Transition‐Metal‐Free Reductive Functionalization of Tertiary Carboxamides and Lactams for α‐Branched Amine Synthesis

A new method for the synthesis of α‐branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional‐group compatibility, operates under transition‐metal‐free reaction conditions, and is suitable for various synthetic applications on both sub‐millimole and on multigram scales.     

Transition-Metal-Free Reductive Functionalization of Tertiary Carboxamides and Lactams for α-Branched Amine Synthesis

A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional-group compatibility, operates under transition-metal-free reaction conditions, and is suitable for various synthetic applications on both sub-millimole and on multigram scales.     

PHOSPHONOMETHYLATION OF AMINOALKANOLS PREPARATION OF 4-(PHOSPHONOMETHYL)-2-HYDROXY-2-OXO-1,4,2-OXAZAPHOSPHORINANES1

Abstract

Treatment of aminoalkanols 1 with phosphorous acid and formaldehyde in presence of conc. hydrochloric acid gave mixtures of [(2-hydroxy alkyl)imino] dimethylene diphosphonic acids 3 and 4-(phosphonomethyl)-2-hydroxy-2-oxo-1,4,2-oxazaphosphorinanes 2 from which 2 were isolated as crystalline solids. Similar treatment of 2-amino-2-methyl-1,3-propanediol 8 gave a complex mixture from which dimethylene diphosphonic acid of 5-amino-5-methyl-1,3-dioxane 9 was isolated. 2-Aminoethanethiol, when subjected to phosphonomethylation. gave an unexpected novel quarternary nitrogen product 11. N-Alkylaminoalkanols 4 on phosphonomethylation gave 3:1 mixtures of [N-alkyl-N-(2-hydroxyalkyl)amino] methane phosphonic acid 6 and N-alkyl-2-hydroxy-2-oxo-1,4,2-oxazaphosphorinane 5. Treatment of the crude mixtures of 5 and 6 with aqueous sodium hydroxide gave disodium salts of [N-alkyl-N-(2-hydroxyalkyl)amino] methanephosphonic acid 7. The ratio of the cyclic to the open chain structures obtained as well as the formation of any unexpected novel products is dependent on the structure of the aminoalkanol that is phosphonomethylated. The ¹H, ¹³C and ³¹P spectra are reported for all new compounds.     

REACTION OF PENTAERYTHRITOL WITH DIETHYL PHOSPHOROCHLORIDATE PENTAERYTHRITOL BIS-, TRIS- AND TETRAKIS(DIHYDROGEN PHOSPHATES)

Abstract

Reaction of pentaerythritol 1 with 1, 2 or 3 equivalents of diethyl phosphorochloridate 2 yielded pentaerythritol tris(diethyl phosphate) 5. Treatment of pentaerythritol with 4 or more equivalents of 2 gave pentaerythritol tetrakis(diethyl phosphate) 6. Transesterification of 5 and 6 with trimethylsilyl chloride and sodium iodide in acetonitrile followed by treatment with water gave pentaerythritol tris (dihydrogen phosphate) 7 and pentaerythritol tetrakis(dihydrogen phosphate) 8 respectively. Pentaerythritol bis(dihydrogen phosphate) 9 was prepared by the hydrolysis of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane 3,9-dioxide 10. The compounds 7,8 and 9 were isolated as anilinium salts and characterized by 1H, 13C and 31P NMR spectra.     

Preparation and Structural Studies of [Mo(N3S2){R2(0)PNP(S)R2}2]

Abstract

The compounds [Mo(N₃S₂){Ph₂(O)PNP(S)Ph₂}₂] 1 [Mo(N₃S₂){ⁱPr₂(O)PNP(S)ⁱPr₂}₂] 2 have been synthesised by treating [MoCl₃(N₃S₂)] with KN(PPh₂S)₂ or KN(PⁱPr₂S)₂. X–Ray structures of 1 and 2 have been solved. On complexation, the MoN₃S₂ ring remained planar, but the Mo(OPNPS)₂ rings are puckered.     

Repulsive van der Waals forces in soft matter: why bubbles do not stick to walls

Measurements of nonequilibrium hydrodynamic interactions between bubbles and solid surfaces in water provide direct evidence that repulsive van der Waals forces of quantum origin control the behavior of liquid films on solids in air. In addition to being the simplest and most universal 3-phase system, the deformable air-water interface greatly enhances the sensitivity of force measurements compared with rigid systems. The strength of the repulsive interaction, controlled by the choice of solid, is sufficient to prevent coalescence (sticking) on separation due to hydrodynamic interactions.     

Low loss, low dispersion and highly birefringent terahertz porous fibers

We demonstrate that porous fibers in addition to low loss and high confinement, have near zero dispersion for 0.5-1 THz resulting in reduced terahertz signal degradation compared to microwires. We also show for the first time that these new fibers can be designed, introducing asymmetrical sub-wavelength airholes within the core, to achieve high birefringence ≈0.026. This opens up the potential for realization of novel polarization preserving fibers in the terahertz regime.     

2-Tree probe interval graphs have a large obstruction set

Probe interval graphs (PIGs) are used as a generalization of interval graphs in physical mapping of DNA. G=(V,E) is a probe interval graph (PIG) with respect to a partition (P,N) of V if vertices of G correspond to intervals on a real line and two vertices are adjacent if and only if their corresponding intervals intersect and at least one of them is in P; vertices belonging to P are called probes and vertices belonging to N are called non-probes. One common approach to studying the structure of a new family of graphs is to determine if there is a concise family of forbidden induced subgraphs. It has been shown that there are two forbidden induced subgraphs that characterize tree PIGs. In this paper we show that having a concise forbidden induced subgraph characterization does not extend to 2-tree PIGs; in particular, we show that there are at least 62 minimal forbidden induced subgraphs for 2-tree PIGs.     

Concentration independent calibration of β–γ coincidence detector using 131mXe and 133Xe

Absolute efficiency calibration of radiometric detectors is frequently difficult and requires careful detector modeling and accurate knowledge of the radioactive source used. In the past we have calibrated the β–γ coincidence detector of the Automated Radioxenon Sampler/Analyzer (ARSA) using a variety of sources and techniques which have proven to be less than desirable (Reeder et al., J Radioanal Nucl Chem, 235, 1989). A superior technique has been developed that uses the conversion-electron (CE) and X-ray coincidence of ^131mXe to provide a more accurate absolute gamma efficiency of the detector. The ^131mXe is injected directly into the beta cell of the coincident counting system and no knowledge of absolute source strength is required. In addition, ¹³³Xe is used to provide a second independent means to obtain the absolute efficiency calibration. These two data points provide the necessary information for calculating the detector efficiency and can be used in conjunction with other noble gas isotopes to completely characterize and calibrate the ARSA nuclear detector. In this paper we discuss the techniques and results that we have obtained.