Methyl 4-(butyrylamino)-5-methyl-2-nitro­benzoate

Lian-shan Yuan; Xiang Li; Cheng Yao

doi:10.1107/S1600536808005576

. 2008 Mar 29;64(Pt 4):o742. doi: 10.1107/S1600536808005576

Methyl 4-(butyrylamino)-5-methyl-2-nitrobenzoate

Lian-shan Yuan ^a,^*, Xiang Li ^a, Cheng Yao ^a

PMCID: PMC2960971 PMID: 21202132

Abstract

The title compound, C₁₃H₁₆N₂O₅, is useful as an intermediate in the field of agrochemicals. Intramolecular C—H⋯O hydrogen bonds result in the formation of one six- and one five-membered nearly planar ring; the six-membered ring is also nearly coplanar with the adjacent benzene ring. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules.

Related literature

For related literature, see: Ries et al. (1993 ▶); Engeli et al. (2000 ▶); Kintscher et al. (2004 ▶); Goossens et al. (2003 ▶); Boustany et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₃H₁₆N₂O₅
M _r = 280.28
Triclinic,
a = 7.6370 (15) Å
b = 8.7880 (18) Å
c = 11.329 (2) Å
α = 81.06 (3)°
β = 78.48 (3)°
γ = 68.39 (3)°
V = 689.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.959, T _max = 0.980
2919 measured reflections
2704 independent reflections
1650 reflections with I > 2σ(I)
R _int = 0.032
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.161
S = 1.01
2704 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005576/hk2408sup1.cif

e-64-0o742-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005576/hk2408Isup2.hkl

e-64-0o742-Isup2.hkl^{(132.7KB, 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—H6A⋯O1	0.93	2.20	2.809 (3)	122
C9—H9A⋯O4	0.93	2.41	2.734 (3)	100
C13—H13A⋯O1ⁱ	0.96	2.33	3.284 (4)	174

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound, (I), is useful as an intermediate and agrochemicals. It is important as an intermediate for the preparation of telmisartan (Ries et al., 1993), that can be used as a therapeutic tool for metabolic syndrome, including visceral obesity (Engeli et al., 2000; Kintscher et al., 2004; Goossens et al., 2003; Boustany et al., 2004). As part of our ongoing studies in this area, we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···O hydrogen bonds (Table 1) result in the formations of one six- and one five-membered nearly planar rings; B (N1/O1/C4—C6/H6A) and C (O4/C8/C9/C12/H9A). Ring A (C5—C10) is, of course, planar and the dihedral angles between them are A/B = 2.01 (3)°, A/C = 6.76 (3)° and B/C = 8.73 (2)°. So, rings A and B are also nearly co-planar.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, methyl 4-amino-3-methylbenzoate (8.25 g, 50 mmol) was acylated with butyryl chloride (50 mmol, 5.3 ml) in chlorobenzene at 373 K. The resulting amide was reacted with fuming nitric acid in sulfuric acid (60%) at 273 K. The reaction mixture was poured into ice-water. The residue was filtered and recrystallized from methylene chloride to give the title compound, (I), (yield; 10.8 g, 77%). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.