Regioselective A-Ring Chlorination of Benzodiazepine Analogues Using tert-Butyl Hypochlorite

Treatment of 2-phenyl-2,3-dihydro-1,4-benzodiazepin-5(4H)-one and a series of 1,4-benzoxazepinone analogues with tert-butyl hypochlorite affords products shown, by NMR and MS spectroscopy, to be chlorinated exclusively in the A-ring at positions 7 and/or 9.     

Preparation of Nitriles by Dehydration of Primary Carboxawides with a Supported phosphorus pentoxide reagent

The use of a supported phosphorus pentoxide reagent in the synthesis of selected nitriles is discussed.     

A Convenient Preparation of Carboxylic Acid Anhydrides Using a “Supported” Phosphorus Pentoxide Reagent

Treatment of carboxylic acids with a “supported” phosphorus pentoxide reagent provides a convenient route to the corresponding anhydrides.     

Sterically congested macrobicycles with heteroatomic bridgehead functionality

A series of cyclophanes composed of two triarylelement caps linked by two-atom bridges has been synthesized. The bridgehead functional groups include phosphines in combination with amines, hydrosilanes, methylsilanes, and ethoxysilanes. Computational studies accurately predicted that when the bridgehead substituents are small (lone pairs or protons), an in_,in bridgehead stereochemistry is strongly favored, but larger bridgehead substituents favor the formations of in_,out stereoisomers. The X-ray structures, spectra, and reactivity of these compounds are discussed, as well as the resolution of one of the cyclophanes into pure enantiomers.     

POLYMERIC SURFACTANTS BASED ON OLEIC ACID III. Copolymerization of Sodium Acrylamidostearate and Oleic Acid in a Lamellar Liquid Crystal

Copolymerization of sodium acrylamidostearate (NaAAS) and oleic acid was performed in the lamellar liquid crystal (LLC) formed by NaAAS, oleic acid and water, in the absence of N.N’-methylenebisacrylamide (MBAA) and in the presence of MBAA, respectively. In the absence of MBAA, after the polymerization the lamellar structure remained, and the disorder of the lamellar liquid crystal was, to some extent, enhanced. Surface tension, small-angle X-ray diffraction, viscosity, and fluorescence methods were used to study the properties of the linear copolymer. The linear polymeric surfactant behaves like     

Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study

Phenols, anilines, and malonates have been arylated under metal‐free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “anti‐ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal‐free reagents.     

Contactless conductivity detector array for capillary electrophoresis

A CE system featuring an array of 16 contactless conductivity detectors was constructed. The detectors were arranged along 70 cm length of a capillary with 100 cm total length and allow the monitoring of separation processes. As the detectors cannot be accommodated on a conventional commercial instrument, a purpose built set‐up employing a sequential injection manifold had to be employed for automation of the fluid handling. Conductivity measurements can be considered universal for electrophoresis and thus any changes in ionic composition can be monitored. The progress of the separation of Na⁺ and K⁺ is demonstrated. The potential of the system to the study of processes in CZE is shown in two examples. The first demonstrates the differences in the developments of peaks originating from a sample plug with a purely aqueous background to that of a plug containing the analyte ions in the buffer. The second example visualizes the opposite migration of cations and anions from a sample plug that had been placed in the middle of the capillary.     

One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts

An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30 min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.     

Ultrasonic properties of a suspension of microspheres supporting negative group velocities

The ultrasonic attenuation coefficient, phase velocity, and group velocity spectra are reported for a suspension that supports negative group velocities. The suspension consists of plastic microspheres with an average radius of 80 microm in an aqueous medium at a volume fraction of 3%. The spectra are measured using a broadband method covering a range from 2 to 20 MHz. The suspension exhibits negative group delays over a band near 4.5 MHz, with the group velocity magnitude exceeding 4.3 x 10(8) m/s at one point. The causal consistency of these results is confirmed using Kramers-Kronig relations.     

Sulfur doping of AlN and AlGaN for improved n‐type conductivity

Achieving high levels of n‐type conductivity in AlN and high Al‐content nitride alloys is a long standing problem; significant decreases in conductivity are observed as the Al content is increased, a phenomenon that has been attributed to donors such as oxygen or silicon forming DX centers. We address this problem through a comprehensive first‐principles hybrid density functional study of potential n‐type dopants, identifying S_N and Se_N as two elements which are potential shallow donors because they do not undergo a DX transition. In particular, S_N is highly promising as an n‐type dopant because it also has a low formation energy and hence a high solubility. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)