New aminomethylphosphines with cyanophenyl substituents at the nitrogen atoms

A condensation of bis(hydroxymethyl)arylphosphines with 3- and 4-aminobenzonitriles leads to the corresponding 3,7-diaryl-1,5-bis(cyanophenyl)-1,5-diaza-3,7-diphosphacyclooctanes. Acyclic (aryl)bis[N-(2-cyanophenyl)aminomethyl]phosphines are formed in the case of 2-aminobenzonitrile. Molecular and crystalline structure of the compounds obtained was studied by X-ray diffraction analysis.     

Reactivity of Diarylnitrenium Ions

Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar₂N⁺. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar₂NH^.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar₂NH₂⁺. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me₅C₆, leading to a novel iminium radical cation, Ar=N^.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N⁺HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions.     

15N NMR Study of the P-N Bonding in Phosphoric Amides

Abstract

A series of phosphoric amidodiesters, diamidoesters and triamides was prepared and their ³¹P and¹⁵ N NMR spectra were recorded in order to evaluate the major structural factors that determine the chemical shifts and coupling contants values. Considering the equation expressing the structural effects on shielding^[1].     

Oxone/Sodium Chloride: A Simple and Efficient Catalytic System for the Oxidation of Alcohols to Symmetric Esters and Ketones

An efficient method for the oxidation of alcohols is presented. The use of catalytic amounts of sodium chloride in combination with oxone allows the conversion primary aliphatic alcohols to symmetric esters. Secondary alcohols can be easily oxidized to ketones, and benzylic alcohols are converted to the corresponding aldehydes. The method is cost effective and enviromentally benign.     

Lead Structures for New Antibacterials: Stereocontrolled Synthesis of a Bioactive Muraymycin Analogue

Naturally occurring muraymycin nucleoside antibiotics represent a promising class of novel antibacterial agents. The structural complexity suggests the investigation of simplified analogues as potential lead structures, which can then be further optimized towards highly potent antimicrobials. Herein we report studies on muraymycin‐derived potential lead structures lacking an aminoribose motif found in most naturally occurring muraymycins. We have identified a 5′‐defunctionalized motif to be ideal in terms of stability and chemical accessibility and have synthesized a full‐length muraymycin analogue based on this structure using a novel fully stereocontrolled route. The obtained 5′‐deoxy analogue of the natural product muraymycin C4 showed good inhibitory properties towards the bacterial target protein MraY, sufficient pharmacokinetic stability and no cytotoxicity against human cells, thus making it a promising lead for antibacterial drug development.     

Study of the structures and photophysical properties of 1,3-diaza-5-phosphacyclohexanes using density functional theory and optical spectroscopy

Russian Chemical Bulletin - The steric and electronic structures of 1,3-diaza-5-phoaphacyclohexane with the pyridyl substituent at the phosphorus atom and a series of model...     

The Elusive Ketene (H2CCO) Channel in the Infrared Multiphoton Dissociation of Solid 1,3,5-Trinitro-1,3,5-Triazinane (RDX)

Understanding of the fundamental mechanisms involved in the decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) still represents a major challenge for the energetic materials and physical (organic) chemistry communities mainly because multiple competing dissociation channels are likely involved and previous detection methods of the products are not isomer selective. In this study we exploited a microsecond pulsed infrared laser to decompose thin RDX films at 5 K under mild conditions to limit the fragmentation channels. The subliming decomposition products during the temperature programed desorption phase are detected using isomer selective single photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). This technique enables us to assign a product signal at m/z=42 to ketene (H₂CCO), but not to diazomethane (H₂CNN; 42 amu) as speculated previously. Electronic structure calculations support our experimental observations and unravel the decomposition mechanisms of RDX leading eventually to the elusive ketene (H₂CCO) via an exotic, four-membered ring intermediate. This study highlights the necessity to exploit isomer-selective detection schemes to probe the true decomposition products of nitramine-based energetic materials.