Methyl 2-(N-ethyl­methane­sulfonamido)benzoate

Muhammad Shafiq; M Nawaz Tahir; Islam Ullah Khan; Waseeq Ahmad Siddiqui; Muhammad Nadeem Arshad

doi:10.1107/S160053680800007X

. 2008 Jan 9;64(Pt 2):o389. doi: 10.1107/S160053680800007X

Methyl 2-(N-ethylmethanesulfonamido)benzoate

Muhammad Shafiq ^a, M Nawaz Tahir ^b, Islam Ullah Khan ^a, Waseeq Ahmad Siddiqui ^a, Muhammad Nadeem Arshad ^a,^*

PMCID: PMC2960301 PMID: 21201419

Abstract

In the molecule of the title compound, C₁₁H₁₅NO₄S, the S atom environment is distorted tetrahedral. The methoxycarbonyl group is oriented at a dihedral angle of 11.8 (2)° with respect to the benzene ring. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For general background, see: Reissenweber & Mangold (1982 ▶); Mookherjee et al. (1989 ▶); Tadashi et al. (1982 ▶). For related literature, see: Siddiqui et al. (2006 ▶,2007a ▶,b ▶); Lombardino (1972 ▶); Hanson & Hitchcook (2004 ▶).

Experimental

Crystal data

C₁₁H₁₅NO₄S
M _r = 257.30
Triclinic,
a = 8.0161 (4) Å
b = 8.4386 (4) Å
c = 10.5329 (5) Å
α = 85.244 (3)°
β = 78.721 (3)°
γ = 62.650 (3)°
V = 620.61 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 (2) K
0.25 × 0.18 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005) T _min = 0.935, T _max = 0.958
11895 measured reflections
3012 independent reflections
1817 reflections with I > 3σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.123
S = 1.00
3012 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 ▶); 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, 2003 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800007X/hk2412sup1.cif

e-64-0o389-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800007X/hk2412Isup2.hkl

e-64-0o389-Isup2.hkl^{(144.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

S1—O1	1.421 (2)
S1—O2	1.4303 (19)
S1—N1	1.6269 (18)
S1—C9	1.747 (2)

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O1—S1—O2	119.88 (12)
O1—S1—N1	107.29 (11)
O2—S1—N1	107.34 (11)
O1—S1—C9	108.32 (13)
O2—S1—C9	106.53 (13)
N1—S1—C9	106.83 (11)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O1ⁱ	0.96	2.50	3.372 (5)	151
C7—H7B⋯O3	0.97	2.57	3.044 (4)	110
C9—H9C⋯O3	0.96	2.59	3.152 (4)	117

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer and for technical support, respectively.

supplementary crystallographic information

Comment

Alkyl anthranilates are valuable starting materials for the preparation of pesticides, dyes and drugs (Reissenweber & Mangold, 1982). They find organoleptic uses in augmenting the aroma or taste of perfume compositions, colognes, perfumed articles, foodstuffs, medicinal products and in enhancing the effects of deodorancy (Mookherjee et al., 1989). Particularly, the N-substituted thioesters of anthranilic acid have been found potent inhibitors of the serine proteases human leukocyte (HL) elastase, porcine pancreatic elastase, cathepsin G, and bovine chymotrypsin A_α (Tadashi et al., 1982). In continuation of our research program to synthesize new biologically important 1,2-benzothiazine 1,1-dioxide molecules (Siddiqui et al., 2006; Siddiqui et al., 2007a,b), we embarked on the syntheses of 2,1-benzothiazine 2,2-dioxide, as well. Contrary to the N-methyl substituent (Lombardino, 1972), the N-ethyl derivative is being reported for the first time.

The title compound, (I), is an important precursor for the synthesis of 2,1-benzothiazine 2,2-dioxide molecule. The structure determination of (I) is undertaken in order to understand the conformational geometry around the sulfur and nitrogen atoms, due to the addition of ethyl group.

In the molecule of (I), (Fig. 1) S1 atom adopts a distorted tetrahedral coordination geometry with two O, one N and one C atoms of methylsulfonyl amino group (Table 1). The sulfur bonds are shortened, while the bond angles aroud it are different with respect to the corresponding values reported in methyl anthranilate N-methanesulfonamide, (II), (Hanson & Hitchcook, 2004).

In (I), the addition of ethyl group at N1, instead of H-atom in (II), has changed the orientation of CH₃ group and O4 atom as compared with (II). On the other hand, the O3—C10 [1.193 (3) Å] and O4—C10 [1.328 (3) Å] bonds in (I), are reported as 1.2202 (16) Å and 1.3324 (16) Å, respectively, in (II). The methyl carboxylate group (O3/O4/C10/C11) is oriented at a dihedral angle of 11.8 (2)° with respect to the phenyl ring (C1—C6).

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, the suspension of hexane-washed sodium hydride (50% in mineral oil) was prepared in dry dimethylformamide (3 ml). A solution of methyl N-methylsulfonylanthranilate (70 mg, 0.306 mmol) in dry dimethylformamide (5 ml) was added to the suspension (76 mg, 0.368 mmol), and stirred for 45 min at room temperature. Then, a solution of ethyl iodide (144 mg, 0.92 mmol) in ether (5 ml) was added to it. The resulting white suspension was stirred for 1.5 h and poured into hydrochloric acid (3 N, 50 ml) to produce a yellow suspension which was extracted with chloroform (4 × 25 ml). The combined extract was dried over calcium sulfate and evaporated under reduced pressure (11 torr) to get the title compound (yield; 58 mg, 73%, m.p. 330–331 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of CHCl₃.