Alternative method for the reduction of aromatic nitro to amine using TMDS-iron catalyst system

The system 1,1,3,3-tetramethyldisiloxane (TMDS)/Fe(acac)₃ is reported here as a new method to obtain amines from aromatic nitro compounds. Amines are synthetized in a straightforward step and are isolated as hydrochloride salts with good to excellent yields. This system has shown a good selectivity toward aryl-chloride, aryl-bromide, ester, carboxylic acid, and cyano groups.The reduction of alkylnitro compounds was unfortunately not possible using this method, only a mixture of mono and dialkylated amine was obtained.     

Cationic polyelectrolytes. V. On macromolecular chain conformational state during amination reactions of CMPS

The macromolecular chain conformational state during the amination of chloromethylated polystyrene (CMPS) with two aliphatic amines, namely methyl(2-hydroxyethyl)amine (MHEA) and N,N-dimethyl(2-hydroxypropyl)amine (DM2HPA), has been studied. Viscosimetric and light scattering measurements were performed during reactions in binary solvent mixtures. The observed kinetic deviations have been related with the conformational transformations of the macromolecular chain.     

Co‐templating Ionothermal Synthesis and Crystal Structure of a New Layered Aluminophosphate from a Protic Deep Eutectic Solvent

Protic deep eutectic mixtures are usually composed of organic amine hydrochloride salts and hydrogen bond donors in a specific molar ratio. Ionothermal synthesis of aluminophosphate as an example, herein, was reported for the first time from an urea‐based protic eutectic mixture, consisting of diethylammonium chloride (DEACl) and 1,3‐dimethyl urea (DMU). As a result, a new two dimensional aluminophosphate with 4.8‐network, [CH₃NH₃]₂[(C₂H₅)₂NH₂]Al₃(PO₄)₄, has been successfully synthesized by co‐templating the DEA and methylamine in situ generated from the decomposition of DMU in the absence of HF. Compared to alkyl quaternary ammonium salts with more alkyl‐group connected with N atom, this kind of organic amine salts are more likely as the structure‐directing agents to synthesize aluminophosphates in urea‐based deep eutectic mixtures. It was also found that HF is crucial to the phase selectivity, a known compound with chain‐like structure was obtained with the single methylamine as a structure‐directing agent in the presence of HF. These materials were characterized by powder XRD, SEM, TG‐DSC, ¹³C CP‐MAS NMR and CHN analyses.     

The role of self-protonation under direct GC-MS determination of amphetamine hydrochloride

Summary We studied the possibility of direct GC-MS determination of amphetamine hydrochloride. In order to avoid the double peak we determined the optimal injector temperature (260°C) and heating rate (40°C min⁻¹). In the direct analysis of amphetamine hydrochloride containing samples, calibration for fragmentm/z=59 (originating from amphetaminium ion fragmentation; the calibrating agent is amphetamine hydrochloride) gave better results than calibration form/z=44 (derived from both free amphetamine and amphetaminium ion; calibration agents were amphetamine or amphetamine hydrochloride). We also compared the mass spectra of amphetamine and amphetamine hydrochloride taken by ion-trap GC-MS. The fragmentation path was cleavage of the C-C bond at benzyl position for the free base or between the phenyl group and the aliphatic moiety, in the case of free base and amphetaminium ion, respectively.     

Principal component analysis of thermal decomposition of magnesium salts used as drugs

Thermal decomposition of magnesium salts of organic acids used in medicine (Mg acetate, Mg valproate, Mg lactate, Mg citrate, Mg hydrogen aspartate, Zn hydrogen aspartate) was analyzed by thermoanalytical, calorimetrical, and computational methods. Thermoanalytical studies were performed with aid of a derivatograph. 50-, 100-, and 200-mg samples were heated in a static air atmosphere at a heating rate of 3, 5, 10, and 15 °C min⁻¹ up to the final temperature of 700–900 °C. By differential thermal analysis (DTA), thermogravimetry (TG), and derivative thermogravimetry (DTG) methods, it has been established that thermal decomposition of the salts under study occurs via two stages. The first stage (dehydratation) was distinctly marked on the thermoanalytical curves. Calorimetrical studies were carried out by using of a heat-flux Mettler Toledo differential scanning calorimetry (DSC) system. Ten milligram samples of compounds under study were heated in the temperature range from 20 to 400 °C at a heating rate of 10 and 20 °C min⁻¹ under an air stream. The studies showed that the values of transitions heats and enthalpies of dehydration for investigated salts varied with the increasing of heating rate. For chemometric evaluation of thermoanalytical results, the principal component analysis (PCA) was applied. This method revealed that points on PC1 versus PC2 diagrams corresponding to the compounds of similar chemical constitution are localized in the similar ranges of the first two PC’s values. This proves that thermal decomposition reflects similarity in the structure of magnesium salts of organic acids.     

Direct Preparation of Amides from Amine Hydrochloride Salts and Orthoesters: A Synthetic and Mechanistic Perspective

The conversion of a wide range of primary and secondary aliphatic and a few arylamine hydrochloride salts to their corresponding acetamides with trimethyl orthoacetate is described. Mechanistic studies using NMR and gas chromatography–mass spectrometry techniques indicate these reactions proceed via an O-methylimidate intermediate that undergoes in situ demethylation by chloride, affording the corresponding acetamides. Synthetically, this reaction represents a practical, high-yielding protocol with a simple workup for the rapid conversion of amine hydrochloride salts to acetamides.     

S→N type Smiles rearrangement of the aminoethanethiol moiety attached to heterocyclic compounds

Base catalysed S→N type Smiles rearrangement of aminoethanethiol-substituted pyridine and triazine compounds led to formation of the corresponding thiol or disulfide compounds. Prior to rearrangement, the heteroaryl sulfanylethylamines could be prepared in high yields as the hydrochloride or trifluoroacetate salts from the corresponding tert-BOC protected amine.     

Thermoanalytical Studies of Ga-substituted MBa2Cu3O7–δ Superconducting Compounds Formation (M=Yb,Eu)

A thermoanalytical study in non-isothermal conditions was realized on Ga-substituted MBa₂Cu₃O_7-δ superconducting compounds formation (M=Yb, Eu). The presence of different oxides in the reaction mixtures leads to different reactivity of the system. The type of lanthanoide ion present in the studied compositions determines the reactivity of the system. In the system containing Eu the solid state reactions start at lower temperature than in the system containing Yb. Ga-substitution does not change evidently the thermal behavior of the unsubstituted samples. Different reactivities of the studied reaction mixtures led, after similar thermal treatment in isothermal conditions, to samples with different structure and superconducting properties. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cyclopalladation and Reactivity of Amino Esters through C?H Bond Activation: Experimental,Kinetic, and Density Functional Theory Mechanistic Studies

The orthopalladation, through C? H bond activation, of a large number of amino esters and amino phosphonates derived from phenylglycine, and having different substituents at the aryl ring and the C‐α atom, as well as on the N‐amine atom, has been studied. The experimental observations indicated an improvement in the yields of the orthopalladated compounds when the N‐amine and/or the C‐α atom are substituted, when compared with the unsubstituted methyl phenylglycinate derivatives. In contrast, substitutions at the aryl ring do not promote significant changes in the orthometalation results. Furthermore, the use of hydrochloride salts of the amino esters has also been shown to have a remarkably favorable effect on the process. All these observations have been fully quantified at different temperatures and pressures by a detailed kinetic study in solution in different solvents and in the presence and absence of added Brønsted acids and chloride anions. The data collected indicate relevant changes in the process depending on these conditions, as expected from the general background known for cyclopalladation reactions. An electronic mechanism of the orthopalladation has been proposed based on DFT calculations at the B3LYP level, and a very good agreement between the trends kinetically measured and the theoretically calculated activation barriers has been obtained. The reactivity of the new orthopalladated amino phosphonate derivatives has been tested and it was found that their halogenation, alkoxylation and carbonylation resulted in formation of the corresponding functionalized ortho‐haloaminophosphonates, ortho‐alkoxyaminophosphonates and oxoisoindolinylphosphonates.     

Unprecedented catalytic asymmetric reduction of N-H imines

[Reaction: see text] Addition of lithium bis(trimethylsilyl)amide to perfluorinated ketones 1a-j affords (E)-N-TMS-ketimines 2a-j that are reduced in situ to afford racemic perfluoromethylated amine hydrochloride salts 3a-j in 54-97% yields. Solvolysis of the N-Si bond in MeOH leads to formation of bench-stable, isolable N-H imine Z/E isomer mixtures along with a methanol adduct. Enantioselective reduction of these three-component mixtures provides the first catalytic asymmetric synthesis of trifluoromethylated amines in 72-95% yields and 75-98% ee.     

Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

Increase in flotation activity of salts of higher aliphatic amines, potassium chloride collectors

For increasing the flotation activity of potassium chloride collector, salts of higher aliphatic amines, effects of a temperature of collector solutions, mixtures of homologues of different chain length, a solubilization of organic oleophilic compounds in the colloidal solutions of amine salts were examined on their micellar structure and ion-molecular composition.     

Über die Darstellung von Trilithium-trisulfimid (Trilithium-1,3,5,2,4,6-trithiatriazin-1,1,3,3,5,5-hexaoxid) und die thermische Zersetzung einiger Salze des Trisulfimids

Trilithiumhexaoxocyclotrithiazane^* (trilithiumtrisulfimid) has been prepared for the first time by reaction of triammoniumtrisulfimid with LiOH in a solid state reaction and by using high boiling alcohols as reaction medium. The thermolysis of different salts of trisulfimid (Na-, K-, Li-, Ag-, NH₄-salt) has been studied by thermoanalytical methods in the region between 25–500 C. The course of decomposition of these compounds is discussed by IR and chromatographic measurements.

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Diesen Namen verwendetI. Haiduc in: The Chemistry of Inorganic Ring Systems. Wiley-Interscience. 1970.     

Starch xanthate–polyethylenimine reaction mechanisms

The chemical nature of starch xanthate (SX)–polyethylenimine (PEI) reaction products has been studied because of their effectiveness as wet-end additives for improving strength properties of paper. Model compounds, in conjunction with ultraviolet, infrared, and chemical analyses, served to elucidate SX–PEI reaction mechanisms. Aqueous solutions of SX (degrees of substitution 0.1–0.5) were titrated with PEI at pH 5–7 (25–30°C) to form SX–PEI flocculent precipitates that were determined to be polyelectrolyte complexes. However, when solutions of SX–PEI were kept at pH 10–12, products were formed that included dithiocarbamic acid salts in major quantities, PEI thioureas, and minor quantities of O-starch PEI thinocarbamate. Acid precipitation of these SX–PEI polymeric reaction products from their alkaline solutions, which contained residual xanthate and PEI, also yielded polyelectrolyte complexes. Model systems suggest that PEI thiuram disulfide and starch xanthide, possible products of air oxidation, could be present in minor amounts and would react rapidly with PEI to yield thioureas and thioncarbamates, respectively. Apparently, mixtures of xanthate and amine gave (1) dithiocarbamic acid salts from both xanthate groups and CS₂ (decomposition from xanthate), (2) thioureas from both dithiocarbamic acid salts and thiuram disulfide, and (3) thioncarbamates, principally from xanthate as opposed to xanthide.     

Production of gaseous matrix-free reference materials

Reference materials are used in every laboratory in order to assure the appropriate quality of analytical results. The production of reference materials is not an easy task especially in the case of gaseous, toxic and malodorous compounds. Thermal decomposition of immobilized compounds is a convenient way for the generation of those kinds of mixtures. Temperature is an important variable in this process. In this case, thermoanalytical techniques (thermogravimetry and differential scanning calorimetry (TG-DSC)) and scanning electron microscopy (SEM) were used for checking the temperature range which had been previously determined using thermal desorber-gas chromatograph-flame ionization detector (TD-GC-FID) system.     

Analytical applications of liquid-liquid phase equilibria: analysis of binary mixtures of chemically similar components

A new, simple and rapid method based on the principle of liquid-liquid phase equilibria has been developed for the analysis of binary mixtures of chemically similar organic compounds. The method does not require elaborate instrumentation and can be used to analyse mixtures of members of homologous series. The application of the method has been illustrated by analysing binary mixtures of n-hexane and n-octane; the maximum uncertainty in this analysis is ~2%.     

Multiwavelength Spectrophotometric Determination of Acid Dissociation Constants. Deconvolution of Binary Mixtures of Ionizable Compounds

ABSTRACT

A spectral deconvolution method based on target factor analysis has been developed to determine pK_a values of binary mixtures of monoprotic and/or diprotic ionizable compounds. The technique makes use of the approach of Frans and Harris, which has been implemented previously for mixtures of monoprotic compounds (Anal. Chem. 1985, 57, 1718-1721), to extract the unknown pK_a values. The method has been illustrated by using the multiwavelength spectrophotometrictitation data of binary mixtures of: I. benzoic acid and phenol, 2. benzoic acid and nicotinic acid, 3. p-aminosalicylic acid and phthalic acid. It was demonstrated that the pK_a values as determined in this study are in good agreement with the literature.     

The Electrochemical Grafting of a Mixture of Substituted Phenyl Groups at a Glassy Carbon Electrode Surface

Two‐component substituted aryl groups are simultaneously grafted onto the surface of a glassy carbon electrode by electrochemical reduction of a binary mixture of two aryl diazonium salts in acetonitrile. The electrochemical deposition is achieved potentiostatically and two different mixtures with four different ratios of diazonium salts are used. The binary mixtures comprise: 1) 4‐nitrophenyl diazonium and 4‐bromophenyl diazonium cations and 2) 4‐bromophenyl diazonium and N,N‐diethylaniline diazonium cations. The chemical composition of the two component films is determined by cyclic voltammetry in an electrolyte inert for electroactive groups such as nitrophenyl and bromophenyl. X‐ray photoelectron spectroscopy is also used to evaluate the surface concentration of each grafted substituted phenyl group. The surface concentration of the substituted phenyl group for which the corresponding diazonium cation is the most easily reduced is higher than its concentration in the mixture of the deposition solution. The usefulness of binary films is also discussed.     

The effect of monoethanolamine on conductivity and efficiency of electrodialysis of acid and salt solutions

Experimental studies of the specific conductivity (SC) are carried out for aqueous solutions of organic and inorganic acids and salts including those containing different amounts of monoethanolamine (MEA), which model the absorption solutions used in purification of gas mixtures from carbon dioxide and containing heatstable salts (HSS). It is shown that the addition of MEA to binary aqueous electrolyte solutions gives rise to changes in the SC: in the MEA concentration range from 0 to ～1.5 M, the SC of the resulting ternary solutions increases but decreases again with the further increase in MEA concentration. This behavior of SC is typical also of aqueous binary amine solutions. It is shown that in the presence of MEA, the quantitative removal of dissolved acids and salts proceeds faster with the simultaneous increase in the specific energy consumption by a factor of 7–9 (up to 85.7–93.6 kJ/dm³). It is assumed that the reason for the decrease in SC and the enhancement of energy consumption at electrodialysis of mixed solutions is the probable existence of monoethanolamine both as free solvated ions and neutral molecules and as self-assembled associated structures (ion pairs and more complex particles) which involve also the ions of salts dissolved in amine-containing solutions.     

The Synthesis and Reactions of 1-(2-Propynyl)pyidinium Salts

The synthesis of 1-(2-propynyl)pyridinium salts 3 described. Compounds 3 react with a second pyridine molecule, in the presence of the corresponding hydrochloride, to form products of type 4, Certain bases cause the 1-(2-propynyl)pyridinium salts 3 to rearrange into 1-propadienylpyridinium salts. 5 . Diethylamine converts compounds 3 into 1-acetonylpyridinium salts 8 . Moreover, treatment of 3 or 5 with sodium methoxide gives enol ether sof type 9, which can be hydrolyzed to teh ketones 8 . Addition of bromine to some of teh unsaturated compounds is also reported.