Methyl 2-amino-4-(3-chloro­prop­oxy)-5-methoxy­benzoate

Min Zhang; Ran-zhe Lu; Lu-na Han; Wen-bin Wei; Hai-bo Wang

doi:10.1107/S1600536809011374

. 2009 Apr 2;65(Pt 5):o942. doi: 10.1107/S1600536809011374

Methyl 2-amino-4-(3-chloropropoxy)-5-methoxybenzoate

Min Zhang ^a,^b, Ran-zhe Lu ^a,^b, Lu-na Han ^a,^b, Wen-bin Wei ^a,^b, Hai-bo Wang ^a,^*

PMCID: PMC2977643 PMID: 21583986

Abstract

The asymmetric unit of the title compound, C₁₂H₁₆ClNO₄, contains two crystallographically independent molecules. The benzene rings of the two independent molecules are oriented at a dihedral angle of 88.50 (3)°. Intramolecular N—H⋯O hydrogen bonds involving the methoxybenzoate carbonyl group in each molecule result in the formation of two planar, six-membered rings, oriented at dihedral angles of 1.39 (3) and 0.68 (3)° with respect to the adjacent benzene rings. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules into chains along the a axis.

Related literature

For general background to quinazoline derivatives, see: Knesl et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₆ClNO₄
M _r = 273.71
Triclinic,
a = 8.1080 (16) Å
b = 9.818 (2) Å
c = 17.739 (3) Å
α = 82.07 (2)°
β = 83.41 (2)°
γ = 89.37 (3)°
V = 1389.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 294 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 = 0.921, T _max = 0.973
5297 measured reflections
4919 independent reflections
2591 reflections with I > 2σ(I)
R _int = 0.041
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.157
S = 1.01
4919 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.22 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: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011374/hk2651sup1.cif

e-65-0o942-sup1.cif^{(25KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011374/hk2651Isup2.hkl

e-65-0o942-Isup2.hkl^{(240.9KB, 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
N1—H1A⋯O3	0.86	2.07	2.709 (4)	131
N1—H1B⋯O8ⁱ	0.86	2.36	3.155 (4)	154
N2—H2C⋯O8	0.86	2.09	2.719 (4)	130
N2—H2C⋯O8ⁱⁱ	0.86	2.43	3.216 (4)	152
N2—H2D⋯O3	0.86	2.31	3.119 (4)	156

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

As part of our ongoing studies on quinazoline derivatives (Knesl et al., 2006), we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C4-C9) and A' (C16-C21) are, of course, planar and they are oriented at a dihedral angle of A/A' = 88.50 (3)°. Intramolecular N-H···O hydrogen bonds (Table 1) link the two molecules, also they result in the formations of two six-membered planar rings: B (O3/N1/C6/C7/C11/H1A) and B' (O8/N2/C19/C20/C23/H2C). The dihedral angles between the adjacent rings in each molecule are A/B = 1.39 (3)° and A'/B' = 0.68 (3)°. So, they are also coplanar.

In the crystal structure, intra- and intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into chains along the a axis (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, a suspension of methyl 4-(3-chloro- propoxy)-5-methoxy-2-nitrobenzoate (0.016 mol) in HCl (100 ml) was heated at 323-333 K for 5 min, and then a solution of tin(II) chloride (16.0 g, 0.1 mol) in HCl (20 ml) was added dropwise. The reaction mixture was heated at 363-373 K for 45 min. The solid formed was collected and dissolved in water (300 ml). A solution of sodium hydroxide (2N) was added to obtain pH = 8-9. The aqueous solution was then extracted with ethyl acetate (3 × 100 ml). The combined organic layers were dried over magnesium sulfate and concentrated in vacuo to give the title compound (yield; 2.3 g, 51.1%, m.p. 377 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.