A Simple Method for N-Phenoxyethylation of Anilines

Abstract: We wanted to search for new reaction conditions to prepare the title compounds, to be checked later in novel syntheses of heterocyclic compounds. To the best of our knowledge, there was no report in the literature of any well-established method for the preparation of N-(2-phenoxyethyl)anilines 1. The scarce previously reported preparations involved large excesses of some starting materials, relatively high temperatures and long reaction times [1, 2]. We have recently reported a general procedure for that preparation [3] although at that stage only moderate yields were obtained. We describe here a better and simpler procedure for achieving not only compounds 1 in good yields, but also for extending the scope of the reaction to the synthesis of the related bis-N-(2-phenoxy-ethyl)anilines 2. In order to avoid β-elimination reactions in molecules bearing a phenoxyethyl group, the reaction was carried out precluding strong acidic or basic media, see Scheme. NH

Vibrational, Electronic, and Structural Properties of 6‑Nitro- and 6‑Amino-2-Trifluoromethylchromone: An Experimental and Theoretical Study

Two 2-trifluoromethylchromones, 6-nitro-2-trifluoromethylchromone <b>(1)</b> and 6-amino-2-trifluoromethylchromone (<b>2</b>) were synthesized and characterized by NMR (¹H, ¹³C, and ¹⁹F), UV–vis, vibrational (IR and Raman) spectroscopy, MS spectrometry, and compound <b>1</b> also by single structural X-ray diffraction methods. This substance crystallizes in the monoclinic <i>P</i>2₁/<i>c</i> space group with <i>Z</i> = 4 molecules per unit cell. In the solid, the fused rings and the amino group of <b>1</b> are coplanar and the trifluoromethyl group adopts a nearly staggered conformation. The NMR, vibrational, and electronic spectra were discussed and assigned with the assistance of DFT calculations

Spectroscopic, Structural, and Conformational Properties of (<i>Z</i>)-4,4,4-Trifluoro-3-(2-hydroxyethylamino)-1-(2-hydroxyphenyl)-2-buten-1-one, C₁₂H₁₂F₃NO₃: A Trifluoromethyl-Substituted β-Aminoenone

The (<i>Z</i>)-4,4,4-trifluoro-3-(2-hydroxyethylamino)-1-(2-hydroxyphenyl)-2-buten-1-one (C₁₂H₁₂F₃NO₃) compound was thoroughly studied by IR, Raman, UV–visible, and ¹³C and ¹⁹F NMR spectroscopies. The solid-state molecular structure was determined by X-ray diffraction methods. It crystallizes in the <i>P</i>2₁/<i>c</i> space group with <i>a</i> = 12.1420(4) Å, <i>b</i> = 7.8210(3) Å, <i>c</i> = 13.8970(5) Å, β = 116.162(2)°, and <i>Z</i> = 4 molecules per unit cell. The molecule shows a nearly planar molecular skeleton, favored by intramolecular OH···O and NH···O bonds, which are arranged in the lattice as an OH···O bonded polymer coiled around crystallographic 2-fold screw-axes. The three postulated tautomers were evaluated using quantum chemical calculations. The lowest energy tautomer (I) calculated with density functional theory methods agrees with the observed crystal structure. The structural and conformational properties are discussed considering the effect of the intra- and intermolecular hydrogen bond interactions