Methyl 5-bromo-2-[meth­yl(methyl­sulfon­yl)amino]benzoate

Muhammad Shafiq; M Nawaz Tahir; Islam Ullah Khan; Muhammad Nadeem Arshad; Muneeb Hayat Khan

doi:10.1107/S1600536809011829

. 2009 Apr 2;65(Pt 5):o955. doi: 10.1107/S1600536809011829

Methyl 5-bromo-2-[methyl(methylsulfonyl)amino]benzoate

Muhammad Shafiq ^a, M Nawaz Tahir ^b,^*, Islam Ullah Khan ^a, Muhammad Nadeem Arshad ^a, Muneeb Hayat Khan ^a

PMCID: PMC2977655 PMID: 21583998

Abstract

The title compound, C₁₀H₁₂BrNO₄S, is an intermediate in the synthesis of benzothiazine. The planar methyl ester group (maximum deviation is 0.0065 Å) is oriented at a dihedral angle of 39.09 (13)° with respect to the aromatic ring. In the crystal structure, weak intermolecular C—H⋯O interactions link the molecules into centrosymmetric dimers, through R ₂ ²(10) ring motifs.

Related literature

For related structures, see: Arshad et al. (2008 ▶); Shafiq et al. (2009 ▶); Tahir et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring-motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₂BrNO₄S
M _r = 322.18
Monoclinic,
a = 6.0798 (1) Å
b = 10.7853 (3) Å
c = 19.5206 (4) Å
β = 90.306 (1)°
V = 1280.00 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.38 mm⁻¹
T = 296 K
0.28 × 0.10 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.675, T _max = 0.766
13682 measured reflections
3170 independent reflections
2215 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.084
S = 1.04
3170 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011829/hk2657sup1.cif

e-65-0o955-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011829/hk2657Isup2.hkl

e-65-0o955-Isup2.hkl^{(152.4KB, hkl)}

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
C6—H6⋯O2ⁱ	0.93	2.43	3.319 (3)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

MS gratefully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him with a Scholaship under the Indigenous PhD Program (PIN 042–120567-PS2–276).

supplementary crystallographic information

Comment

We have reported the crystal structures of some benzothiazine derivatives (Shafiq et al., 2009; Tahir et al., 2008; Arshad et al., 2008). The title compound is an intermediate for the synthesis of benzothiazine and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is of course planar. The methyl ester moiety B (O2/C7/O1/C8) is also planar, and they are oriented at a dihedral angle of 39.09 (13)°.

In the crystal structure, weak intermolecular C-H···O interactions link the molecules into centrosymmetric dimers through R₂²(10) ring motifs (Fig. 2) (Bernstein et al., 1995).

Experimental

For the preparation of the title compound, methyl-2-amino-5-bromobenzoate (1 g, 4 mmol) was added into dichloromethane (10 ml) in a round bottom flask. Then, a solution of methanesulfonyl chloride (0.55 g, 48 mmol) in dichloromethane (10 ml) was added to the mixture in 10-15 min. The mixture was stirred at 333-343 K for 2-3 d. After the completion of reaction, the solvent was evaporated under reduced pressure to get methyl-5-bromo-2-[(methylsulfonyl)amino]benzoate. Methyl-5-bromo-2-[(methylsulfonyl)amino] benzoate (1 g, 33 mmol) was added into dimethylformamide (5 ml), and then to a suspension of NaH (0.15 g, 66 mmol) in dimethylformamide (10 ml). The mixture was stirred at room temperature for 14-16 h, then the title compound was obtained.