Synthesis and Crystal Structure of the Derivative of Hydroquinone from Mannich Reaction

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【出版日期】2005-03-30

【刊名】结构化学

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1 INTRODUCTION Mannich reaction plays an important role in theconstruction of a large variety of nitrogen-containingmolecules, for instance, some pharmaceuticals andnatural products[1, . In practice, phenols and naph- 2]thanols can serve as the substrate of Mannich reac-tion to obtain aminomethylate by the treatment withformaldehyde and amines or nitrogen heterocycliccompounds[3~5]. We report herein the synthesis andcrystal structure of a new nitrogencontaining com-pound, using one-pot process involving condensa-tion of phenols, morpholine and paraformaldehyde.2 EXPERIMENTAL2. 1 Physical measurements Melting points were obtained on a YanagimotoMP-500 apparatus and uncorrected. IR spectra weremeasured on a BIO-RAD FT3000 (KBr disc).2. 2 Synthesis Compound A was synthesized by the followingreaction shown in Scheme 1. The mixture of hydroquinone (1.1 g, 10 mmol),morpholine (1.74 g, 20 mmol) and paraformalde-hyde (1 g, 33.3 mmol) in ethanol (20 mL) was heatedto reflux and kept at this temperature for 20 h, andthen the resulting solution was cooled to room tem-perature. After filtration, the filtrate was stood at am-bient temperature. Upon slowly evaporating ethanolfrom the solution, colorless flake-like crystals suita-ble for X-ray diffraction analysis were isolated threedays later. m.p.: 207~209 ℃. IR: 3336 (b), 3027(w), 2981 (s), 2849 (s), 2760 (m), 1765 (w), 1608(w), 1483 (s), 1453 (s), 1383 (m), 1296 (s), 1195 (m),1118 (s), 863 (s), 752 (m), 611 (m). OH OH CH2 N O EtOH O NH + ( HCHO )n + reflux O N H2C OH OH A Scheme 12. 3 Crystallographic data collection atoms were added according to theoretical modes, and structure determination attached on the parent atoms and refined with fixed A single crystal of compound A with approximate thermal factors. The final refinement converged to Rdimensions of 0.24mm × 0.18mm × 0.14mm was =0.0508 and wR=0.1075 (w=1/[σ2(Fo ) + (0.0427P)2 2selected and mounted in a thin capillary. All of the + 0.5707P], where P = (Max(Fo , 0) + 2Fc )/3). S = 2 2diffraction data were collected on a Bruker SMART 1.078, (?/σ)max = 0, (?ρ)max = 0.206 and (?ρ)min =1000 diffractometer equipped with a graphite-mono- –0.179 e/?3. Molecular graphics was drawn with thechromatized MoKα radiation (λ = 0.71073 ?) by program package XP.using the θ-ω scan mode (3.09<θ<25.00o) at 293(2)K. A total of 5906 reflections were collected with 3 RESULTS AND DISCUSSION1416 unique ones (Rint=0.0450), of which 1416 wereobserved with I > 2σ(I). The intensity data were cor- The final atomic coordinates and thermal para-rected by SADABS absorption and the structure was meters of all non-hydrogen atoms of compound Asolved by direct methods with SHELXL97 program are listed in Table 1, and the selected bond lengthspackage[6, . All non-hydrogen atoms were located 7] and bond angles in Table 2. The molecular structurein successive difference Fourier syntheses, and the and packing diagram of A are shown in Figs. 1 and 2,final refinement was performed by full-matrix least- respectively. The hydrogen bonds and bond angelssquares techniques with anisotropic thermal parame- of A are given in Table 3.ters for the non-hydrogen atoms on F2. All hydrogen Table 1. Atomic Coordinates (× 104) and Equivalent Isotropic Displacement Parameters (?2 × 103) of A Atom x y z Ueq Atom x y z Ueq O(1) 6963(2) 5022(2) 7009(1) 71(1) C(4) 4908(3) 4589(2) 6319(2)

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