Optimised microwave-assisted synthesis of methylcarbonate salts: a convenient methodology to prepare intermediates for ionic liquid libraries

The reaction of 1-butylpyrrolidine with dimethyl carbonate to yield the ionic liquid precursor, 1-butyl-1-methylpyrrolidinium methylcarbonate, has been investigated under microwave heating conditions and the reaction parameters optimised to achieve 100% yield of the pyrrolidinium salt with no by-products in under 1 h. The reactions of tributylamine, trioctylphosphine, and 1-butylimidazole with dimethyl carbonate under comparable conditions have also been evaluated, yielding the corresponding methylcarbonate salts which can be used as intermediates for the preparation of halide-free ionic liquids without generating any undesirable salt wastes.

Catalytic Mo2C coatings for the water gas shift reaction: Electrosynthesis in molten salts

Electrosynthesis methods using molten salts are suggested for obtaining a new catalytic system based on the Mo2C/Mo composition for the water gas shift reaction. The coatings obtained by the discharge of the carbonate ion on a molybdenum substrate and by the simultaneous reduction of the electroactive species MoO42 and CO32- are catalytically more active than bulk Mo2C or the commercial catalyst Cu-ZnO-Al2O3 by one and three orders of magnitude, respectively.

Synthesis of protective Mo-Si-B coatings in molten salts and their oxidation behavior in an air-water mixture

The formation of various phases during boronizing of silicided molybdenum substrates (MoSi2/Mo) was investigated. Boronizing treatments were conducted in molten salts under an inert gas atmosphere in the 700-1000 degrees C temperature range for 3-7 h. Depending on the process type (non-current or electrochemical) and molten salt temperature, the formation of different boride phases (MoB, Mo2B5, MoB2, MoB4) was observed. At the same time, substantial oxidation of the bulk molybdenum disilicide phase (MoSi2) to the Mo5Si3 phase was observed in non-current boronizing. The oxidation resistance of the coatings was investigated by the weight change in an air-water (2.3 vol.%) mixture at a temperature of 500 degrees C for a period up to 700 h. Results indicated that a two-phase microstructure consisting of the MoSi2, matrix phase with 12-15 wt.% of the MoB4 phase greatly improved the oxidation resistance of the molybdenum substrates. The weight gain rate observed was 6.5 center dot 10(-4) mg/cm(2) h. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis of molybdenum borides and molybdenum silicides in molten salts and their oxidation behavior in an air-water mixture

The formation of various coatings in molybdenum-boron and molybdenum-silicon systems was investigated. Boronizing and siliciding treatments were conducted in molten salts under inert gas atmosphere in the 850-1050 degrees C temperature range for 7 h. The presence of boride (e.g. Mo2B, MoB, Mo2B5) and silicide (MoSi2, Mo5Si3) phases, formed on the surface of Mo plates, was confirmed by X-ray diffraction analysis. The distribution of elements was determined by means of wavelength dispersive spectroscopy (WDS) spectra of the surface and line-scan analyses from surface to interior. Depending on the process type (diffusional or electrochemical) and temperature, the thickness of the protective layers formed on the substrate ranged from 6 to 40 gm. The oxidation resistance of obtained phases was investigated in an air-water mixture in the temperature range of 500-700 degrees C for a period up to 400 h. An improved oxidation behavior of coated plates in comparison with that of pure molybdenum was observed. (c) 2004 Elsevier B.V. All rights reserved.

Chiral thiouronium salts: synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions

Chiral thioureas and functionalised chiral thiouronium salts were synthesised starting from the relatively cheap and easily available chiral amines: (S)-methylbenzylamine and rosin-derived (+)-dehydroabietylamine. The introduction of a delocalised positive charge to the thiourea functionality, by an alkylation reaction at the sulfur atom, enables dynamic rotameric processes: hindered rotations about the delocalised CN and CS bonds. Hence, four different rotamers/isomers may be recognised: syn-syn, syn-anti, anti-syn and anti-anti. Extensive H-1 and C-13 NMR studies have shown that in hydrogen-bond acceptor solvents, such as perdeuteriated dimethyl sulfoxide, the syn-syn conformation is preferable. On the other hand, when using non-polar solvents, such as CDCl3, the mixture of syn-syn and syn-anti isomers is detectable, with an excess of the latter. Apart from this, in the case of S-butyl-N,N'-bis(dehydroabietyl)thiouronium ethanoate in CDCl3, the H-1 NMR spectrum revealed that strong bifurcated hydrogen bonding between the anion and the cation causes global rigidity without signs of hindered rotamerism observable on the NMR time scale. This suggested that these new salts might be used as NMR discriminating agents for chiral oxoanions, and are indeed more effective than their archetypal guanidinium analogues or the neutral thioureas. The best results in recognition of a model substrate, mandelate, were obtained with S-butyl-N,N'-bis(dehydroabietyl) thiouronium bistriflamide. It was confirmed that the chiral recognition occurred not only for carboxylates but also for sulfonates and phosphonates. Further H-1 NMR studies confirmed a 1 : 1 recognition mode between the chiral agent (host) and the substrate (guest); binding constants were determined by H-1 NMR titrations in solutions of DMSO-d(6) in CDCl3. It was also found that the anion of the thiouronium salt had a significant influence on the recognition process: anions with poor hydrogen-bond acceptor abilities led to the best discrimination. The presence of host-guest hydrogen bonding was confirmed in the X-ray crystal structure of S-butyl-N,N'-bis(dehydroabietyl)thiouronium bromide and by computational studies (density functional theory).

Understanding the Effects of Ionicity in Salts, Solvates, Co-Crystals, Ionic Co-Crystals, and Ionic Liquids, Rather than Nomenclature, Is Critical to Understanding Their Behavior

The incorporation of active pharmaceutical ingredients (APIs) into multicomponent solid forms (such as salts and co-crystals) or liquid forms (such as ionic liquids (ILs) or deep eutectic mixtures) is important in optimizing the efficacy and delivery of APIs. However, there is a current debate regarding the classification of these multicomponent systems based on their ionicity which could interfere with their consideration in important applications. Multicomponent systems of intermediate ionicity can show a combination of properties, leading to behavior that is neither strictly typical of either purely ionic or purely neutral compounds, nor easily described as intermediate between the two. In this perspective, we attempt to illustrate the problems in classifying multicomponent APIs based on one of two categories by discussing selected literature regarding solid and liquid multicomponent APIs and presenting the crystal structures of some relevant systems as case studies. It is clear that a focus on restrictive nomenclature carries with it the risk that a thorough examination of the physicochemical properties of the compounds will be overlooked.

Some aspects of the chemistry of 1, 3, 4 - Thiadiazolium salts and related compounds

The work described in this thesis has been divided into seven sections. The first section involves the preparation of N'-acyl-N'-arylN- benzothiohydrazides by the acylation of N'-aryl-N-benzothiohydrazides and is followed by a brief discussion of their possible conformation in solution. The second section deals with the preparation of 1,3,4-thiadiazolium salts by the action of perchloric acid/acetic anhydride on N'-acylN'- aryl-N-benzothiohydrazides and also by the reaction of N'-arylN- benzothiohydrazides with nitriles in an acidic medium. The preparation of 2-methylthio-I,3,4-thiadiazolium methosulfate by methylating the corresponding thione is also described. The third section deals with the reaction of 2-phenyl- and 2-methyl-I,3,4-thiadiazolium salts with alcohols in the presence of base. The stability and spectra of these compounds are discussed. Treatment of the 2-methyl-I,3,4-thiadiazolium salt with base was found to give rise to a dimeric anhydrobase and evidence supporting its structure is given. The anhydrobase could be trapped by a variety of acylating and thioacylating agents before dimerization occurred. In the fourth section, the reaction of N'-acyl-N'-aryl-N-benzothiohydrazides with a variety of acid anhydrides is described. These compounds were found to be identical with those obtained by acylating the anhydrobase. The mass spectral fragmentation of these compounds is described and the anomolous product obtained upon thiobenzoylation of 3-methyl-l-phenyl-pyrazal-5-one is also discussed. The fifth section deals with thioacyl derivatives of the anhydrobase which were prepared by the action of phosphorus pentasulfide upon the oxygen analogues and also obtained as the major product of the reaction of thioacetic acid with compounds related to N'-aryl-N-benzothiohydrazides. The mass spectra and p.m.r. spectra of these compounds are discussed. In the sixth section, the reaction of the 2-methylthio-l,3,4- thiadiazolium salt with active methylene compounds to give acyl and diacyl derivatives of the anhydrobase is described. Some aspects of these compounds are discussed. The seventh section describes the synthesis of ncyanine~' type dyes incorporating the l,3,4-thiadiazole ring and their spectra are briefly discussed.