Competition of substituents for ortho direction of metalation of veratric acid

LTMP (5 equiv) metalates randomly veratric acid (1). Under external quench conditions, the thermodynamically more stable lithium 2-lithio-3,4-dimethoxybenzoate (2) reacts with a variety of electrophiles to give versatile building units that are not easily accessible by conventional means. Under in situ quench conditions (LTMP/TMSCl), a reversal of regioselectivity is observed and 6-trimethylsilyl-3,4-dimethoxybenzoic acid (10) is formed predominantly.     

Efficient Friedel–Crafts benzoylation of aniline derivatives with 4-fluorobenzoyl chloride using copper triflate in the synthesis of aminobenzophenones

An efficient pathway for the synthesis of the aminobenzophenone derivatives via Friedel–Crafts benzoylation using copper triflate as catalyst is proposed. New derivatives are synthesized. The copper triflate could be easily recovered and reused without loss of catalytic activity. Both the use of ionic liquids and microwave heating turned out to be fruitful.     

Schiff bases of gossypol: an NMR and DFT study

Schiff bases of gossypol with benzylamine, methylamine, 4-aminoacetophenone and 4-fluoroaniline have been synthesized and characterized by NMR spectroscopy. All the Schiff bases of gossypol are in the enamine form according to (3)J(HC,NH) and (1)J(N,H) coupling constants. The spectra are basically unchanged by change of solvent (CD(2)Cl(2), THF-d(8) and CD(3)OD) and by variation of temperature. For the derivative of benzylamine, deuterium isotope effects on (13)C chemical shifts are determined. They support strongly the enamine form and serve as a reference for other tautomeric Schiff bases. Structures and NMR nuclear shieldings of model compounds (the second monomer is replaced by a 2-hydroxybenzene ring) have been calculated by density functional theory (DFT) methods. A good correlation is observed between calculated (13)C nuclear shieldings of the enamine form and observed (13)C chemical shifts.     

Convergent Synthesis of Naphthylisoquinoline Alkaloids: Total Synthesis of (+)-O-Methylancistrocline

A highly convergent synthesis of the methyl ether derivative 2a of the naphthylisoquinoline alkaloid ancistrocline (2) is described. The key step involves a stereoselective biaryl coupling between the chiral oxazoline 3 and the Grignard reagent 4 derived from the optically active tetrahydroisoquinoline 8. The atropisomeric mixture was then converted to the separable acetamides 11 and 12, which were obtained in a ratio of 16:84 and an overall yield of 32% for the three steps. The major atropisomer 12 was then converted into O-methylancistrocline (2a), which was identical to a semisynthetic sample derived from the related alkaloid ancistrocladinine (14).     

NMR of a series of novel hydroxyflavothiones

Alkylated hydroxyflavothiones, namely flavothione, 5‐hydroxyflavothione, 5,7‐dihydroxyflavothione (chrysinthione), 7‐dodecyloxy‐5‐hydroxyflavothione, 7‐butyloxy‐5‐hydroxyflavothione, 2′,3,4′,7‐tetramethoxy‐5‐hydroxyflavothione, 3,3′,4′,7‐tetramethoxy‐5‐hydroxyflavothione, 7‐butyloxy‐4′,5‐dihydroxyflavothione and 7‐butyloxy‐4′,5‐hydroxyflavanonethione have been synthesized from the corresponding hydroxyflavones in two steps, alkylation of the non‐hydrogen‐bonded hydroxyl groups by bromoalkanes or dimethyl sulfate followed by conversion of the carbonyl group to a thione using Lawesson's Reagent under microwave irradiation and solvent‐free conditions. Part of the alkylated flavanone, 7‐butyloxy‐4′,5‐dihydroxyflavanone, was oxidized during the treatment with Lawesson's reagent to yield a second product 7‐butyloxy‐4′,5‐dihydroxyflavothione in addition to the target product butyloxy‐4′,5‐hydroxyflavanonethione. Deuterium isotope effects on 13C chemical shifts have been measured in hydroxyflavones, isoflavones, flavanones and the thio analogs. Formal four‐bond deuterium isotope effects on 13C chemical shifts, nΔC?S(OD) are very sensitive to variations in structures and substitution patterns. Density functional theory (DFT) calculations are carried out to obtain geometries. Correlations relating distances around the hydrogen bond system to the deuterium isotope effects on 13C chemical shifts are discussed. 13C chemical shifts are calculated by DFT methods. Effects of thiocarbonyl anisotropies are suggested. Copyright © 2009 John Wiley & Sons, Ltd.     

Optical bistable behavior of single-mode fabry-perot lasers with saturable absorber

The present paper is devoted to the optical bistable behavior of Gaussian inhomogeneously broadened single-mode Fabry-Perot lasers with saturable absorber (LSA) in both resonance and nonresonance. The system is described by rate equations based on the dual two-level model with allowance for spontaneous emission and spatial hole-burning. The conditions under which optical bistability (OB) occurs are clearly displayed in phase diagrams. The OB characteristics and stability behavior are investigated in connection with their dependence on the detuning and LSA parameters. Paper submitted by authors in English April 20, 1999.     

Recent advances in enhancing the sensitivity of electrophoresis and electrochromatography in capillaries and microchips (2016–2018)

One of the most cited limitations of capillary and microchip electrophoresis is the poor sensitivity. This review continues to update this series of biannual reviews, first published in Electrophoresis in 2007, on developments in the field of online/in‐line concentration methods in capillaries and microchips, covering the period July 2016–June 2018. It includes developments in the field of stacking, covering all methods from field‐amplified sample stacking and large‐volume sample stacking, through to isotachophoresis, dynamic pH junction, and sweeping. Attention is also given to online or in‐line extraction methods that have been used for electrophoresis.     

Chemical constituents of the lichen Usnea baileyi (Stirt.) Zahlbr

Investigation of the chemical constituents of the lichen Usnea baileyi (Stirt.) Zahlbr led to the isolation of a new dimeric xanthone, bailexanthone (1), and a novel depsidone, bailesidone (2), along with twenty-five known metabolites (3–27). Their structures were established by means of extensive spectroscopic analysis and comparison with data reported in the literatures. Compound 1 derives from secalonic acid scaffold with C-8/8′ reduction and compound 2 represents the first example of menegazziaic acid derivative with an unprecedented B-ring moiety. Two new compounds 1–2 were evaluated for their cytotoxic activities against A549 (human lung carcinoma) and HT29 (human colorectal adenocarcinoma) cell lines. All of them showed weak or no activity against two cell lines.     

Bang-bang property for time optimal control of semilinear heat equation

This paper studies the bang-bang property for time optimal controls governed by semilinear heat equation in a bounded domain with control acting locally in a subset. Also, we present the null controllability cost for semilinear heat equation and an observability estimate from a positive measurable set in time for the linear heat equation with potential.     

Vertex-minimal planar graphs with cyclic 2-group symmetry

Journal of Algebraic Combinatorics - For the positive integer m, let $${mathbb {Z}}_m$$ denote the cyclic group of order m. Vertex-minimal planar graphs with prescribed automorphism group...