New investigation of the reaction of 2-amino-2-oxazolines with isocyanates and isothiocyanates. Evidence of a transposition during the second step

1996 ◽  
Vol 74 (7) ◽  
pp. 1341-1347 ◽  
Author(s):  
Jean-Jacques Bosc ◽  
Christian Jarry ◽  
Jamal Ouhabi ◽  
Michel Laguerre ◽  
Alain Carpy
Keyword(s):  
Quantum Mechanics ◽  
Key Words ◽  
Second Step ◽  
Experimental Conditions ◽  
Key Words 2 ◽  
X Ray ◽  
Disubstituted Derivative ◽  
Chemical Behaviour

The reaction of some 2-amino-2-oxazolines with isocyanates and arylisothiocyanates yields 3-monosubstituted or 2,3-disubstituted 2-iminooxazolidines depending on the experimental conditions and on the nature of the electrophile reactants. The structures of a mono- and a disubstituted derivative were established by X-ray analysis. The chemical behaviour of the compounds was investigated by molecular and quantum mechanics calculations. An intramolecular transposition during the second step of the reaction was found. Key words: 2-amino-2-oxazolines, iso(thio)cyanates, transposition. X-ray structure, MOPAC calculations.

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

1996 ◽  
Vol 74 (3) ◽  
pp. 287-294 ◽  
Author(s):  
Antonio Lorente ◽  
Marta Casillas ◽  
Pilar Gomez-Sal ◽  
Antonio Manzanero
Keyword(s):  
Double Bond ◽  
Nucleophilic Substitution ◽  
Key Words ◽  
Sodium Methoxide ◽  
Stereoselective Synthesis ◽  
X Ray Diffraction ◽  
Key Words 2 ◽  
X Ray ◽  
Nitrogen Double Bond

The synthesis of (E)-1-methoxy-2-azabuta-1,3-diene-4-carbonitriles was performed by methylation of N-alkenylamides 9 and 11. The Z isomers were obtained by treatment of (E)-1-methylthio-2-azabuta-1,3-diene-4,4-dicarbonitriles with sodium methoxide in methanol. We also describe the reactions of (E)-1-methylthio-2-azabuta-1,3-diene-4,4-dicarbonitriles with pyrrolidine, which afforded 1-(1-pyrrolidinyl) derivatives 20, 21, and 23. X-ray crystallographic analyses of 21 and 23 established the E stereochemistry of the C—N double bond. Key words: 2-azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis, nucleophilic substitution and X-ray diffraction; N-alkenylamides: methylation.

Optimizing conditions for x-ray microchemical analysis in analytical electron microscopy

1978 ◽  
Vol 36 (1) ◽  
pp. 548-549 ◽  
Author(s):  
N. J. Zaluzec
Keyword(s):  
Solid Angle ◽  
Analytical Electron Microscopy ◽  
Incident Beam ◽  
Thin Foil ◽  
Experimental Conditions ◽  
X Ray ◽  
Microchemical Analysis ◽  
Analytical Electron ◽  
Image Position ◽  
Incident Beam Energy

The ultimate sensitivity of microchemical analysis using x-ray emission rests in selecting those experimental conditions which will maximize the measured peak-to-background (P/B) ratio. This paper presents the results of calculations aimed at determining the influence of incident beam energy, detector/specimen geometry and specimen composition on the P/B ratio for ideally thin samples (i.e., the effects of scattering and absorption are considered negligible). As such it is assumed that the complications resulting from system peaks, bremsstrahlung fluorescence, electron tails and specimen contamination have been eliminated and that one needs only to consider the physics of the generation/emission process.The number of characteristic x-ray photons (Ip) emitted from a thin foil of thickness dt into the solid angle dΩ is given by the well-known equation

scholarly journals The internal conversion of gamma-rays.—Part II

1928 ◽  
Vol 121 (787) ◽  
pp. 447-456
Keyword(s):  
Magnetic Field ◽  
Quantum Mechanics ◽  
Wave Equation ◽  
Gamma Rays ◽  
Internal Conversion ◽  
Scalar Potential ◽  
X Ray ◽  
Electro Magnetic Field ◽  
Γ Rays ◽  
Electro Magnetic

In a previous paper the absorption of γ-rays in the K-X-ray levels of the atom in which they are emitted was calculated according to the Quantum Mechanics, supposing the γ-rays to be emitted from a doublet of moment f ( t ) at the centre of the atom. The non-relativity wave equation derived from the relativity wave equation for an electron of charge — ε moving in an electro-magnetic field of vector potential K and scalar potential V is h 2 ∇ 2 ϕ + 2μ ( ih ∂/∂ t + εV + ih ε/μ c (K. grad)) ϕ = 0. (1) Suppose, however, that K involves the space co-ordinates. Then, (K. grad) ϕ ≠ (grad . K) ϕ , and the expression (K . grad) ϕ is not Hermitic. Equation (1) cannot therefore be the correct non-relativity wave equation for a single electron in an electron agnetic field, and we must substitute h 2 ∇ 2 ϕ + 2μ ( ih ∂/∂ t + εV) ϕ + ih ε/ c ((K. grad) ϕ + (grad. K) ϕ ) = 0. (2)

scholarly journals Zeolite NaP1 Functionalization for the Sorption of Metal Complexes with Biodegradable N-(1,2-dicarboxyethyl)-D,L-aspartic Acid

Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2518
Author(s):  
Dorota Kołodyńska ◽  
Yongming Ju ◽  
Małgorzata Franus ◽  
Wojciech Franus
Keyword(s):  
Experimental Data ◽  
Aspartic Acid ◽  
Ph Value ◽  
Complexing Agents ◽  
X Ray Diffraction ◽  
Experimental Conditions ◽  
Modified Zeolite ◽  
X Ray ◽  
Slow Release Fertilizers ◽  
Pseudo Second Order

The possibility of application of chitosan-modified zeolite as sorbent for Cu(II), Zn(II), Mn(II), and Fe(III) ions and their mixtures in the presence of N-(1,2-dicarboxyethyl)-D,L-aspartic acid, IDHA) under different experimental conditions were investigated. Chitosan-modified zeolite belongs to the group of biodegradable complexing agents used in fertilizer production. NaP1CS as a carrier forms a barrier to the spontaneous release of the fertilizer into soil. The obtained materials were characterized by Fourier transform infrared spectroscopy (FTIR); surface area determination (ASAP); scanning electron microscopy (SEM-EDS); X-ray fluorescence (XRF); X-ray diffraction (XRD); and carbon, hydrogen, and nitrogen (CHN), as well as thermogravimetric (TGA) methods. The concentrations of Cu(II), Zn(II), Mn(II), and Fe(III) complexes with IDHA varied from 5–20 mg/dm3 for Cu(II), 10–40 mg/dm3 for Fe(III), 20–80 mg/dm3 for Mn(II), and 10–40 mg/dm3 for Zn(II), respectively; pH value (3–6), time (1–120 min), and temperature (293–333 K) on the sorption efficiency were tested. The Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin adsorption models were applied to describe experimental data. The pH 5 proved to be appropriate for adsorption. The pseudo-second order and Langmuir models were consistent with the experimental data. The thermodynamic parameters indicate that adsorption is spontaneous and endothermic. The highest desorption percentage was achieved using the HCl solution, therefore, proving that method can be used to design slow-release fertilizers.

New pseudohalide ligands in Ru-catalyzed olefin metathesis — A robust, air-activated iminopyrrolato catalyst

2005 ◽  
Vol 83 (6-7) ◽  
pp. 748-754 ◽  
Author(s):  
Samantha D Drouin ◽  
Heather M Foucault ◽  
Glenn PA Yap ◽  
Deryn E Fogg
Keyword(s):  
Key Words ◽  
Olefin Metathesis ◽  
High Reactivity ◽  
Ring Closing Metathesis ◽  
Grubbs Catalyst ◽  
X Ray ◽  
X Ray Crystallography

Reaction of the Grubbs catalyst RuCl2(PCy3)2(CHPh) (1) with lithium 2-[(2,6-diisopropylphenyl)imino]pyrrolide·Et2O (LiNN′·Et2O) gives alkylidene complex 5, containing a chelating, σ-bound iminopyrrolato unit. The structure of 5 is confirmed by X-ray crystallography. Treatment of 5 with pyridine generates RuCl(NN′)(py)2(CHPh) (6) via displacement of PCy3. Complex 5 effects ring-closing metathesis in air, displaying high reactivity relative to 6.Key words: ruthenium, alkylidene, metathesis, pyrrolimine, iminopyrrolato.

scholarly journals Nanotechnology in Roman Opaque Red Glass from the 2nd Century AD. Archaeometric Investigation in Red Sectilia from the Decoration of the Lucius Verus Villa in Rome

Heritage ◽  
2019 ◽  
Vol 2 (3) ◽  
pp. 2597-2611 ◽  
Author(s):  
Mario Bandiera ◽  
Patrice Lehuédé ◽  
Marco Verità ◽  
Luis Alves ◽  
Isabelle Biron ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Chemical Characterization ◽  
Second Step ◽  
Colorimetric Analysis ◽  
Historical Sources ◽  
Pixe Analysis ◽  
X Ray ◽  
Colorimetric Measurements ◽  
Shed Light

This work aims to characterise the chemical composition of Roman opaque red glass sectilia dated to the 2nd century A.D and to shed light on Roman glassmaking production of different shades of red, from red to reddish-brown. Due to the lack of technical historical sources for this period many questions about technological aspects still remain. In this project a multi-disciplinary approach is in progress to investigate the red glass sectilia with several red hues from the Imperial Villa of Lucius Verus (161–169 A.D.) in Rome. First, colorimetric measurements were taken to identify the various red hues. The second step was chemical characterization of the samples and the identification of crystalline colouring phases. Particle Induced X-Ray Emission (PIXE) analysis was used to investigate the chemical composition of these glass samples, while the crystalline phases were identified by Raman Spectroscopy and Scanning Electrons Microscope with Energy Dispersive X-ray Spectrometry (SEM-EDS). Using SEM-EDS nanoparticles were detected as a colouring agent, the chemical composition and the morphology of which has been studied in depth. This information has been compared with the colorimetric analysis to establish any correlation with the different colour hues.

An anti-settling sample delivery instrument for serial femtosecond crystallography

2012 ◽  
Vol 45 (4) ◽  
pp. 674-678 ◽  
Author(s):  
Lukas Lomb ◽  
Jan Steinbrener ◽  
Sadia Bari ◽  
Daniel Beisel ◽  
Daniel Berndt ◽  
...  
Keyword(s):  
Constant Flow ◽  
Syringe Pump ◽  
Experimental Conditions ◽  
Flow Rates ◽  
X Ray ◽  
Constant Flow Rate ◽  
Significant Impairment ◽  
Working Principle ◽  
After Hours ◽  
Serial Femtosecond Crystallography

Serial femtosecond crystallography (SFX) using X-ray free-electron laser (FEL) sources has the potential to determine the structures of macromolecules beyond the limitation of radiation damage and without the need for crystals of sufficient size for conventional crystallography. In SFX, a liquid microjet is used to inject randomly oriented crystals suspended in their storage solution into the FEL beam. Settling of crystals in the reservoir prior to the injection has been found to complicate the data collection. This article details the development of an anti-settling sample delivery instrument based on a rotating syringe pump, capable of producing flow rates and liquid pressures necessary for the operation of the injector. The device has been used successfully with crystals of different proteins, with crystal sizes smaller than 20 µm. Even after hours of continuous operation, no significant impairment of the experiments due to sample settling was observed. This article describes the working principle of the instrument and sets it in context with regard to the experimental conditions used for SFX. Hit rates for longer measuring periods are compared with and without the instrument operating. Two versions of the instrument have been developed, which both deliver sample at a constant flow rate but which differ in their minimum liquid flow rates and maximum pressures.

Photocatalytic Degradation of Methylene Blue over Co-Ag3VO4 under Visible Light Irradiation

2011 ◽  
Vol 335-336 ◽  
pp. 1385-1390 ◽  
Author(s):  
Shuo Wiei Zhao ◽  
Hui Xu ◽  
Hua Ming Li ◽  
Yuan Guo Xu
Keyword(s):  
Methylene Blue ◽  
Photocatalytic Activity ◽  
Visible Light ◽  
Visible Light Irradiation ◽  
Absorption Edge ◽  
Diffuse Reflectance Spectroscopy ◽  
Dye Degradation ◽  
Light Irradiation ◽  
Experimental Conditions ◽  
X Ray

In order to improve the photocatalytic activity, Co was successfully loaded into Ag3VO4 by using impregnation process. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS) and diffuse reflectance spectroscopy (DRS). The XRD and SEM–EDS analyses revealed that Co ion was dispersed on Ag3VO4. The DRS results indicated that the absorption edge of the Co–Ag3VO4 catalyst shifted to longer wavelength. The enhanced photocatalytic activity of Co–Ag3VO4 for Methylene Blue(MB) dye degradation under visible light irradiation was due to its wider absorption edge and higher separation rate of photo-generated electron and holes. In the experimental conditions, it is demonstrated that the MB was effectively degraded by more than 95% within 40 min when the Co–Ag3VO4 catalyst was calcined at 300°C with 1 wt.% Co content.

Crystal structures of highly stabilized ylides: methyl(3-methoxy,2-methoxycarbonylbenzoyl) triphenyl- phosphoranylideneacetate and methyl(2-methoxycarb-6-nitrobenzoyl)triphenyl phos phoranyl ideneacetate and the salt methyl(triphenylphosphoranylidene)acetate tetrafluoroborate

1998 ◽  
Vol 76 (12) ◽  
pp. 1844-1852
Author(s):  
Fernande D Rochon ◽  
Robert Melanson ◽  
Margaret M Kayser
Keyword(s):  
Key Words ◽  
Crystal Structures ◽  
Nitro Derivative ◽  
Transient Species ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ionic Salt ◽  
Higher Temperature ◽  
Cyclic Anhydrides ◽  
Wittig Reactions

At lower temperatures stabilized ylides react with unsymmetrically substituted phthalic anhydrides to give two acyclic adducts. When the reactions are allowed to proceed at higher temperature enol lactones are formed. Identification of the acyclic intermediates was necessary to understand the mechanism of these Wittig reactions. The transient species trapped in the reaction with trimethyloxonium tetrafluoroborate were unambiguously identified by crystallographic methods. The crystal structures of the tetrafluoroborate salt of methyl(triphenylphosphoranyl idene)- acetate (8), methyl(3-methoxy,2-methoxycarbonylbenzoyl)triphenylphosphoranylideneacetate (6β), and methyl(2-methoxycarbonyl,6-nitrobenzoyl)triphenylphosphoranylideneacetate (7α) were studied by X-ray diffraction. The ionic salt (8) is monoclinic, P21c,a= 12.640(5), b = 13.945(9), c = 14.825(6) Å, β = 125.32(3)°, Z = 4, and R = 0.065 (F >5.4 σ(F)). Crystal 6 β is monoclinic, P21c,a = 16.391(16), b = 9.029(6), c = 19.835(19) Å, β = 116.60(6)°, Z = 4, and R = 0.070 (F > 4.6 σ(F)), while crystal 7α is also monoclinic, P21c,a = 9.513(5), b = 9.361(3), c = 30.908(13) Å, β = 98.42(3)°, Z = 4, and R = 0.057 (F >5 σ(F)). In the BF 4- salt (12), the four P-C distances are equal (1.791(5)-1.801(7) Å) with identical tetrahedral angles. For the two triphenylphosphoranylideneacetate compounds, the fourth P-C(1) bond is shorter (1.762(6)-1.734(5) Å) than the three P-C(Ph) bonds (avg. 1.809(5) Å). The angles C(1)-P-C(Ph) are also larger (avg. 112.9(2)° for 6β and 111.9(2)° for 7α) than the C(Ph)-P-C(Ph) angles (avg. 105.8(2)° for 6 β and 106.9(2)° for 7α). These values suggest a multiple nature for the P-C(1) bond. In the nitro derivative, the nitro and the ester groups are disordered equally in positions 2 and 6. Key words: Wittig reactions, cyclic anhydrides, stabilized ylide, phosphoranylidenes, crystal structures.

Synthesis and aldol cyclotrimerization of 4,7-di-tert-butylacenaphthenone

2006 ◽  
Vol 84 (10) ◽  
pp. 1268-1272 ◽  
Author(s):  
Aaron W Amick ◽  
Keith S Griswold ◽  
Lawrence T Scott
Keyword(s):  
Key Words ◽  
Crystal Structures ◽  
Silica Gel ◽  
Room Temperature ◽  
Titanium Tetrachloride ◽  
X Ray ◽  
Synthetic Intermediates

An efficient gram scale synthesis of the previously unknown 4,7-di-tert-butylacenaphthenone (3b) is reported. The facile isomerization of epoxide 9b to ketone 3b occurs simply on stirring a solution of 9b with silica gel at room temperature. Aldol cyclotrimerization of 3b with titanium tetrachloride gives 2,5,8,11,14,17-hexa-tert-butylde cacyclene (1b) in 58% isolated yield. X-ray crystal structures have been obtained for the synthetic intermediates 4,7-di-tert-butylacenaphthene (2b) and 4,7-di-tert-butylacenaphthylene (8b).Key words: aromatic, decacyclene, hydrocarbon, nonalternant, polycyclic.

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