Methanolysis of (Triphenyl Phosphazenyl) Celoro and Fluorocyclotriphosphazenes

Abstract

The different mechanistic features involved in the replacement of chlorine and fluorine atoms from N₃P₃ (NPPh₃)X₅[X [dbnd] Cl(I) or F(II)] by methoxide have been identified. An oxophosphazadiene derivative is also isolated.     

Synthesis of Novel Spiro[indol-2,2′-pyrroles] Using Isocyanide-Based Multicomponent Reaction

An efficient and facile method for the synthesis of novel spiro[indole-2,2′-pyrroles] from N-methyl-3-isatin imines, t-butyl isocyanide, and dialkyl acetylenedicarboxylate has been achieved by [3 + 2] cyclo addition reaction. All the products were purified by column chromatography as yellow solids and confirmed with ¹H NMR, ¹³C NMR, fast atom bombardment, mass, and infrared. Compound 11 was further confirmed with x-ray analysis.     

An algorithm for overlapped chromatogram separation

Non-negative matrix factorization (NMF) is a recently developed method for real time data analysis. In the past it has been used for facial recognition and spectral data analysis. Most of the NMF algorithms do not converge to a stable limit point and uniqueness in results is also a problem in NMF. To improve the convergence, a new NMF algorithm with modified multiplicative update (ML-NMFmse) has been proposed in this work for strongly overlapped and embedded chromatograms separation. To get same results for all the runs, instead of random initialization, three different initialization methods have been used namely, ALS–NMF (robust initialization), NNDSVD based initialization and EFA based initializations. The proposed ML-NMFmse algorithm is applied on the simulated and experimental overlapped chromatograms obtained for acetone and acrolein mixture, using Gas Chromatography–Flame Ionization Detector. Before applying NMF, Principal Component Analysis (PCA) was applied to determine number of components in the mixture taken. The result of proposed ML-NMFmse is compared with that of existing Multivariate Curve Resolution-Alternating Least Squares method in optimal conditions for both the algorithms. In the case of embedded chromatogram, the proposed ML-NMFmse with Robust method (ALS-NMF) of initialization performs better than all other methods. For a resolution of severely overlapped chromatograms, the proposed ML-NMFmse with NNDSVD method of initialization outperforms all other methods.     

pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways

The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative ¹³C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis of Peptide Cysteine Dimedone Using Fmoc-Cys(Dmd)-OH: Glutathione Cysteine Dimedone as a Probe in Investigating the Sulfenic Acid Mediated Oxidation of Glutathione

Dimedone is the most widely used chemical probe for detection of cysteine sulfenic acid in peptides and proteins. The reaction of dimedone with cysteine sulfenic acid results in the formation of unique cysteine dimedone motif containing thioether bridge. Based on the structure of cysteine dimedone residue in polypeptide, a new building block of Fmoc-Cys(Dmd)-OH was developed for solid phase synthesis of peptide cysteine dimedone. Mass spectrometric sequencing of synthetic peptides have confirmed successful incorporation of cysteine dimedone in peptide chain using HBTU/HOBt as a coupling agent. The new method permits synthesis of peptides containing both cysteine thiol and cysteine dimedone in the same sequence which was difficult to achieve by conventional methods. The synthetic peptide of glutathione cysteine dimedone was used as a standard in probing the air-mediated oxidation of thiol to disulfide form of glutathione. The co-elution of standard peptide and reaction mixture of oxidation of glutathione in presence of dimedone using RP-HPLC have confirmed the formation of glutathione cysteine sulfenic as an intermediate in the air-mediated oxidation of glutathione. The synthetic peptides of cysteine dimedone may find application in the field of redox proteomics and generation of antibodies against modified cysteine residue.     

Preparation,spectral characterization,and single crystal X-ray structures of cis and trans isomers of 2,4,6-trifluoroethoxy-1,3,5-triethyl-1,3,5,2λ5, 4λ5, 6λ5-triazatriphosphorinane-2,4,6-trioxide, [ETNP(O)(OCH2CF3)]3

Oxidation of the cis isomer of the λ³-cyclotriphosphazane [EtNP(OCH₂CF₃)]₃ with trimethylamine-N-oxide (TMNO) gives the cis isomer of trioxo-λ⁵-cyclotriphosphazane [EtNP(O)(OCH₂CF₃)]₃; the trans isomer of [EtNP(O)(OCH₂CF₃)]₃ is obtained by the treatment of a cis and trans mixture of [EtNP(OCH₂CF₃)]₃ with aqueous H₂O₂. The two trioxocyclotriphosphazanes have been characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ¹⁹F, and ³¹P) spectroscopy. The solid state structures of both the isomers have been determined by single crystal X-ray diffraction. The six-membered P₃N₃ ring in both the isomers exhibits a twist-boat conformation; in the cis isomer, the trifluoroethoxy substituents lie on the same side of the ring, whereas, in the trans isomer, two trifluoroethoxy groups are on one side of the ring and the third on the other side of the ring. Crystal data for cis-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 13.593(3), b = 9.721(2), c = 17.539(3) Å, β = 99.49(2)°, V = 2286(1) ų, Z = 4, and Final R = 0.047. Crystal data for trans-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 11.685(4), b = 15.115(5), c = 13.233(5) Å, - = 102.21(3)°, V = 2284(1) ų, Z = 4, and Final R = 0.078.     

Forty years of hydride reductions

Forty years ago, it was observed that diborane, a hydride, reduces aldehydes and ketones with exceptional ease even at 0°. Since then various hydride reagents have evolved for the convenient reduction of typical organic functional groups. Electrophilic reducing agents such as borane and alane possess markedly different reducing characteristics than those of nucleophilic reducing agents such as sodium borohydride and lithium aluminum hydride. Explorations have revealed means of both enhancing and diminishing the electrophilic character of borane and alane on the one hand and both enhancing and diminishing the nucleophilic character of borohydrides and aluminohydrides on the other. Such derivatives reveal unique characteristics making possible valuable selective reductions, not practical previously. These developments have completely altered the procedures normally used in organic chemistry for the reduction of functional groups.     

Finite segmentp-adic number systems with applications to exact computation

Proceedings - Mathematical Sciences - A fractional weighted number system, based on Hensel’sp-adic number system, is proposed for constructing a unique code (called Hensel’s code) for...     

Theory of insulator metal transition and colossal magnetoresistance in doped manganites

The persistent proximity of insulating and metallic phases, a puzzling characteristic of manganites, is argued to arise from the self-organization of the twofold degenerate e(g) orbitals of Mn into localized Jahn-Teller (JT) polaronic levels and broad band states due to the large electron-JT phonon coupling present in them. We describe a new two band model with strong correlations and a dynamical mean-field theory calculation of equilibrium and transport properties. These explain the insulator metal transition and colossal magnetoresistance quantitatively, as well as other consequences of two state coexistence.