2-(1-Methyl­ethoxy)-5-nitro­phenyl N-methyl­carbamate

Guang-Ming Sang; Shi-Neng Luo; Jian-Guo Lin; Hai-Lin Yang; Yong-Mei Xia

doi:10.1107/S1600536808040622

. 2008 Dec 10;65(Pt 1):o47. doi: 10.1107/S1600536808040622

2-(1-Methylethoxy)-5-nitrophenyl N-methylcarbamate

Guang-Ming Sang ^a, Shi-Neng Luo ^b,^*, Jian-Guo Lin ^b, Hai-Lin Yang ^c, Yong-Mei Xia ^a

PMCID: PMC2967962 PMID: 21581688

Abstract

In the title compound, C₁₁H₁₄N₂O₅, the nitro group is approximately coplanar with the benzene ring, making a dihedral angle of 4.26 (17)°. The dihedral angle between the methylcarbamate group and the benzene ring is 72.47 (6)°. There is a strong intermolecular N—H⋯O hydrogen bond between the N and O atoms from adjacent methylcarbamate groups, forming a one-dimensional network along the a axis.

Related literature

For general background, see: Wang et al. (1998 ▶); Moreno et al. (2001 ▶). For related structures, see: Czugler & Kalman (1975 ▶); Xu et al. (2005 ▶). For the synthesis, see: Allan et al. (1926 ▶).

Experimental

Crystal data

C₁₁H₁₄N₂O₅
M _r = 254.24
Triclinic,
a = 5.034 (2) Å
b = 10.4221 (16) Å
c = 12.6319 (12) Å
α = 91.361 (3)°
β = 97.492 (2)°
γ = 94.6930 (10)°
V = 654.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 291 (2) K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.97, T _max = 0.98
7186 measured reflections
3172 independent reflections
2005 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.105
S = 1.03
3172 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040622/fj2175sup1.cif

e-65-00o47-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040622/fj2175Isup2.hkl

e-65-00o47-Isup2.hkl^{(155.6KB, 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
N2—H2A⋯O5ⁱ	0.86	2.05	2.788 (2)	143

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Wu Jieping Medical Foundation (32067500615) and National "863" Project of China (No. 2006AA10Z449)

supplementary crystallographic information

Comment

2-(1-Methylethoxy)phenyl methylcarbamate (Trade name: Propoxur) is an important economical insecticide. It is widely used to control agricultural and household insect pests due to its low toxicity to mammals and other vertebrates (Wang et al., 1998; Moreno et al., 2001). Immunoassay is one of effective analytical methods of determining the residua of the methylcarbamate pesticide propoxur. Propoxur, like most pesticides, is a small and simple organic molecule, which lacks a functional group (amido or carboxylic acid) for coupling to proteins and is non immunogenic by itself. Therefore, it is necessary to synthesis hapten resembling as much as possible the structural and electronic distribution of propoxur for the production of highaffinity antibodies (Moreno et al., 2001). With this idea in mind, we intend to synthesis 5-amino-2-(1-methylethoxy)phenyl methylcarbamate. As a vital intermediate compound for the stepwise reactions of hapten synthesis, the synthesis and crystal structure of the title compound has been reported herein.

In the title compound (I) (Fig. 1), C₁₁H₁₄N₂O₅, the nitro group is approximately coplanar with the phenyl ring [dihedral angle = 4.26 (17)°]. All the nonhydrogen atoms in the methylcarbamate group are almost in a plane, and the dihedral angle between methylcarbamate group and phenyl is 72.47 (6)°. There is a strong N—H···O intermolecular hydrogen bond between the N2 atom and O5 atom from adjacent methylcarbamate groups (Table 1). And the crystal structure is stabilized by these strong hydrogen bond interactions to form one-dimensional supramolecular network along a axis (Table 1 and Fig. 2).

Experimental

The title compound (I) was synthesized as follows (Allan et al., 1926): Nitric acid (25 ml, d 1.42, 0.6 mol) was added to a solution of 2-(1-methylethoxy)-phenyl methylcarbamate (20.9 g, 0.1 mol) in acetic acid (30 ml), and the mixture was heated on the oil-bath until the onset of a vigorous reaction was manifested by the copious evolution of red fumes and temperature rising to around 100 °C. Then, the reaction mixture was heated on this condition for 3 h, poured into cool water, and stirred for 30 min. After filtering, washing with water and drying in vacuum, a white powder was then obtained (yield: 75%). mp 120–121 °C. The title compound was recrystallized from ethanol solvent; colourless block-shaped crystals were formed after several days (yield 58%). Analysis calculated for C₁₁H₁₄N₂O₅: C 51.97, H 5.55, N 11.02%; found: C 51.92, H 5.49, N 11.08%.