Efficient synthesis of 4-aminoquinazoline and thieno[3,2-d]pyrimidin-4-ylamine derivatives by microwave irradiation

[reaction: see text] A simple, efficient, and high-yielding synthesis of quinazolin-4-ylamine and thieno[3,2-d]pyrimidin-4-ylamine derivatives is reported under microwave irradiation conditions. Reaction conditions including temperature, solvent, and reaction time have been studied. An efficient parallel workup procedure was developed to generate a small library (23 compounds) in a short time period.     

Purification by solid layer melt crystallization

The application of solid layer crystallization techniques in industry is arousing ever more interest. One reason is the increasing demand for ultrapure products, and another is the energysaving potential of this separation technology.This article examines solid layer melt crystallization as concerns its purification efficiency. The crystallization process was carried out in two different modes, whereby the process parameters were varied and post-crystallization treatments were additionally applied. The experimental results were used as the basis for a mathematical fit of a semi-empirical expression which predicts the purification efficiency. It was used for a design of different multistage plants, which operate with different crystallization strategies. One result is that a comparable product quality is attainable with a simple process technique in combination with post-crystallization treatments, instead of a more complicated and therefore more expensive process technique.The authors wish to acknowledge support by the EU (JOULE program), which helped attainment of some results presented here.     

Carbon-carbon and carbon-nitrogen coupling reactions catalyzed by palladium nanoparticles derived from a palladium substituted Keggin-type polyoxometalate

Palladium 15-20 nm particles stabilized by a Keggin-type polyoxometalate were prepared by reduction of K(5)PPdW(11)O(39) with H(2). The nanoparticles were shown to be effective catalysts for Suzuki-, Heck-, and Stille-type carbon-carbon coupling and carbon-nitrogen coupling reactions of bromoarenes in aqueous media. Chloroarenes were also reactive in reaction media without solvent. [reaction: see text]     

Three‐Component Reactions with (S)‐Methyl Pyroglutamate: An Efficient Way to Diversely Substituted Asymmetric Amidocyclohexenes

Chiral N‐dienyl lactams are crucial building blocks for the synthesis of complex organic compounds. However, their generation is rather challenging. This paper reports the novel one‐pot reaction of (S)‐methyl pyroglutamate as the a mide component with different a ldehydes and d ienophiles (AAD reaction) to give novel chiral 1‐amido‐2‐cyclohexenes. The corresponding N‐dienyl lactams generated in situ undergo subsequent Diels–Alder reactions in good yield and diastereoselectivity. The scope and limitations of the three‐component protocol were investigated. X‐ray and NMR spectroscopic analysis of the products as well as DFT calculations of the intermediates were also performed to explain the observed stereoselectivity and structural features.     

A new ionic liquid dimethyldinonylammonium bromide as a flow modifier for the simultaneous determination of eight carboxylates by capillary electrophoresis

Two new methods of capillary zone electrophoresis based on aqueous phosphate running buffers with UV spectrophotometric detection were developed and optimized for the determination of eight carboxylates as copper complexes. Metalcomplexes are negatively charged, so measurements were made as anion analyses with flow reversal in the capillary. Two flow modifiers were used: a common tetradecyltrimethylammonium bromide (TTAB) and a new ionic liquid dimethyldinonylammonium bromide (DMDNAB). The methods were compared to each other. Better separation was achieved with DMDNAB as the flow modifier. Method development was done using a fused silica capillary (61 cm x 50 microm i.d.).Optimization was done using 95 mmol L(-1) phosphate buffer with TTAB or DMDNAB in the concentration 0.5 mmol L(-1) at pH 7.1. A -20 kV voltage and direct UV detection at 254 nm was used in measurements. In both CE methods all the peaks in the electropherograms were properly separated, the calibration plots gave good correlation coefficients and all eight carboxylates were detected in less than 7.5 min. The two methods were tested with natural water samples and a paper mill sample, and proved to be feasible.     

Helical coordination polymers and cyclic dimers formed from heteroleptic thioether-dipyrrinato copper(II) complexes

Heteroleptic copper complexes containing an acetylacetonato ligand and a thioether derivatized dipyrrinato ligand are shown to form oligomers and polymers in the solid state.     

A mild hydrolysis of esters mediated by lithium salts

When treated with amine bases such as triethylamine and various lithium salts in wet solvents, esters are efficiently hydrolyzed to the corresponding acids in good yields. Esters incorporating an α- or β-heteroatom with respect to the ester carbonyl group are hydrolyzed rapidly even at room temperature. To further demonstrate the usefulness of this method, one example is provided where hydrolysis of acetylated camphorsultam is mediated by LiBr.     

Chiral [2H]-Labelled Methylene Groups in Trienoic- and Dienoic Fatty Acids: A Facile Approach via Asymmetric Epoxidation of [2H] Allyl Alcohols

Chiral [²H] -labelled methylene groups flanked by two double bonds within (poly)unsaturated fatty acids are readily available from trans-2,3-epoxy[2,3-²H₂] alk-4-yn-l-ols, obtained in their turn by asymmetric epoxidation of the corresponding (E)-[2,3-²H₂] alk-2-en-4-yn-l-ols (see Scheme 3). The procedure is exemplified for (8S,3Z,6Z,9Z)-[7,8-²H₂] trideca-3,6,9-trienoic acid ((8S)- 11 ) and (8R)- 11 (Scheme 4) as well as for (5S,3Z,6Z)-[4,5^?2H₂]deca-3,6-dienoic acid ((5S)- 13 ) and (5R)- 13 (Scheme 5).     

Determination of line tension for systems near wetting

Contact angle measurements for three n-alkanes, heptane, octane, and nonane, on two different self-assembled surfaces (SAM) are reported as a function of drop size. These liquids all formed low contact angles (below 20 degrees ); the measurements were performed using an accurate method for systems with low contact angle, ADSA-D. The observed drop size dependence of the contact angles was interpreted using the modified Young equation. It was concluded that the observed drop size dependence of contact angles was due to line tension. The choice of systems also provided the opportunity to examine the behavior of the line tension for systems near wetting (i.e., low contact angles). It was determined that the line tension is positive and ranges from below 10(-7) to just below 10(-6) J/m for the systems studied; the observations suggested that the line tension decreases as the contact angle decreases and likely vanishes at complete wetting.     

Über die Aufnahme von Blei und Wismut durch Glasoberflächen

Zusammenfassung Versuche über die Adsorption von Radioblei an Glas zeigen, daß aus wäßrigen Lösungen aufgenommene Bleiionen in zwei verschiedenen Zuständen am Glas vorliegen — einem lockeren Adsorptions-Zustand, der auf Ionenaustauschadsorption beruht, und einer festen, vorwiegend homöopolaren Bindung an das Glasnetzwerk. Weitere Versuche gaben Aufschluss über den Mechanismus der Aufnahme in die beiden Zustände. Die Messung der Adsorption und Desorption von Radioblei ist zur Untersuchung von Glasoberflächen geeignet: So ist es — wie durch Versuche an Natronglas und Quarzglas gezeigt wird —möglich, charakteristische Unterschiede zwischen den Oberflächen verschiedener Gläser festzustellen. Weiters erhält man für Glasproben gleicher Zusammensetzung Einblick in die chemische und thermische Vorgeschichte der Oberflächen. Schließlich liefert die Ablösung von Radioblei von Gläsern unter gewissen Bedingungen Aussagen über den Angriff von Lösungen auf das Glas. Auch Wismut kann an Glasoberflächen sehr fest gebunden werden.Herrn Prof. Dr.L. Ebert in Verehrung zum 60. Geburtstag gewidmet.