Synthesis and Crystal Structure of 3-(2-Hydroxy-phenyl)-5-(2-methyl-phenyl)-6-thoxycarbonyl-cyclohexen-2-one

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1 INTRODUCTION The molecular assembly of one- or multi-dimen-sional aggregation by hydrogen bonds is now an im-portant subject of supramolecular chemistry and crys-tal engineering[1, . Supramolecular structures formed 2]via intermolecular hydrogen bonds X–H…X or C–H…X (X = O, Cl, N, et al.) are very common inorganic compounds[3~12], and they generally possessdifferent properties due to these hydrogen bonds. Concerning about the spectra of benzene-contai-ning compounds, substituent effect of benzene para-substituent has been well presented. Orlov[13, 14] stu-died the IR and UV spectra of 3,5-bis(phenyl)-6-ethoxycarbonyl-cyclohexen-2-one and revealed theimpact of para substituent which connects with cyc-lohexen ketone by sp2 hybrid C on its spectra. Inorder to further discover the influence of benzeneortho-substituent on the molecular spectrum, a series of3,5-bis(phenyl)-6-ethoxycarbonyl-cyclohexen-2-onederivatives were synthesized. At the same time, IR,UV, solid fluorescence spectra and photo-physicalbehavior in solution were investigated. And ultima-tely, a conclusion was drawn that spectral propertiesof these compounds have something to do with thetwo benzene ortho-substituents. Photo-physical be-haviors in solution of partial molecules that can formintermolecular hydrogen bonds are obviously diffe-rent from those of others. Herein synthesis and crys-tal structure of 3-(2-hydroxyphenyl)-5-(2-methyl-phenyl)-6-ethoxycarbonyl-cyclohexen-2-one are re-ported and the existence of intermolecular hydrogenbonds is verified.2 EXPERIMENTAL Saturated ethanol solution of the title compound was prepared and kept at room temperature for four2. 1 Reagents and physical measurements weeks, obtaining colorless transparent flaky crystals. All reagents from commercial sources were of AR A crystal with dimensions of 0.483mm × 0.230mm ×grade. Solvent was purified according to standard 0.102mm was selected and the crystal measurementprocess before use. Melting point was recorded on a was carried out on a Bruker Smart Apex diffracto-WRS-1A digital melting point apparatus. Elemental meter equipped with a graphite-monochromatizedanalysis was performed on a PE-2400(II) elemental MoKα(λ =0.71073 ?) radiation at 293(2) K. A total ofanalyzer. IR spectra were carried out on a PE-2000 9946 reflections were collected, of which 3777 (Rintspectrometer with KBr pellets. UV spectra were re- = 0.0774) were independent in the range of 1.90o≤θcorded on a PE Lambda-35 spectrometer. NMR spec- ≤26.50o and 3142 were observed with I>2σ(I). Thetrum was obtained on a Bruker DPX-400 nuclear structure was solved by direct methods. The non-Hmagnetic resonance apparatus. Mass spectrum was atoms were determined with successive differencecarried on an Agilent 5973N low-resolution mass Fourier syntheses; the hydrogen atoms were deter-spectrometer. The crystal determination was carried mined with the same method or located at the calcu-out on a Bruker Smart Apex diffractometer. lated positions. The anisotropic thermal parameters2. 2 Synthesis of the title compound for non-hydrogen atoms were refined by full-matrix According to Knoevenagel method[14, 15], the title least-squares techniques on F2 for 323 parameters.compound was synthesized by the reaction of 2- All calculations were performed on a computer withmethyl-2?-hydroxyl-chalcone and acetoacetate ester SHELX 97 program package. The final R = 0.0680,in EtONa/EtOH solvent with heating. White clavi- wR = 0.1498 (w = 1/[σ2(Fo )+(0.0432P)2+0.9226P], 2form crystals were obtained after repeated recrys- where P = (Fo + 2Fc )/3), (?/σ)max = 0.017, S = 2 2tallization with ethanol. Yield: 67%. m.p.: 153.4~ 1.159, (?ρ)max = 0.242 and (?ρ)min = –0.182 e/?3.153.9 ℃. Anal. Calcd. (%) for C22H22O4: C, 75.41;H, 6.33; O, 18.26. Found (%): C, 75.30; H, 6.39; O, 3 RESULTS AND DISCUSSION18.31. IR ν: 3391, 3123, 2985, 1733, 1635, 1596,1574, 1449 cm-1. UV-vis (EtOH) λmax: 202, 243, 3. 1 Crystal structure276, 324 nm. H NMR (CDCl3, 400MHz) δ: 1.02(t, 1 The atomic coordinates and thermal parameters of3H, CH3), 2.48(s, 3H, ArCH3), 2.87~2.96(m, 2H, non-hydrogen atoms are listed in Table 1. The selec-CH2-), 3.88~4.14(m, 4H, CH-CH, O-CH2), 6.90~ ted bond lengths and bond angles are given in Table7.34(m, 10H, C=CH-CO, Ph-OH, ArH). MS (70eV): 2. The crystal structure and intermolecular hydrogenm/z 350(M

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