Alkylammonium carbonates

This includes alkylammonium hydroxides, alkylammonium carbonates, alkylammonium biscarbonates, alkylammonium borates, 1,4-dia2abicyclo [2.2.2] octane... 

Ishikawa, M., Morita, M., lhara, M. and Matsuda, Y., Electric double layer capacitor composed of activated carbon fiber cloth electrodes and solid polymer electrolytes containing alkylammonium salt, J. Electrochem. Soc., 1994, 141(7), 1730 1734. 

Theng BKG, Newman RH, Whitton JS (1998) Characterization of an alkylammonium-montmorillonite-phenanthrene intercalation complex by carbon-13 nuclear magnetic resonance spectroscopy. Clay Miner 33 221-229... 

The inductive effect of the carbon chain in the clay phase amounts to (only) 5 to 7 % of the effect in the gas phase. Ammonium cations in the interlamellar region of clay minerals are therefore less hydrated than in equilibrium solution. The free energy of alkylammonium exchange increases with charge density from Laponite (42) < Red Hill montmorillonite (40) < Camp Berteau montmorillonite (41) in line with the smaller interlamellar hydration status of the adsorbed cation at higher charge density. 

Alkylation of P-dicarbonyl compounds and p-keto esters occurs preferentially on the carbon atom, whereas acylation produces the 0-acyl derivatives (see Chapter 3). There are indications that C- and 0-alkylated products are produced with simple haloalkanes and benzyl halides, but only C-alkylated derivatives are formed with propargyl and allyl halides [e.g. 90]. Di-C-alkylation frequently occurs and it has been reported that the use of tetra-alkylammonium 2-oxopyrrolidinyl salts are more effective catalysts (in place of aqueous sodium hydroxide and quaternary ammonium salt) for selective (-90%) mono-C-alkylation of p-dicarbonyl compounds [91]. 

Typically, values for the receptor carbons fall in the range of 200-3(X) ps, which is a reasonable value for a molecule of its size, with guest complexation not providing any perturbation, as might have been expected. For more rapidly tumbling alkylammonium ions of the type incorporated, values for CH2 and CH groups are typically 4-10 ps in the uncomplexed state. For a number of... 

Carbon disulphide reacts additively with primary and secondary aliphatic amines to form alkylammonium salts of alkyldithiocarbamic acids. The products obtained with dimethylamine, diethylamine and piperidine, also certain derivatives of these products, are manufactured on a large scale for use as accelerators in the vulcanisation of rubber. With aromatic amines the disulphide reacts with elimination of hydrogen sulphide and formation of substituted thio-ureas, e.g. thiocarbanilide. 

Abstract—The nature of the product of the reaction between an aminated silane and carbon dioxide was re-examined with the aid of simple model compounds, several amines, and several aminosilanes. Since the reaction products previously proposed include the amine bicarbonate and a carbamate derived from the amine, ammonium bicarbonate and ammonium carbamate were studied as models for the anions. Carbon dioxide adducts of neat model amines were prepared and studied. Results from a variety of techniques are summarized. Among the most useful was Fourier transform infrared (FTIR) spectroscopy of fluorolube mulls. FTIR spectra were distinctive and assignments characteristic of the two species were extracted from the spectral data. Comparisons of these assignments with the products of the reaction between carbon dioxide and various amines were made. The results indicate that alkylammonium carbamates are the principal product. Nuclear magnetic resonance (NMR) spectra in D20 indicated much dissociation and were not helpful in defining the products. 

Keywords Silane coupling agents alkylammonium carbamates aminosilane-carbon dioxide salts amine-carbon dioxide salts. 

Aresta and Quaranta studied the reactivity of alkylammonium N-alkylcarbamates (RNH3)02CNHR towards a different acylating substrate, such as dimethyl carbonate (DMC) [62a, b]. Carbamate salts (RNH3)02CNHR (R = benzyl, allyl, cyclohexyl), prepared in situ from aliphatic primary amines and C02, reacted with DMC to afford N-alkyl methylcarbamates (Equation 6.6). The reaction requires mild conditions (343-363 K 0.1 MPa C02 pressure) and can be carried out in DMC used as solvent and reagent. At 363 K, carbamate esters were obtained in satisfactory yield (45-92%) with high selectivity, as side products such as ureas, N,N-dialkylcarbamate esters, and alkylated amines were formed in very small amounts. 

Scheme 6.8 Interaction of alkylammonium carbamate ion pair with dimethyl carbonate (DMC).

Figure 4. Log k °j for tributylamnanium CWEs vs. carbon number for various alkylammonium ions < > = primary ammonium ions, = secondary amnonium ions, = tertiary amnonium ions, S = quaternary amnonium ions.

Fig. 11. Inhibitory constants of tetra-alkylammonium salts, R4N, as function of n, the number of carbon atoms in the four substituents together (according to Table IV and V). O------O Eel esterase. ------ Human plasma ChE.

The most widely used sensor for chloride ions in clinical analyzers is based on an ion-exchanger, a quaternary alkylammonium chloride, dispersed in a plastic membrane. It is not an ideal sensor due to the interference of lipophilic anions (e.g., salicylates, bromides) and lip-ophylic cations (e.g., bacteriostatic agents, anesthetics) and a relatively poor selectivity towards hydrogen carbonates (bicarbonates). However, compared to charged anion- and neutral carrier-based membranes that have been tested, it is still the best-suited for automated analyzers. 

In another paper Fendler et al.59) investigated again the CMC dependence of alkylammonium propionates on the number of carbon atoms in the alkyl group of the quaternary ammonium cation (Fig. 12). The same feature as mentioned with octylammonium carboxylates is observed, i.e., the constancy of the CMC values for these alkylammonium propionates in carbon tetrachloride, while in benzene a linear plot is obtained. The latter is taken to indicate the decreased solubility of the monomers with increasing alkyl chain length in benzene. Table 471 exhibits in addition... 

This decision excludes a large literature [26, 42, 43], but simplifies questions of the solvent environment, as indicated above. We place DIMCARB [44] and similar ionic liquids in this category as well. These salts are formed by the equilibration of carbon dioxide and protic alkylammonium species at high... 

The compound K2 [Rh6(CO)15C] is a yellow powder. It is sensitive to air both in the solid state and in solution and is quite soluble in water, methanol, ethanol, acetone, THF, and acetonitrile. The salts of other cations can be obtained by metathesis, in water for the cesium salt and in methanol for the larger tetra-alkylammonium or phosphonium cations. The tetraethylammonium salt is sparingly soluble in THF, whereas the benzyltrimethylammonium and bis-(triphenylphosphine)imminium salts are soluble. All of these salts are soluble in acetone and acetonitrile. The yellow solution of the potassium salt in THF shows characteristic IR bands at 2040 (vw), 1990 (vs), 1885 (vw), 1845 (s), 1830 (sh, m) 1815 (sh, br) and 1775 (vw, br) cm-1. The IR spectral band shapes depend on solvents and cations. The oxidation of K2 [Rh6(CO)i5C] with iron-(III) ammonium sulfate in water under carbon monoxide leads to the octa-nuclear carbido carbonyl cluster Rhg(CO)i9C,6 whereas under nitrogen RhntCO sQ7 or [H30] [Rhls(CO)28C2]8 is obtained. 

As might be expected, the values for the tetra-n-alkylammonium ions decrease fairly regularly as the number of carbon atoms in the alkyl chain is increased. Paul and co-workers have used Xjjj values to estimate apparent solvation numbers for several singly-charged ions8S ... 

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