Improved Synthesis of CsN3

Cesium azide can conveniently be prepared from anhydrous CsF and (CH₃)₃SiN₃ in SO₂ solvent in high purity and yield. In this reaction, the initially generated SO₂F^— anion is converted in SO₂ solvent to solvated azide, (SO₂)_nN₃^—, which is labile and releases SO₂ under dynamic vacuum yielding pure CsN₃.     

Stability-indicating methods for the determination of linezolid in the presence of its alkaline-induced degradation products

Three methods are presented for the determination of linezolid in the presence of its alkaline-induced degradation products. The first method was based on separation of linezolid from its alkaline degradation product by TLC followed by densitometric measurement of the spots of intact drug at 244 nm. The separation was carried out on silica gel 60 F₂₅₄ using isobutanol:ammonia (9:1 v/v) as a mobile phase. The second method was based on first derivative ¹D ultraviolet spectrophotometry with zero crossing point and peak to base measurement. The ¹D value at 251.4 nm was selected for the assay of linezolid in the presence of degradation product. The third method was depended on the first derivative of the ratio spectra ¹DD by measurement of the value at 263.6 nm. The proposed methods were successfully applied to the determination of the drug in bulk powder, in laboratory prepared mixtures with its degradation product and in commercial tablets.     

Beiträge zur Chemie der selteneren Elemente. LXVII*)1). Infrarotabsorptionsspektren von amorphem und kristallinem ScPO42

The IR spectra (400–4000 cm^?1) of hydrated and amorphous scandium phosphate and crystalline ScPO₄ were recorded on samples prehented at 20–1100°C. The course of dehydration and crystallisation of amorphous scandium phosphate was recorded. The PO₄^3?-ion in amorphous anhydrous phosphate shows C_3v symmetry, while in the anhydrous crystalline product V_d site-symmetry occurs. Anhydrous crystalline ScPO₄ spectrum belongs to the xeno-time-type group. The latter represents one from two groups of spectra of anhydrous rare earth phosphates.     

Reaction of [Cp12W2O5] with mercaptocarboxylic acids: Addition rather than reduction. Isolation and characterization of Cp1WO2(SCH2CH2COOH)

The reaction of Cp¹₂W₂O₅ with HS(CH₂)_nCOOH (n = 1, 2) in MeOH or in CH₂Cl₂ solutions at room temperature proceeds in slightly different ways depending on the value of n. For n = 2, it selectively yields compound Cp¹WO₂(SCH₂CH₂CO₂H), which has been isolated and characterized by elemental analysis, NMR and single crystal X-ray diffraction. The reaction is equilibrated, being shifted to the product by absorption of water by anhydrous Na₂SO₄ in CH₂Cl₂, and to the reactants by addition of water. Contrary to the Mo analogue, no products resulting from metal reduction are obtained. The corresponding reaction for n = 1 occurs similarly at low substrate/W ratios (<0.5), but proceeds further to several uncharacterized products for greater substrate amounts. The primary product could not be isolated, but its ¹H NMR spectrum suggests a different, asymmetric structure.     

Alkylation of acylmetalates with alkyl halides to prepare Fischer carbene complexes: an improved protocol

Alkoxy Fischer carbene complexes have been synthesized by alkylation of lithium acylmetalates with alkyl halides in the presence of catalytic amount (5-10 mol %) of n-tetrabutylammonium bromide (n-Bu₄NBr) restricting the temperature below 55 °C to minimize decomposition of the product. The reaction occurs in a biphasic condition involving water and alkyl halide. The effect of cesium on this alkylation reaction has been studied. The presence of a radical quencher, di-tert-butyl phenol, neither affects the yield nor leads to the formation of dimer of di-tert-butyl phenol, which rules out the possibility of radical pathway mechanism. The kinetic study and the ¹H NMR spectra of products suggest an S_N2 pathway particularly involving alkyl halides.     

Lithium‐ und Caesium‐Alkoxometallate

Lithium and Cesium Alkoxometalates The aluminium alkoxide, Al(OCH₂Ph)₃ ( 1 ), can be obtained from a direct synthesis of Al and PhCH₂OH under HgCl₂ catalysis. The formation of the metalate [{(Diglyme)Li}{Al(O^tBu)₄}] ( 2 ) from LiAlH₄ and ^tBuOH in THF under evolution of hydrogen takes place, if the reaction product is heated under reflux with additional ^tBuOH in diglyme. The nucleophilic attack of F^– ions leads during the treatment of CsF on a THF solution of Al(O^cHex)₃ after ligand redistribution to the coordination polymer [{Cs(THF)₂}{Cs(THF)}{Al(O^cHex)₄}₂]_n ([3]_n). 1 , 2 , and 3 were characterized by NMR, IR and MS techniques as well as by crystal structure analyses. According to them 1 is present as tetramer in solution and the solid state. The central structural motif of the metalate 2 is a heteronuclear and planar LiO₂Al four‐membered ring with a penta‐coordinated Li⁺ ion. In the chainlike coordination polymer [ 3 ]_n Cs⁺ ions with coordination number five and six occupy alternating positions.     

Regioselective ring opening of 2-methylaziridine derivatives with F- and F-fluoride

Regioselectivity of the nucleophilic ring opening of N-benzoyl (Bz) and N-benzyloxycarbonyl (Cbz) activated 2-methylaziridines with anhydrous tetramethylammonium fluoride, anhydrous hydrogen fluoride, and ¹⁹F or [¹⁸F]-labelled potassium cryptand fluoride ([K₂₂₂][^18/19F]) were investigated. Whereas all reactions with rigorously anhydrous N(CH₃)₄F did not ring-open the aziridines, reactions with anhydrous HF exclusively yielded the 2-fluoropropanamine derivatives. Reactions of Bz-protected and Cbz-protected 2-methylaziridine with [K₂₂₂][^18/19F] yielded the 2-fluoropropanamine and 1-fluoro-2-propanamine derivatives as the major products, respectively, and represents the first example of regiocontrol during ring opening of aziridines with [¹⁸F]-fluoride.     

Thermal decomposition of potassium tetraborate tetrahydrate to anhydrous potassium tetraborate in a fluidized bed

Production of anhydrous potassium tetraborate from potassium tetraborate tetrahydrate (PTT) was investigated in a controlled fluidized bed calcinatory (FBC). Single step calcination gives a puffed product with very low bulk density and the calcination of potassium tetraborate tetrahydrate is incomplete since agglomeration starts at temperature higher than 250 °C. Effect of the temperature on the bulk density of the product obtained at the end of single step is given and compared with theoretical calculation. In order to obtain anhydrous potassium tetraborate, dehydration should be carried out at least two stages. The most important step dominating the final bulk density is the first step. Dehydration of potassium tetraborate tetrahydrate up to 85% K₂B₄O₇ content and temperature lower than 150 °C in the first step gives commercial available product at final stage. As a result, both puffed and denser anhydrous potassium tetraborate of 99.5% purity with bulk density around 0.4 and 0.7 g cm⁻³ has been produced by two and three stage calcinations.     

ChemInform Abstract: On the Existence of Pentacoordinated Nitrogen.

The thermal decomposition of NF₄HF₂, prepared by reaction of NF₄PF₆ and CsHF₂ in anhydrous HF, is studied by the use of 18F labeled HF₂^- and a radioassay of the decomposition products.     

The lead tetraacetate oxidation of bisacetylhydrazones of α-dicarbonyl compounds

The oxidative cyclization of the title compounds results in generally two different kinds of products. The first, 1-(N,N-bisacetylamino)-1,2,3-triazole 7 (R³ = CH₃) is the primary product, while the second, 1-N-acetylamino-1,2,3-triazole 8 (R³ = CH₃), when observed, is obtained via hydrolysis from the former during work-up and separation of the reaction mixture. The primary products are considered as resulting from intramolecular nucleophilic attack on the acetyl group, of the presumed zwitterionic intermediate 5 (R³ = CH₃), by the N of the ambident N-acetylimine site of 5 .     

Influence of FeCl3‐modified chloroaluminate ionic liquids on long‐chain alkenes alkylation

The influence of anhydrous ferric chloride on the catalytic properties of chloroaluminate ionic liquids catalyst for Friedel–Crafts alkylation was investigated. The catalysts were characterized by Fourier‐transform infrared (FT‐IR) (acetonitrile molecule as probe), specific gravity, and ²⁷Al NMR. Besides, the effect of the mass ratio of FeCl₃ to AlCl₃, catalysts dosage, toluene/olefin molar ratio, reaction temperature, and reaction time on long‐chain alkenes alkylation were investigated thoroughly. And bromine value and high‐performance liquid chromatography (HPLC) were employed as the evaluation method for alkylation products. It was observed that the addition of anhydrous ferric chloride results in improvement in terms of Lewis acid and its catalytic recyclability. Among these catalysts studied, the catalyst modified with 1.0 wt.% anhydrous FeCl₃ showed the best catalytic performance in terms of yield and stability, which can be attributed to the formation of new stronger acidic ions [Al₂FeCl_l0]^? when the added ferric chloride reacts with acidic ions [Al₂Cl₇]^?.     

Calorimetric Investigation of the Complexation of Didodecylcalix[4]arene-crown-6 with Alkali Metal and Ammonium Cations in Acetonitrile

Abstract

The Cs⁺ selectivity of some calix-crown ligands makes them excellent candidates for use in separation systems such as liquid membranes. Separation performance can be understood and predicted from thermodynamic data for cation complexation. We have therefore determined the log K, ΔH and ΔS for the interaction of Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄ ⁺ with didodecyl-calix[4]arene-crown-6 in acetonitrile at 25°C by titration calorimetry. The ligand is strongly selective for Cs⁺, and the selectivity trend results entirely from the enthalpy contribution, with entropy effects opposing the trend. These results are discussed in light of some corresponding data obtained by other researchers with similar ligands.     

Isotopic product rule for solid state lithium nitrate

TheTeller-Redlich type isotopic product rule within the harmonic approximation is found to be satisfactorily applicable to solid state vibrations of anhydrous lithium nitrate,⁶LiNO₃ and⁷LiNO₃.

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Die isotopische Produktenregel für Lithiumnitrat im Festzustand

Zusammenfassung Es wurde festgestellt, daß die Isotopenproduktenregel vomTeller-Redlich-Typ innerhalb der harmonischen Näherung für die Vibrationen von wasserfreiem Lithiumnitrat (⁶LiNO₃ und⁷LiNO₃) im festen Zustand befriedigende Ergebnisse bringt.

     

Ureas as a New Nucleophilic Reagents for SNAr Amination and Carbamoyl Amination Reactions in 1,3,7‐Triazapyrene Series

The ability of urea anions to react as nucleophiles with alkoxy derivatives of 1,3,7‐triazapyrenes has been investigated. It was found that against all expectations, the products of the substitution of an alkoxy groups (S_N^ipso ) by amino group were isolated in good yields. The reactions proceed in anhydrous dimethyl sulfoxide solution at room temperature. But when anions of the mono‐substituted ureas containing bulky substituents were used, the first products of the earlier unknown S_NAr reactions of alkyl carbamoyl amination were obtained.     

Synthese und Kristallstruktur von CsAu(SO4)2

Synthesis and Crystal Structure of CsAu(SO₄)₂ Light yellow single crystals of CsAu(SO₄)₂ were obtained upon evaporation of a solution of Au(OH)₃ and Cs₂SO₄ in sulfuric acid (96 % H₂SO₄). In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 1029.7(2), b = 893.4(2), c = 901.0(1) pm, β = 111.08(1)°) Au³⁺ is in square planar coordination of oxygen atoms which belong to four SO₄^— ions. According to [Au(SO₄)_4/2]^— puckered layers are formed which are connected by the Cs⁺ ions. The latter are surrounded by five chelating and three monodentate sulfate groups leading to a CN of 13.     

Platinum- and CuOx-Decorated TiO2 Photocatalyst for Oxidative Coupling of Methane to C2 Hydrocarbons in a Flow Reactor

Oxidative coupling of methane (OCM) is considered one of the most promising catalytic technologies to upgrade methane. However, C₂ products (C₂H₆/C₂H₄) from conventional methane conversion have not been produced commercially owing to competition from overoxidation and carbon accumulation at high temperatures. Herein, we report the codeposition of Pt nanoparticles and CuO_x clusters on TiO₂ (PC-50) and use of the resulting photocatalyst for OCM in a flow reactor operated at room temperature under atmospheric pressure for the first time. The optimized Cu_0.1Pt_0.5/PC-50 sample showed a highest yield of C₂ product of 6.8 μmol h⁻¹ at a space velocity of 2400 h⁻¹, more than twice the sum of the activity of Pt/PC-50 (1.07 μmol h⁻¹) and Cu/PC-50 (1.9 μmol h⁻¹), it might also be the highest among photocatalytic methane conversions reported so far under atmospheric pressure. A high C₂ selectivity of 60 % is also comparable to that attainable by conventional high-temperature (>943 K) thermal catalysis. It is proposed that Pt functions as an electron acceptor to facilitate charge separation, while holes could transfer to CuO_x to avoid deep dehydrogenation and the overoxidation of C₂ products.     

Structural Diversity in the Solid-State Structures of the Rubidium and Cesium Salts of 2,6-Dimesitylphenylphosphane

A coordination environment reminiscent of a paddle-wheel is exhibited by aryl groups about one of the two cesium ions in CsP(H)Dmp (Dmp=2,6-dimesitylphenyl; structure depicted on the right), which has now been synthesized and is found to exhibit Cs⁺{Cs₂[P(H)Dmp]₃}⁻ contact ion pairs in the solid state. In contrast, the analogous rubidium compound displays a Rb₄P₄ cube as the central structural motif.     

Linear-free energy relationships in solid-state reactions: I. Reactions of cobalt acetate with substituted aniline hydrochlorides

Solid-solid reactions of anhydrous cobalt(II) acetate with various substituted aniline hydrochlorides have been studied. The reaction products, CoCl₂(4-XC₆H₄NH₂)₂, where X = OCH₃, CH₃, F, Br, or Cl, have been characterized. The kinetics have been studied by noting the thickness of the colored boundary of the product. The values of energy of activation are 162.3, 148.6, 120.4, 102.9, and 104.6 kJ mole⁻¹ for X = OCH₃, CH₃, F, Br, and Cl, respectively. A plot of Hammett's constant σ versus log k is linear with values of ϱ 2.321, 2.012, 1.781, and 1.615 at 353, 358, 363, and 368 K, respectively.     

Cs2[Pr6(C2)]I12 - das erste quaternäre reduzierte Halogenid mit isolierten [M6(C2)]-Clustern

Cs₂[Pr₆(C₂)]I₁₂ — the First Quaternary Reduced Halide with Isolated [M₆(C₂)] Clusters . Cs₂[Pr₆(C₂)]I₁₂ is obtained as one of the major products from the reaction of PrI₃, cesium and carbon in sealed tantalum containers at 850°C. The crystal structure triclinic, P 1 ; a=948.1(2), b=953.6(3), c=1 005.2(3) pm; α=71.01(2); β=84,68(3), γ=89.37(2)°; Z=1 contains discrete Pr₆I₁₂-type clusters elongated along the pseudo-four-fold axis to accommodate the C₂ units (d(C—C)=139 pm). The clusters are connected through common ^i?aI and ^a?iI linkages at metal vertices and edges according to Cs₂[Pr₆(C₂)ⁱI₆^i?aI_6/2]^a?iI_6/2. The cesium cations occupy interstices within the (distorted) iodide layers in a way that “Cs₂I₁₈” dimers are formed, in which Cs⁺ is surrounded by eleven I^?. On the basis of the MO scheme of [Sc₆(C₂]I₁₁, the bonding of the C² unit is discussed and compared with other cluster compounds containing C₂ units.     

Development of new methods for the reduction of UF6

Methods for the preparation of UF₅ are discussed with respect to the formation of β-UF₅. The reduction of UF₆ by HBr in liquid HF /1/ can be used to synthesize pure β-UF₅ even if greater amounts are required.Details of the direct photolysis of UF₆ without scavenger /2/ are presented. In an advanced version a simplified photo-reactor is used which consists of a stainless steel vessel with a diameter of 100 mm and a volume of about 3 liters. UV-light of a 1000 W super high pressure mercury lamp is used to photolyze about 50 g of high purity UF₆ within 12 h, giving pure β-UF₅ in about 90 % yield without intermediately removing the F₂ formed.Two simple new methods have been developed to synthesize β-UF₅. UF₆ is reduced by H₂ in liquid anhydrous HF at room temperature. This reaction which is hindered kinetically at room temperature can be catalyzed by metallic Au which is applied as a foil in the stirred reaction mixture.In addition, it was found that anhydrous HCl catalyzes the reaction, too. 200 mbar of HCl were added, together with 4 bar H₂, to UF₆ in liquid HF, and the reaction mixture was magnetically stirred for 66 hours. β-UF₅ could be obtained in 91 % yield as a very pure product. This latter method is recommended for large scale production of β-UF₅.Reactions of UF₆ with other reducing agents like HCl, SO₂, and CO in liquid HF were studied. These reactions give poor yields or impure products.UF₆ yields with CO and Au in the presence of HF a carbonyl compound of Au with the very high ν_CO at 2205 cm^?1. Analytical and spectroscopic data suggest the formula Au(CO)₂U₂F₁₁.