylacetamido)-3,5-dibromobenzoate: In a 500 mL round bottomed flask, acetic anhydride (150 mL) warmed at 353 K, 2-amino-3,5-dibromobenzoic acid ( 50 g, 0.1695 mol) was added over 30 minutes. The mixture was refluxed at 411-413 K and maintained for 4 hrs, cooled to room temperature and filtered.

The crystallization was done using methanol. The title compound was obtained as an unexpected product as shown in Scheme 1. X-ray quality crystals were obtained by a slow evaporation from methanol solution (m.p.: 380-383 K).