1-(3-Mesityl-3-methyl­cyclo­butyl)-2-phenoxy­ethanone

Murat Koca; Cumhur Kirilmiş; Cengiz Arici

doi:10.1107/S1600536810003910

. 2010 Feb 6;66(Pt 3):o523. doi: 10.1107/S1600536810003910

1-(3-Mesityl-3-methylcyclobutyl)-2-phenoxyethanone

Murat Koca ^a, Cumhur Kirilmiş ^a, Cengiz Arici ^b,^*

PMCID: PMC2983636 PMID: 21580296

Abstract

In the title compound, C₂₂H₂₆O₂, the cyclobutane ring is puckered, with a dihedral angle of 24.97 (9)° between the two C₃ planes. In the crystal, intermolecular non-classical C—H⋯O interactions between the methylcyclobutyl CH group and the O atom of the phenoxy group are found.

Related literature

For related cyclobutanes, see: Çukurovali et al. (2005 ▶); Dinçer et al. (2004 ▶); Kirilmiş et al. (2005a ▶,b ▶); Sari et al. (2002 ▶, 2004 ▶). For the anti-inflammatory and anti-depressant activity of three-substituted cyclobutane acid derivatives, see: Roger et al. (1977 ▶); Gerard (1979 ▶); Sawhney et al. (1978 ▶); Brown et al. (1974 ▶); for anti-microbial activity, see: Suziki et al. (1979 ▶); for anti-parasitic activity, see: Slip et al. (1974 ▶), for herbicidal activity, see: Foerster et al. (1979 ▶) and for their liquid-crystal properties, see: Dehmlow & Schmidt (1990 ▶).

Experimental

Crystal data

C₂₂H₂₆O₂
M _r = 322.43
Triclinic,
a = 8.5884 (12) Å
b = 10.1725 (11) Å
c = 11.1018 (12) Å
α = 82.364 (4)°
β = 68.170 (3)°
γ = 86.235 (2)°
V = 892.24 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.42 × 0.33 × 0.24 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker–Nonius, 2002 ▶) T _min = 0.969, T _max = 0.982
23641 measured reflections
3921 independent reflections
2968 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.129
S = 1.07
3921 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Bruker–Nonius, 2002 ▶); cell refinement: EVALCCD (Bruker–Nonius, 2002 ▶); data reduction: EVALCCD 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003910/rk2189sup1.cif

e-66-0o523-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003910/rk2189Isup2.hkl

e-66-0o523-Isup2.hkl^{(188.3KB, 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
C10—H10A⋯O1ⁱ	0.99	2.44	3.419 (3)	172 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This study was supported financially by grant DPT/2003 K 120440-1 from the Scientific and Technical Research Council of Turkey (Project Manager Yıldırım Aydogdu). The authors extend special thanks to Frank W. Heinemann for the data collection.

supplementary crystallographic information

Comment

It is well known that three-substituted cyclobutane acid derivatives exhibit anti-inflammatory and anti-depressant activities (Roger et al., 1977; Gerard, 1979) and liquid-crystal properties (Dehmlow & Schmidt, 1990), moreover their of various thiazoles derivatives showed herbicidal (Foerster et al., 1979), anti-inflammatory (Sawhney et al., 1978; Brown et al., 1974), anti-microbial (Suziki et al., 1979) or anti-parasitic activity (Slip et al., 1974). Substituted cyclobutane contained similar structures, have been reported in the recent years (Kirilmiş et al., 2005a, 2005b; Sari et al., 2002, 2004;Çukurovali et al., 2005; Dinçer et al., 2004).

The four-atom bridge O2/C16/C15/C11 linking the cyclobutane and phenoxy rings is planar (Fig. 1). The torsion angle of O2—C16—C15—C11 is -1.0 (1)°. It corresponds to the (-) synclinical configuration. The cyclobutane ring is similar puckered as in a related compounds; the C9/C7/C10 plane forms a dihedaral angle of 24.97 (9)° with the C10/C11/C9 plane in the title compound. The same dihedral angles are presented in the literature: 25.74 (6)° - Çukurovali et al., (2005) and 19.8 (3)° - Dinçer et al., (2004). The mesityl and phenoxy rings are planar. The dihedral angle between these ring is 73.90 (5)°. The maximum deviation from mean plane of the atoms for mesityl and phenoxy rings are -0.046 (6)Å for C5 and 0.016 (3)Å for C17, respectively.

There is one intermolcular non-classical C—H···O hydrogen-bonding interactions in the crystal structure. This interactions lead to close packing between the neighbouring molecules. And the structure is stabilized by van der Waals interactions and symmetry-related molecules are linked to form dimerization chains via C—H···O intermolecular non-classical hydrogen bond. Intermolecular van der Waals interactions between the methylcyclobutyl CH group and the O atom of the phenoxy group (Fig. 2, Table 1).

In the IR spectra of 1-(3-mesityl-3-methylcyclobutyl)-2-phenoxy-1-ethanone very important bonds were observed as (ν, cm^-1); 1711 (sharp C═O stretching) respectively and between 3063–2852 (broad aliphatic and aromatic C—H stretching) and 1070 (ether C–O–C stretching). The ¹H-NMR spectra were reported in p.p.m. (δ) relative to tetramethylsilane (SiMe₄) as the internal standard and referenced to deuterochloroform (CDCl₃). In the ¹H-NMR spectra were H signals obtained as (p.p.m.) 1.7 (s, 3H, cyclobutane-CH₃), 2.2 (s, 9H, CH₃-mesitylene), 2.5–2.9 (m, 4H, cyclobutane CH₂), 3.9 (p,1H, cyclobutane CH), 4.2 (s, 2H, O—CH₂) and aromatic protons observed at 6.7–7.3 (m, 7H, ArH). Elemental Analysis Calc. for C₂₂H₂₆O₂ (322.44 g mol^-1): C, 81.95; H, 8.13 Found: C, 81.88; H, 8.05.

Experimental

Elemental analysis were determined on a LECO CHNS–932 auto elemental analysis apparatus. Infrared spectra were obtained by using a Mattson 1000 F T–IR Spectrometer, from 4000–400 cm^-1 in KBr pellet. ¹H-NMR spectra were recorded on a Jeol FX–90Q Spectrometer 90 MHz.

Synthesis of 1-(3-mesityl-3-methylcyclobutyl)-2-phenoxy-1-ethanone: a mixture of 1-mesityl-1-methyl-3-(2-chloro-1-oxoethyl)cyclobutane (2.64 g, 10 mmol), phenol (1.035 g, 11 mmol) and K₂CO₃ (1.51 g, 11 mmol) in 200 ml dry acetone was refluxed for 8 h. The reaction mixture was poured into water (500 ml), the insoluble portion was filtered off, washed with water and crystallized from ethanol (yield 85%).