Methyl 2-{N-[2-(2,4-dichloro­phen­oxy)acet­yl]-4-[(4,6-dimeth­oxy­pyrimidin-2-yl)­oxy]anilino}propano­ate

Lihong Ning; Hao Peng; Hongwu He

doi:10.1107/S1600536812025494

. 2012 Jun 13;68(Pt 7):o2046. doi: 10.1107/S1600536812025494

Methyl 2-{N-[2-(2,4-dichlorophenoxy)acetyl]-4-[(4,6-dimethoxypyrimidin-2-yl)oxy]anilino}propanoate

Lihong Ning ^a, Hao Peng ^a, Hongwu He ^a,^*

PMCID: PMC3393314 PMID: 22807871

Abstract

In the title molecule, C₂₄H₂₃Cl₂N₃O₇, the central benzene ring forms dihedral angles of 65.71 (1) and 44.42 (1)° with the pyrimidine ring and the terminal benzene ring, respectively. In the crystal, molecules are linked via C—H⋯O hydrogen bonds.

Related literature

For reference bond-length data, see: Allen et al. (1987 ▶). For the synthesis of 4-(4,6-dimethoxypyrimidin-2-yloxy)benzenamine, see: Jin et al. (2011 ▶). For biological properties of fungicides, see: Gozzo & Garlaschelli (1985 ▶).

Experimental

Crystal data

C₂₄H₂₃Cl₂N₃O₇
M _r = 536.35
Triclinic,
a = 8.2438 (9) Å
b = 11.2405 (12) Å
c = 14.2502 (15) Å
α = 85.178 (2)°
β = 78.702 (2)°
γ = 80.032 (2)°
V = 1273.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
15581 measured reflections
6204 independent reflections
4390 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.174
S = 1.06
6204 reflections
329 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812025494/wn2477sup1.cif

e-68-o2046-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025494/wn2477Isup2.hkl

e-68-o2046-Isup2.hkl^{(303.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812025494/wn2477Isup3.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
C9—H9⋯O4ⁱ	0.93	2.57	3.402 (3)	150

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support of this work by the National Basic Research Program of China (2010CB126100) and the National Natural Science Foundation of China (Nos. 21172090 and 21002037). The research was supported in part by the PCSIRT (No. IRT0953) and the self-determined research funds of CCNU from the college’s basic research and operation of MOE (No. CCNU10A01007).

supplementary crystallographic information

Comment

N-acylalanine fungicides are mainly used in crop protection because of their systemic properties, with both curative and protective activity against fungal pathogens of the Peronosporales (Gozzo & Garlaschelli, 1985). The pyrimidinyl group is widely used in fungicides and drug molecular design (Jin et al., 2011), so we have introduced the pyrimidinyl group into acylalanine derivatives in order to decrease resistance and increase activity.

Here we report the crystal structure of the title compound (Fig.1). The bond lengths (Allen et al., 1987) and angles show normal values. The central benzene ring forms dihedral angles of 65.71 (1)° and 44.42 (1)° with the pyrimidinyl ring and the terminal benzene ring, respectively. The C9—H9···O4 intermolecular hydrogen bond plays an important role in determining the crystal structure.

Experimental

4-(4,6-Dimethoxypyrimidin-2-yloxy)benzenamine (Jin et al., 2011) (1 mmol) and methyl 2-chloropropanoate (1.2 mmol) were dissolved in 15 ml dimethylformamide, then 1 mmol K₂CO₃ was added with constant stirring. The temperature was maintained at 100 °C for 10 h. The reaction mixture was poured into water and extracted with ethyl acetate, dried with Na₂SO₄, then purified by column chromatography on silica gel with petroleum ether/ethyl acetate (4:1) to give the compound methyl 2-(N-(4-(4,6-dimethoxypyrimidin-2-yloxy)phenyl)amino)propanoate.

To a mixture of methyl 2-(N-(4-(4,6-dimethoxypyrimidin-2-yloxy) phenyl)amino)propanoate (2 mmol) and triethylamine (2 mmol) in CH₂Cl₂ (20 ml), 2,4-dichlorophenoxyacetyl chloride (2 mmol) was added at 2–5 °C and the mixture was stirred for another 3 h, then washed with saturated sodium hydrogen carbonate solution and dried with Na₂SO₄. The residue was purified by column chromatography on silica gel with petroleum ether/ethyl acetate (3:1) to give the pure title compound as a white solid. Recrystallization from ethanol over a period of one week gave colourless crystals of the title compound.