Ethyl 2-[(Z)-2-benzyl­hydrazin-1-yl­idene]-2-bromo­acetate

Qian-Jiao Yang; Dan Liu; Jian Zuo; Guo-Dong Hu; Lin-Xiang Zhao

doi:10.1107/S1600536810032071

. 2010 Aug 18;66(Pt 9):o2334. doi: 10.1107/S1600536810032071

Ethyl 2-[(Z)-2-benzylhydrazin-1-ylidene]-2-bromoacetate

Qian-Jiao Yang ^a, Dan Liu ^a, Jian Zuo ^b, Guo-Dong Hu ^a, Lin-Xiang Zhao ^a,^*

PMCID: PMC3007982 PMID: 21588679

Abstract

In the title compound, C₁₁H₁₃BrN₂O₂, the dihedral angle between the phenyl ring and the almost planar (r.m.s. deviation = 0.011 Å) C—C(Br)=N—N(H)— fragment is 74.94 (16)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, which generate C(6) chains propagating in [010]. Weak aromatic π–π stacking [centroid–centroid separation = 3.784 (3) Å] may also help to consolidate the packing.

Related literature

For the use of the title compound in the preparation of heterocyclic compounds via the diploar cycloaddition of thiadiazole, see Feddouli et al. (2004 ▶); Abouricha et al. (2005 ▶); Hafez et al. (2008 ▶). For the synthesis of the title compound, see Bach et al. (1994 ▶).

Experimental

Crystal data

C₁₁H₁₃BrN₂O₂
M _r = 285.14
Monoclinic,
a = 9.046 (1) Å
b = 11.235 (1) Å
c = 12.326 (2) Å
β = 92.935 (4)°
V = 1251.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.27 mm⁻¹
T = 294 K
0.25 × 0.14 × 0.07 mm

Data collection

Siemens APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ▶) T _min = 0.495, T _max = 0.803
4952 measured reflections
2188 independent reflections
1475 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.111
S = 1.02
2188 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536810032071/hb5585sup1.cif

e-66-o2334-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032071/hb5585Isup2.hkl

e-66-o2334-Isup2.hkl^{(107.6KB, 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
N1—H1⋯O1ⁱ	0.86	2.24	2.965 (4)	141

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the China International Science and Technology Cooperation Plan (2009DEA31200).

supplementary crystallographic information

Comment

(Benzylhydrazono)acetate is a key intermediate in the preparation for pyrazoline compounds (Bach et al., 1994), which are selective for the NMDA receptors and show weak antagonists. In addition, it plays an important role in the synthesis of thiadiazole nucleus (Feddouli et al., 2004; Abouricha et al., 2005), which have been exhibited potential anti-inflammatory and analgesic activities (Hafez et al., 2008). Herein, the structure of ethyl 2-bromo-(Z)-2-(2-benzylhydrazono)acetate has been determined.

The crystal structure of the title compound is given in Fig. 1. In the crystal, the adjacent molecules are stabilized by N—H···O hydrogen bonding, with the distance of 2.965 (4) Å (Table 1). Molecules are linked into chain along the b axis by the above hydrogen bond (Fig. 2).

Experimental

To a stirred solution of ethyl 2,2-diethoxyacetate (1 ml, 5.6 mmol) and acetyl chloride (0.8 ml, 11.2 mmol) was added iodine (3 mg, 0.01 mmol). After the mixture was stirred for overnight, excess acetyl chloride was removed in vacuo, the residue in 1,4-dioxane (25 ml) was treated with benzylhydrazine dihydrochloride (1.09 g, 5.6 mmol) in water (10 ml), then the mixture was adjusted to pH 4. After 1 h the mixture was neutralized to pH 8 with saturated NaOH and evaporated in vacuo. The residue was added water and extracted with CH2Cl2, the organic layer was dried over MgSO4, filtered and concentrated. The crude compound was dissolved in AcOEt (8 ml), which was reacted with NBS (1.1 g, 6.2 mmol) for 2 h. After evaporation of the solvent, the residue was dissolved in CH2Cl2 and filtered, the filtrate was concentrated and purified by column chromatography (eluent: PE/AcOEt = 28/1) to give the title compound (0.67 g, 2.35 mmol) as a white solid. Colorless blocks of (I) were grown in PE/AcOEt (14/0.5, V/V) solution by slow evaporation at room temperature.