2-(4-Chloro­phen­yl)-3-methyl-N-(5-methyl­thia­zol-2-yl)butanamide

Jing-Li Cheng; Jin-Hao Zhao; Guo-Nian Zhu; Fu-Cheng Lin

doi:10.1107/S1600536808043031

. 2008 Dec 20;65(Pt 1):o184. doi: 10.1107/S1600536808043031

2-(4-Chlorophenyl)-3-methyl-N-(5-methylthiazol-2-yl)butanamide

Jing-Li Cheng ^a, Jin-Hao Zhao ^a, Guo-Nian Zhu ^a, Fu-Cheng Lin ^b,^*

PMCID: PMC2968093 PMID: 21581639

Abstract

In the title compound, C₁₅H₁₇ClN₂OS, the thiazole ring, which is essentially planar with a maximum deviation of 0.044 (3) Å, makes a dihedral angle of 54.76 (8)° with the benzene ring. In the crystal, adjacent molecules related by twofold rotation symmetry are linked by pairs of N—H⋯N hydrogen bonds.

Related literature

For background, see: Holmstead et al. (1978 ▶); Forlani (1978 ▶). For a related structure, see: Zhao et al. (2006 ▶).

Experimental

Crystal data

C₁₅H₁₇ClN₂OS
M _r = 308.83
Monoclinic,
a = 14.9649 (6) Å
b = 17.6062 (7) Å
c = 12.5606 (5) Å
β = 99.9482 (11)°
V = 3259.6 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 298 (1) K
0.41 × 0.33 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.858, T _max = 0.911
15655 measured reflections
3708 independent reflections
2559 reflections with F ² > 2σ(F ²)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.172
S = 1.01
3708 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536808043031/is2368sup1.cif

e-65-0o184-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043031/is2368Isup2.hkl

e-65-0o184-Isup2.hkl^{(181.9KB, 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—H111⋯N2ⁱ	0.86	2.08	2.929 (2)	168

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful for support from the National Natural Science Foundation of China (No. 30700532) and also thank Professor Jian-Ming Gu for help with the analysis of the crystal data.

supplementary crystallographic information

Comment

2-(4-Chlorophenyl)-3-methylbutanoyl chloride is an intermediate in the synthesis of fenvalerate, an excellent insecticide (Holmstead et al., 1978). 2-Amino-5-methyl-thiazole is another heterocyclic intermediate (Forlani, 1978). As part of our continuing interest in the design and synthesis of new pesticides, we have isolated the title compound, (I), the product of the condensation reaction between 2-(4-chlorophenyl)-3-methylbutanoyl chloride and 5-methyl-2-aminothiazole, as colourless crystals suitable for X-ray analysis.

The molecular structure of (I) is illustrated in Fig. 1. Atoms N2, C10, C11, S1, C9 and N1 are coplanar, the largest deviation being 0.044 (3) Å for N1. As expected, the benzene ring is planar, and atom Cl1 lies only 0.018 (4) Å from the plane defined by the ring C atoms and itself. The angle between these two rings is 54.76 (8)°, smaller than the angle between the thiazole and benzene rings of the compound 2-(4-chlorophenyl)-3-methyl-N-(thiazol-2-yl) butanamide (Zhao et al., 2006). There are N—H···N interactions in the crystal structure, which lead to the formation of hydrogen-bonded dimers (Figs. 2 and 3).

Experimental

2-Amino-5-methylthiazole (1.14 g, 10 mmol), 4-dimethylaminopyridine (0.12 g), triethylamine (1.31 g) and chloroform (100 ml) were added to a 250 ml round flask. The mixture was stirred and cooled to 273 K, and then 2-(4-chlorophenyl)-3-methylbutanoyl chloride (3.47 g) was added dropwise within 30 min. The mixture was stirred at room temperature for 3 h and then 1% aqueous HCl was added (5 ml). The organic layer was washed with water to a neutral pH and dried over Na₂SO₄. After being filtered and concentrated, the organic residue was purified by silica-gel column chromatography, eluted with ethyl acetate-petroleum ether-formic acid (10:80:1, v/v/v), to give a white solid (yield 85%, 2.5 g), (I). It was then recrystallized from ethyl acetate-petroleum ether (2:1, v/v) to give colourless blocks (m.p. 460–461 K).