N′-tert-Butyl-N′-(3,5-dimethyl­benzo­yl)-2,2-dimethyl-4-oxochroman-6-carbo­hydrazide

Zhongzhen Zhou; Wenwei You; Zhongkun Tang; Peiliang Zhao

doi:10.1107/S1600536809028815

. 2009 Jul 29;65(Pt 8):o2015. doi: 10.1107/S1600536809028815

N′-tert-Butyl-N′-(3,5-dimethylbenzoyl)-2,2-dimethyl-4-oxochroman-6-carbohydrazide

Zhongzhen Zhou ^a, Wenwei You ^a, Zhongkun Tang ^a, Peiliang Zhao ^a,^*

PMCID: PMC2977281 PMID: 21583686

Abstract

In the crystal structure of the title compound, C₂₅H₃₀N₂O₄, the steric size of the tert-butyl group causes the 3,5-dimethylphenyl ring to adopt a transoid geometry with respect to the N—C(O) bond. The six-membered heterocyclic ring is disordered over two sites, with occupancies of 0.553 (4) and 0.447 (4). Intramolecular C—H⋯O interactions are present. In the crystal, molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For general background to dibenzoylhydrazines and their derivatives, see: Sawada et al. (2003 ▶). For a related structure, see: Zhao et al. (2005 ▶). For the preparation of the title compound, see: Zhao et al. (2007 ▶); Mao et al. (2008 ▶).

Experimental

Crystal data

C₂₅H₃₀N₂O₄
M _r = 422.51
Monoclinic,
a = 14.1260 (12) Å
b = 10.6964 (9) Å
c = 15.4370 (13) Å
β = 96.426 (2)°
V = 2317.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 297 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2005 ▶) T _min = 0.976, T _max = 0.984
13199 measured reflections
5043 independent reflections
3983 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.142
S = 1.04
5043 reflections
338 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 global, I. DOI: 10.1107/S1600536809028815/fj2236sup1.cif

e-65-o2015-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028815/fj2236Isup2.hkl

e-65-o2015-Isup2.hkl^{(247KB, 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
C16—H16C⋯O4	0.96	2.39	3.007 (2)	121
C15—H15A⋯O4	0.96	2.36	2.918 (2)	117
C8—H8⋯O4ⁱ	0.93	2.48	3.3214 (18)	151
N1—H1⋯O4ⁱ	0.862 (17)	2.096 (18)	2.9442 (15)	167.8 (15)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from the Science Foundation of the Southern Medical University for New Excellent Talents (No. B1000374).

supplementary crystallographic information

Comment

Dibenzoylhydrazines are well known as nonsteroidal ecdysone agonists that have the potential to control the Lepidopteran pests while exerting only a low toxicity against non-target insects. (Sawada et al., 2003). While chroman derivatives also have broad-spectrum biological activity. Hence, to search for novel lead compounds for crop protection, The title compound, (I), was designed and synthesized in our laboratory. In this paper, we present the X-ray crystallographic analysis of (I).

As shown in Fig. 1, the six-membered heterocyclic ring adopts a half-chair conformation. the dihedral angle between the phenyl ring and the benzene ring of the chromanone is 58.14 (2)°. The six-memebered heterocyclic ring is disordered over two sites with occupancies of 0.553 (4) and 0.447 (4). The steric size of the N-tert-butyl group causes the 3,5-dimethylphenyl group to be directed away from it.

One intermolecular N—H···O hydrogen bond and one intermolecular C—H···O hydrogen bonds exist in the crystal structure (Table 1 and Fig. 2), atoms N1 and C8 in the molecule act as donors, via the H atoms H1 and H8, to the O4 of a adjacent molecule(Tabel 2). As a result, an seven-membered ring is formed between molecules (Fig. 2). No π-π stacking interactions are observed in the crystal structure.

Experimental

To A solution of 2,2-Dimethyl-4-oxo-chroman-6-carboxylic acid N'-tert-butyl-hydrazide (1.5 mmol) in 10 ml of dichloromethane was added dropwise to a stirred mixture of 3,5-dimethylbenzoyl chloride (1.5 mmol), triethylamine (1.6 mmol) and dichloromethane (5 ml) in an ice bath.After stirring the mixture at room temperature for 3 h,ethyl acetate (30 ml) was added to the reaction mixture. The organic layer was separated and washed successively with water (15 ml) and brine (15 ml), and then dried with anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by column chromatography on silicagel using hexane/ethyl acetate (9:1 v/v) as eluent to afford (I) (yield 80%, m.p. 435 K) Spectroscopic analysis: ¹H NMR(CDCl3, 400 MHz) 8.06 (s, 1H, N—H), 7.74 (d, 2H, C10—H, C11—H), 7.05 (s, 2H, C19—H, C23—H), 6.81 (m, 2H, C8—H, C21—H), 2.70 (s, 2H, C2—H), 2.21 (s, 6H, C24—H, C25—H), 1.57 (s, 9H, C14—H, C15—H,C16—H),1.44 (s, 6H, C6—H,C7—H); MS (EI 70 eV)m/z(%):422 (16), 367 (95), 349 (35), 203 (62), 146 (20),133 (100), 105 (49),102 (19). Crystals suitable for an X-ray diffraction study were grown from methanol at 292 K.