Sulfamic acid: an efficient, cost-effective and recyclable solid acid catalyst for the three-component synthesis of α-amino nitriles

α-Amino nitriles are synthesized by the three-component coupling reaction of aldehydes, amines and trimethylsilyl cyanide using sulfamic acid as a heterogeneous solid acid catalyst, under solvent-free conditions in excellent yields. The catalyst was recovered by simple filtration and was recycled in subsequent reactions.     

N-tert-Butoxycarbonylation of amines using H3PW12O40 as an efficient heterogeneous and recyclable catalyst

The commercially available heteropoly acid H₃PW₁₂O₄₀ (0.5 mol %) is a very efficient and environmentally benign catalyst for N-tert-butoxycarbonylation of amines (primary, secondary) with di-tert-butyl dicarbonate at room temperature in short reaction times (<10 min). No competitive side products such as isocyanates, ureas, N,N-di-tert-butoxycarbonyls, O-Boc and oxazolidinones were observed. Chiral α-amino alcohols and esters afforded the corresponding N-Boc derivatives chemoselectively in excellent yields.     

IR study of ammonia adsorption on Lewis acidic sites on a V2O5/Al2O3 catalyst

Reduction of V₂O₅/Al₂O₃ catalyst has been shown to affect the adsorption of ammonia on Lewis acid sites. The band of NH₃ (ad) at 1243 cm^–3 is sensitive to oxygen under mild conditions. An adsorbed species with IR absorption at 1300 cm^–1 is likely to undergo dissociation to form NH₂.

---

V₂O₅/Al₂O₃ . NH₃ () 1243 ^–1 . 1300 ^–1 , NH₂.

     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.     

Preparation of poly(vinylalcohol)/poly(acrylamide‐co‐vinyl imidazole)/γ‐Fe2O3 semi‐IPN nanocomposite and their application for removal of heavy metal ions from water

A series of magnetic semi‐interpenetrating polymer network (semi‐IPN) hydrogels was prepared in one‐stage strategy composed of linear poly(vinyl alcohol) (PVA) chains and magnetic γ‐Fe₂O₃ nanoparticles entrapped within the cross‐linked poly(acrylamide‐co‐vinylimidazole) (poly(AAm‐co‐VI)) network. The influence of PVA, weight ratio of AAm:VI, γ‐Fe₂O₃, and MBA on the swelling properties of the obtained nanocomposite hydrogels was evaluated. The prepared magnetic semi‐IPN hydrogels were fully characterized and used as absorbent for removal of Pb(II) and Cd(II) from water. Factors that influence the metal ion adsorption such as solution pH, contact time, initial metal ion concentration, and temperature were studied in details. The experimental results were reliably described by Langmuir adsorption isotherms. The adsorption capacity of semi‐IPN nanocomposite for Pb(II) and Cd(II) were175.80 and 149.76 mg g^?1, respectively. The kinetic experimental data indicated that the chemical sorption is the rate‐determining step. According to thermodynamic studies, Pb(II) and Cd(II) adsorption on the hydrogels was endothermic and also chemical in nature. The prepared magnetic PVA/poly(AAm‐co‐VI) semi‐IPN hydrogels could be employed as efficient and low‐cost adsorbents of heavy metal ions from water. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis of Amaryllidaceae Constituents and Unnatural Derivatives

This update covers the syntheses of Amaryllidaceae alkaloids since the publication of the last major review in 2008. A short summary of past syntheses and their step count is provided for the major constituents; pancratistatin, 7‐deoxypancratistatin, narciclasine, lycoricidine, lycorine, and for other natural constituents, as well as for unnatural derivatives. Discussion of biological activities is provided for unnatural derivatives. Future prospects and further developments in this area are covered at the end of the review. The literature is covered to the end of August 2015.     

The first phosphoramide–mercury(II) complex with a Cl2Hg–OP[N(C)(C)]3 segment

Mercury(II) exhibits a strong preference for linear coordination which has been attributed to relativistic effects splitting the 6p orbitals and promoting sp hybridization. If the two ligands attached to the mercury(II) ion are weak donors, the metal ion can act as a good Lewis acid and expand its coordination number. Moreover, mercury has a special affinity for softer bases, such as S and N atoms, and has much less affinity for hard bases, such as those including an O atom. The asymmetric unit of dichlorido[tris(piperidin‐1‐yl)phosphane oxide‐κO]mercury(II)–dichloridomercury(II) (2/1), [HgCl₂{(C₅H₁₀N)₃PO}]₂·[HgCl₂], is composed of one HgCl₂{(C₅H₁₀N)₃PO} complex and one half of a discrete HgCl₂ entity located on an inversion centre. The coordination environment around the Hg^II centre in the complex component is a distorted T‐shape. Bond‐valence‐sum calculations confirm the three‐coordination mode of the Hg^II atom of the complex molecule. The noncovalent nature of the Hg…Cl and Hg…O interactions in the structure are discussed.     

Ether and Relativity

We consider one of the fundamental debates in performing the relativity theory, namely, the ether and the relativity points of view, in a way to aid the learning of the subjects. In addition, we present our views and prospects while describing the issues that being accessible to many physicists and allowing broader views. Also, we very briefly review the two almost recent observations of the Webb redshift and the ultra high energy cosmic rays, and the modified relativity models that have been presented to justify them, wherein we express that these justifications have not been performed via a single model with a single mechanism.     

Phase-Transition Thermal Charging of a Channel-Shape Thermal Energy Storage Unit: Taguchi Optimization Approach and Copper Foam Inserts

Thermal energy storage is a technique that has the potential to contribute to future energy grids to reduce fluctuations in supply from renewable energy sources. The principle of energy storage is to drive an endothermic phase change when excess energy is available and to allow the phase change to reverse and release heat when energy demand exceeds supply. Unwanted charge leakage and low heat transfer rates can limit the effectiveness of the units, but both of these problems can be mitigated by incorporating a metal foam into the design of the storage unit. This study demonstrates the benefits of adding copper foam into a thermal energy storage unit based on capric acid enhanced by copper nanoparticles. The volume fraction of nanoparticles and the location and porosity of the foam were optimized using the Taguchi approach to minimize the charge leakage expected from simulations. Placing the foam layer at the bottom of the unit with the maximum possible height and minimum porosity led to the lowest charge time. The optimum concentration of nanoparticles was found to be 4 vol.%, while the maximu possible concentration was 6 vol.%. The use of an optimized design of the enclosure and the optimum fraction of nanoparticles led to a predicted charging time for the unit that was approximately 58% shorter than that of the worst design. A sensitivity analysis shows that the height of the foam layer and its porosity are the dominant variables, and the location of the porous layer and volume fraction of nanoparticles are of secondary importance. Therefore, a well-designed location and size of a metal foam layer could be used to improve the charging speed of thermal energy storage units significantly. In such designs, the porosity and the placement-location of the foam should be considered more strongly than other factors.     

3D vs. turbostratic: controlling metal–organic framework dimensionality via N-heterocyclic carbene chemistry

Using azolium-based ligands for the construction of metal–organic frameworks (MOFs) is a viable strategy to immobilize catalytically active N-heterocyclic carbenes (NHC) or NHC-derived species inside MOF pores. Thus, in the present work, a novel copper MOF referred to as Cu-Sp5-BF₄, is constructed using an imidazolinium ligand, H₂Sp5-BF₄, 1,3-bis(4-carboxyphenyl)-4,5-dihydro-1H-imidazole-3-ium tetrafluoroborate. The resulting framework, which offers large pore apertures, enables the post-synthetic modification of the C² carbon on the ligand backbone with methoxide units. A combination of X-ray diffraction (XRD), solid-state nuclear magnetic resonance (ssNMR) and electron microscopy (EM), are used to show that the post-synthetic methoxide modification alters the dimensionality of the material, forming a turbostratic phase, an event that further improves the accessibility of the NHC sites promoting a second modification step that is carried out via grafting iridium to the NHC. A combination of X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) methods are used to shed light on the iridium speciation, and the catalytic activity of the Ir–NHC containing MOF is demonstrated using a model reaction, stilbene hydrogenation.

A new MOF with a saturated N-heterocyclic carbene ligand undergoes a series of structural transformations to produce a turbostratic material, which serves as a better support for an iridium hydrogenation catalyst, when compared to the parent material.