Tertiary Ammonium Salts Research Articles

Bis(triethylammonium) tetrachloridomanganate(II)

The title compound, (Et3NH)2[MnCl4], was obtained unexpectedly in an attempt to prepare a carboxyl­ate-bridged coordination network. It is the first reported structure of a tertiary ammonium salt of the tetra­hedral [MnCl4]2− anion (Table 1). Each of the two crystallographically independent cations forms an N—H⋯Cl hydrogen bond to the anion (Table 2), generating discrete ion triples. The Mn—Cl bonds involving the hydrogen-bonded Cl atoms are longer than the others.

Synthesis, characterization and crystal structures of boron-containing intermediates in the reductive amination of ferrocenecarboxaldehyde to a bis(ferrocenylmethyl) amine

Reaction of ferrocenecarboxaldehyde with aqueous methylamine leads to [(methylimino)methyl]ferrocene, which is reduced to N-(ferrocenylmethyl)- N-methylamine by NaBH 4. This amine reacts with ferrocenecarboxaldehyde and NaCNBH 3 to give the tertiary ammonium salt, di( N-(ferrocenylmethyl))- N-methylammonium cyanoborohydride. Hydrolysis of the NaCNBH 3 reaction mixture produces the free amine, di( N-(ferrocenylmethyl))- N-methylamine. Thermolysis of di( N-(ferrocenylmethyl))- N-methylammonium cyanoborohydride in refluxing tetrahydrofuran converts it to the cyanoborane adduct, di( N-ferrocenylmethyl)- N-methylamine–cyanoborane, with elimination of H 2. The new compounds are fully characterized by using spectroscopic and physical methods, including X-ray crystal structure determinations of di( N-(ferrocenylmethyl))- N-methylammonium cyanoborohydride, di( N-(ferrocenylmethyl))- N-methylamine, and di( N-(ferrocenylmethyl))- N-methylamine–cyanoborane.

Homopolymerization of epoxy monomers initiated by 4-(dimethylamino)pyridine

The anionic epoxy homopolymerization initiated by tertiary amines, imidazoles, and ammonium salts is a complex reaction exhibiting two undesired characteristics for practical applications: (a) slow reaction rates with long induction periods, and (b) short primary chains due to the high rate of chain transfer reactions. Therefore, these systems have not found an important place in commercial applications. In this study, it is shown that using 4-(dimethylamino)pyridine (DMAP) as initiator of the polymerization of phenyl glycidyl ether (PGE) or diglycidyl ether of bisphenol A (DGEBA) enables to obtain high polymerization rates and longer primary chains than those generated using typical initiators. A critical molar ratio DMAP/epoxy groups was necessary to attain complete conversion. Networks resulting from the DMAP-initiated homopolymerization of DGEBA exhibited a high crosslink density and corresponding high values of the glass transition temperature (Tg = 160°C) and of the rubbery elastic modulus (higher than 100 MPa). An intense brown color of reaction products, associated with an absorption band with a maximum at 360 nm, was ascribed to the presence of initiator fragments with conjugated double bonds in chain ends. These results might revalorize the anionic homopolymerization of epoxy monomers for commercial applications. POLYM. ENG. SCI. 46:351–359, 2006. © 2006 Society of Plastics Engineers

Combination of ring-opening polymerization and “click” chemistry towards functionalization of aliphatic polyesters

Azide pendent groups of aliphatic polyesters have been derivatized into tertiary amines, ammonium salts and poly(ethylene oxide) grafts. The experimental conditions have been optimized (organic solvent, 35 degrees C), such that the aliphatic polyesters are not degraded, including even poly(lactide) which is very sensitive to attack by weak nucleophiles.

Complexation of an acrylic resin by tertiary amines: synthesis and characterisation of new binders for antifouling paints

Antifouling coatings are the most reliable way to prevent biofouling of immersed surfaces. As concerning the high toxicity of organotin paints, the tendency is the development of coatings, which do not present environmental risks. In this work, we prepare binders from modification of acrylic copolymers containing free carboxylic acid groups. Biocides chosen are tertiary ammonium salts; alkyl chain substituents with different length are considered. The chemical modifications of resins are carried out via a single step reaction. Modification extents are monitored through proton nuclear magnetic resonance and thermogravimetric analysis and the modified resins are characterised by Fourier transform infrared spectroscopy. The glass transition temperature of the acrylate systems is assessed by dynamical mechanical analysis (pin point method) and compared with data obtained by differential scanning calorimetry. The erosion and antifouling properties of the binders are followed during an exposure to marine environment by a visual observation.

Hydrogen bonding. Part 73. IR, NMR, and ab initio molecular orbital study of N, N-dimethyl-1-adamantamine-hydrogen fluoride, a crystalline, H 2O stable compound with a three-center N–H–F bond

N, N-dimethyl-1-adamantamine-hydrogen fluoride is not a tertiary ammonium salt. It is a highly crystalline molecular complex whose infrared spectrum demonstrates the presence of covalent type three-center N–H–F bonds. The compound is obtained from ethanol–water solution, and FT-NMR spectra indicate that it is stable in aqueous solution. An ab initio molecular orbital study of this and potentially similar tertiary amine–hydrogen fluoride complexes suggests a value of about −18 kcal mol −1 for the formation of N–H–F bond, and in addition predicts that secondary C–H⋯F hydrogens bonding by β-hydrogens of the amine may be present in such compounds.

The Influence of Tertiary Butyl Alcohol and Volatile Salts on the Sublimation of Ice from Frozen Sucrose Solutions: Implications for Freeze-Drying

ABSTRACTThe purpose of this work was to investigate the phase behavior of tertiary butanol (TBA) and volatile ammonium salts in frozen mixtures with some commonly used excipients and the efficacy of such volatile additives in accelerating the sublimation of ice from frozen solutions. Differential scanning calorimetry was employed to determine first-order phase transformations and glass transition temperatures in binary and ternary mixtures. Ice sublimation rates were studied by conventional freeze-drying and mass loss with time. A eutectic temperature (268 K) was identified for the anhydrous TBA-sucrose system. In frozen ternary water-excipient-TBA systems, the relative amplitudes of the glass and phase transitions, as measured during warming scans, were found to depend critically on the previous cooling rates. Glass transitions of all the freeze-concentrated mixtures used were determined. The sublimation studies indicated an ability of all volatile additives to accelerate ice sublimation from amorphous, freeze-concentrated solutions, but no clear ranking order, applicable to all systems studied, could be established.

ChemInform Abstract: Synthesis of Monomers on the Basis of Tertiary Ammonium Salts of N,N‐ Dimethylaminoalkylacrylamides

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Colloidal Rhodium: A New Catalytic System for the Reduction of Dibenzo-18-crown-6 Ether

The stereoselective hydrogenation of dibenzo-18-crown-6 ether in the cis-syn-cis isomer of dicyclohexano-18-crown-6 ether has been investigated using either supported metal catalysts or colloidal metal particles prepared under phase transfer catalysis conditions. Supported catalysts generally lead to a mixture of isomers with a poor stereoselectivity in cis-syn-cis. In contrast, when phase transfer agents like tertiary amines and ammonium salts were used in a biphasic system, a good selectivity was achieved under mild conditions. The effect of different factors such as the nature and concentration of the phase transfer agents upon the selectivity has been investigated. An increase of the hydrogen pressure to 5 MPa leads to a cis-syn-cis/cis-anti-cis isomer ratio of 95/5. Strong evidence for the heterogeneous nature of the catalysis involved is presented. A mechanism involving the phase transfer agent as a modifier on the surface of the colloidal rhodium particles is proposed.

Mutagenicity of urine from mice exposed orally to nitrite and various aminated antiparasitic drugs

Mutagenic N-nitroso compound formation from the in vitro reaction of amebicides and anthelmintic drugs, which are pyrimidine derivatives or contain secondary aliphatic amines or heterocyclic nitrogens, has been previously described (Arriaga Alba et al.: Environmental and Molecular Mutagenesis 12:65-73, 1988). Under similar conditions, antiparasitic drugs containing halogenated derivatives of tertiary amines or quaternary ammonium salts do not form mutagenic nitrosated compounds. In the present study the mutagenic activity of mouse urine was determined after oral administration of sodium nitrite and the two above-mentioned groups of drugs (pyrantel pamoate, chloroquine, piperazine and dehydroemetine/iodochlorhydroxyquin and bephenium hydroxynaphthoate, respectively). Results show that the simultaneous administration of piperazine or chloroquine with sodium nitrite produced urinary mutagens that appeared conjugated as glucuronides, whereas pyrantel pamoate and dehydroemetine in the presence of nitrite caused only slightly mutagenic urine. No mutagenic activity was detected in the urine of mice to which halogenated derivatives of tertiary amines (iodochlorhydroxyquin) or quaternary ammonium salts (bephenium hydroxynaphthoate) were administered together with nitrite.

Halogen-containing spiro compounds based on a 4-vinyloxyethyl-1,4-perhydrothiazine 1-oxide

Depending on the nature of the halogen and the polarity of the solvent, the chlorination and iodination of 4-vinyloxyethyl-1,4-perhydrothiazine 1-oxide leads to new heterocyclic tertiary or quaternary ammonium salts, including halogen-containing spiro compounds.

Amines as extracting agents for the quantitative determinations of actinides in biological samples

The present manuscript reviews the use of amines (primary, secondary and tertiary chains and quaternary ammonium salts) as extracting agents for the quantitative determination of actinides in biological samples. Among the primary amines, only Primene, JM-T is used to determine Pu in urine and bone. No one has investigated the possibility of using secondary amines to quantitatively extract actinides from biological samples. Among the tertiary amines, tri-n-octylamine, tri-iso-octylamine, tricaprylamine (Alamine) and trilaurylamine (tridodecylamine) are used extensively to extract and separate the actinides from biological samples. Only one quanternary ammonium salt, methyltricapryl ammonium chloride (Aliquat-336), is used to extract Pu from biological samples.

Palladium extraction from nitrate solutions by tertiary amines and quaternary ammonium salts

The mechanism of palladium extraction by trilaurylamine and trilaurylmethylammonium nitrate from nitric acid solutions was studied. The composition of the extracted compounds was determined by the Job method as well as by organic phase saturation. Both reagents were found to extract palladium as Am2Pd/NO3/4 /Am=ammonium cation/.

Flotation of apatite from calcareous ores with primary amines

Primary amines are strong collectors of apatite and they can selectively float sedimentary phosphates from calcareous ores. However, secondary and tertiary amines and trimethyl ammonium salts are ineffective. Kerosene reduces the collector requirements because hydrocarbon is co-adsorbed along with the amine on the mineral surface. The heats of reaction of aminium ions with such anions as phosphate, carbonate, and sulfate were measured in a microcalorimeter. They are discussed in terms of the solubility of the precipitates formed and their relationship with the adsorption mechanism of primary amines on phosphate minerals. Experimental evidence supports a view that primary amines are adsorbed through chemical interaction between the aminium and phosphate ions at the mineral surface.

N, N-Bis (2-Oxo-3-Oxazolidinyl) Phosphordiamidic Chloride (CLSPO) : A New Strategy for the Ester Function Preparation

Abstract Many methods for conversion of carboxylic acids into the corresponding esters with various reagents have been described.1 We report now a one-step synthesis of esters 4 (see Table) from the tertiary ammonium salt of 1 and N,N-bis(2-oxo-3-oxazolidiny1)phosphordiamidic chloride 2. This reagent has been succesfully used in thioestes formation1 and lactonization;2,3 furthemore, 2 is considered interesting for macrolide synthesis.

Some aspects of the separation of nuclear fission products by liquid-liquid extraction

The technique for and methods of separation of products of nuclear fission play a major role in many stages of the nuclear fuel cycle. The extraction of these products from effluent solution after the processing of the burnt-up nuclear fuel is receiving considerable attention. Trivalent lanthanoides are usualy extracted together with Am(III) and their mutual separation is rather difficult.1–4 The extraction of lanthanoides with tertiary amines or quaternary ammonium salts involving the benzyl group as one of substituents has been studied in order to find the influence of the alkyl chain length on the extraction selectivity and capacity.3–5 Suitable extractants for the separation of Am(III) and Ln(III) from the acidic nitrate solutions were recommended. Using vapour phase osmometry and cryoscopy the association of these compounds was measured at 5.25 and 50°C allowing a rough estimation of medium association degree for the formation of the aggregates. The method of apparent molar volumes, supplemented by the spectrophotometric method, was used for identification of the chemical composition of the aqueous phase.

Backbending and other deviations from ideality in extraction systems

The use of slope analysis for interpreting extraction data is usually coupled with the assumption that the activity coefficients of the new chemical species that yield the changes in slope are ideal. This assumption is shown to be wrong in several extraction systems that are described. In particular, the phenomenon of ''backbending'' in certain tertiary ammonium salt systems is completely inexplicable under such an assumption, and incorrect extractant coordination numbers are obtained for trioctylphosphine oxide--strong acid species in poor solvents. As a result of this assumption literature values for aggregation numbers determined for alkylammonium salts in poor solvents may be too large.

ChemInform Abstract: ION‐SOLVENT INTERACTION, THE EFFECT OF ADDED POLAR APROTIC SOLVENTS ON THE CONDUCTANCES OF TERTIARY AMMONIUM SALTS IN O‐DICHLOROBENZENE AT 25 DEGREES

Chemischer InformationsdienstVolume 5, Issue 11 Article ChemInform Abstract: ION-SOLVENT INTERACTION, THE EFFECT OF ADDED POLAR APROTIC SOLVENTS ON THE CONDUCTANCES OF TERTIARY AMMONIUM SALTS IN O-DICHLOROBENZENE AT 25 DEGREES H. W. AITKEN, H. W. AITKENSearch for more papers by this authorW. R. GILKERSON, W. R. GILKERSONSearch for more papers by this author H. W. AITKEN, H. W. AITKENSearch for more papers by this authorW. R. GILKERSON, W. R. GILKERSONSearch for more papers by this author First published: March 19, 1974 https://doi.org/10.1002/chin.197411105AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume5, Issue11March 19, 1974 RelatedInformation

Ion-solvent interaction. Effect of added polar aprotic solvents on the conductances of tertiary ammonium salts in o-dichlorobenzene at 25.deg.

Ion-solvent interaction. Effect of added polar aprotic solvents on the conductances of tertiary ammonium salts in o-dichlorobenzene at 25.deg.

Far-infrared spectra of tertiary ammonium salts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFar-infrared spectra of tertiary ammonium saltsJohn R. Kludt, Gilbert Y. W. Kwong, and R. L. McDonaldCite this: J. Phys. Chem. 1972, 76, 3, 339–342Publication Date (Print):February 1, 1972Publication History Published online1 May 2002Published inissue 1 February 1972https://doi.org/10.1021/j100647a011RIGHTS & PERMISSIONSArticle Views283Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (446 KB) Get e-Alerts