Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

N‐(Bis(4‐(2‐ethylhexyloxy)phenyl)(phenyl)‐methyl)methacrylamide was synthesized and polymerized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The chain‐transfer agent (4‐cyano‐4‐(phenylcarbonothioylthio) pentanoic acid (CPADB)), combined with a chiral additive, and a radical initiator yielded polymers with dispersities between 1.2 and 1.4. At low concentrations, the polymers are soluble in hexanes and chloroform while at higher concentrations they swell in these solvents. Characterization of the polymers by wide‐angle X‐ray scattering (WAXS) revealed an interplanar distance of 19.0 Å. The WAXS data combined with polarized optical microscopy support a lamellar crystallization and lyotropic liquid crystalline behavior in hexanes and chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2563–2568     

Efficient and convenient oxidation of alcohols to aldehydes and ketones with molecular oxygen mediated by In(NO3)3 in ionic liquid [C12mim][FeBr4]

A simple, efficient, and ecofriendly procedure for the aerobic oxidation of alcohols to aldehydes and ketones in the presence of In(NO₃)₃/[C₁₂mim][FeBr₄] in aqueous media has been developed. The oxidation reactions afford the target products in good to high yields and no over-oxidation was observed. The products can be separated by a simple extraction with dichloromethane, and the system can be recycled and reused without loss of activity.     

Na2S–Carbon Nanotube Fabric Electrodes for Room‐Temperature Sodium–Sulfur Batteries

A unique sodium sulfide (Na₂S) cathode is developed, which will allow the use of sodium‐free anodes for room‐temperature sodium–sulfur (Na–S) batteries. To overcome the “inert” nature of the Na₂S, a special cathode structure is developed by spreading the multi‐walled carbon nanotube (MWCNT)‐wrapped Na₂S particles onto MWCNT fabrics. Spectroscopic and electrochemical analyses reveal a series of polysulfide intermediates involved in the charge/discharge of the cell. The Na–S battery prepared in full discharge state with the Na₂S/MWCNT cathode provides a remarkable capacity of 500 A h kg^?1 (based on sulfur mass) after 50 cycles.     

Columnar Liquid‐Crystalline Dinaphthoperylenetetracarboxdiimides

Although the double Friedel–Crafts acylation of arenes with ethyl chloroglyoxylate is hindered by the strongly deactivating effect of the first‐entering glyoxylic substituent, the double reaction is successful with the reactive arene perylene under long reaction times and with concomitant ester hydrolysis. The reaction is regiospecific, giving the 3,9‐regioisomer exclusively. This perylenylenediglyoxylic acid is condensed first with o‐bromophenylacetic acid and then with α‐branched alkylamines to yield the title compounds. Whilst the corresponding tetraalkyl esters only show monotropic mesophases, these diimides show enantiotropic columnar mesophases that can be maintained at room temperature if racemically branched alkyl chains of moderate size are used. A palladium‐induced C?C bond migration during the build‐up of the arene system leads to an isomeric side product of reduced symmetry that can be isolated by aggregation‐controlled chromatographic separation. The HOMO and LUMO energies of the title compounds are considerably higher than those of established perylenetetracarboxdiimides.     

The Role of Ate Complexes in the Copper‐Mediated Trifluoromethylation of Alkynes

Trifluoromethylation reactions have recently received increased attention because of the beneficial effect of the trifluoromethyl group on the pharmacological properties of numerous substances. A common method to introduce the trifluoromethyl group employs the Ruppert–Prakash reagent, that is, Si(CH₃)₃CF₃, together with a copper(I) halide. We have applied this method to the trifluoromethylation of aromatic alkynes and used electrospray‐ionization mass spectrometry to investigate the mechanism of these reactions in tetrahydrofuran, dichloromethane, and acetonitrile as well as with and without added 1,10‐phenanthroline. In the absence of the alkyne component, the homoleptic ate complexes [Cu(CF₃)₂]^? and [Cu(CF₃)₄]^? were observed. In the presence of the alkynes RH, the heteroleptic complexes [Cu(CF₃)₃R]^? were detected as well. Upon gas‐phase fragmentation, these key intermediates released the cross‐coupling products R?CF₃ with perfect selectivity. Apparently, the [Cu(CF₃)₃R]^? complexes did not originate from homoleptic cuprate anions, but from unobservable neutral precursors. The present results moreover point to the involvement of oxygen as the oxidizing agent.     

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl

Grignard reagents RMgCl and their so‐called turbo variant, the highly reactive RMgCl?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity‐enhancing effect. A combination of electrospray‐ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion‐ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron‐rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.     

A novel method for determination of inorganic oxyanions by electrospray ionization mass spectrometry using dehydration reactions

Novel methods for the determination of inorganic oxyanions by electrospray (ES) ionization mass spectrometry have been developed using dehydration reactions between oxyanions and carboxylic acids at the ES interface. Twelve oxyanions (VO₃^?, CrO₄^2?, MoO₄^2?, WO₄^2?, BO₃^3?, SiO₃^2?, SiO₄^4?, AsO₄^4?, AsO₂^?, SeO₄^2?, SeO₃^2? and NO₂^?), out of 16 tested, reacted with at least one of four aminopolycarboxylic acids, i.e. iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), trans‐1,2‐diaminocyclohexane‐N,N,N′,N′‐tetraacetic acid and triethylenetetramine‐N,N,N′,N″,N′″,N′″‐hexaacetic acid, at the ES interface to produce the dehydration products that gave intense mass ion responses, sufficient for trace analysis. As examples, trace determinations of Cr^VI and silica in water samples were achieved after online ion exchange chromatography, where the dehydration product of CrO₄^2? and NTA (m/z 290) and that of SiO₄^4? and IDA (m/z 192) were measured. The limits of detection of the respective methods were 17 nM (0.83 ng Cr/ml) for Cr^VI and 0.17 μM (4.8 ng Si/mL) for SiO₄^4?. Copyright © 2016 John Wiley & Sons, Ltd.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526