Solvent systems highly acidic

Protonated and diprotonated carbonic acid and carbon dioxide may also have implications in biological carboxylation processes. Although behavior in highly acidic solvent systems cannot be extrapolated to in vivo conditions, related multidentate interactions at enzymatic sites are possible. 

In superacidic media, the carbocationic iatermediates, which were long postulated to exist duting Friedel-Crafts type reactions (9—11) can be observed, and even isolated as salts. The stmctures of these carbocations have been studied ia high acidity—low nucleophilicity solvent systems usiag spectroscopic methods such as nmr, ir, Raman, esr, and x-ray crystallography. 

Instmmental methods of analysis provide information about the specific composition and purity of the amines. QuaUtative information about the identity of the product (functional groups present) and quantitative analysis (amount of various components such as nitrile, amide, acid, and deterruination of unsaturation) can be obtained by infrared analysis. Gas chromatography (gc), with a Hquid phase of either Apiezon grease or Carbowax, and high performance Hquid chromatography (hplc), using siHca columns and solvent systems such as isooctane, methyl tert-huty ether, tetrahydrofuran, and methanol, are used for quantitative analysis of fatty amine mixtures. Nuclear magnetic resonance spectroscopy (nmr), both proton ( H) and carbon-13 ( C), which can be used for quaHtative and quantitative analysis, is an important method used to analyze fatty amines (8,81). 

DAG is treated with ethanol and hydrochloric acid in the presence of inert solvent, eg, chlorinated solvents, hydrocarbons, ketones, etc. The L-ascorbic acid precipitates from the mixture as it forms, minimising its decomposition (69). Cmde L-ascorbic acid is isolated through filtration and purified by recrystallization from water. The pure L-ascorbic acid is isolated, washed with ethanol, and dried. The mother Hquor from the recrystallization step is treated in the usual manner to recover the L-ascorbic acid and ethanol contained in it. The cmde L-ascorbic acid mother Hquor contains solvents and acetone Hberated in the DAG hydrolysis. The solvents are recovered by fractional distillation and recycled. Many solvent systems have been reported for the acid-catalyzed conversion of DAG to L-ascorbic acid (46). Rearrangement solvent systems are used which contain only the necessary amount of water required to give >80% yields of high purity cmde L-ascorbic acid (70). 

Liquid—hquid extraction can be used to obtain high purity linoleic acid from safflower fatty acids or linoleic acid from linseed fatty acids using furfural and hexane as solvents (18). High purity linoleic acid has been obtained from sunflower fatty acids using a dimethylformamide and hexane solvent system (19). 

Because of the high acidity of H2SO4 itself, bases form the largest class of electrolytes and only few acids (proton donors) arc known in this solvent system. As noted above, H2S2O7 acts as a proton donor to H2SO4 and HSO3F is also a weak acid ... 

Another issue important to the success of this chiral titanium reagent 31 was the discovery of a marked solvent effect. When the fumaric acid derivative is reacted with isoprene in the presence of 10 mol% of the titanium reagent 31 in toluene, poor optical purity results (36-68% ee). Interestingly the optical purity of the adduct greatly increased in the order benzene, toluene, xylenes, and mesitylene, with 92% ee obtained in the last. Mesitylene is difficult to remove, because of its high boiling point, and other solvents were screened in detail. As a result, the mixed solvent system toluene petroleum ether (1 1) was discovered to be very effective. 

Despite all the advantages of this process, one main limitation is the continuous catalyst carry-over by the products, with the need to deactivate it and to dispose of wastes. One way to optimize catalyst consumption and waste disposal was to operate the reaction in a biphasic system. The first difficulty was to choose a good solvent. N,N -Dialkylimidazolium chloroaluminate ionic liquids proved to be the best candidates. These can easily be prepared on an industrial scale, are liquid at the reaction temperature, and are very poorly miscible with the products. They play the roles both of the catalyst solvent and of the co-catalyst, and their Lewis acidities can be adjusted to obtain the best performances. The solubility of butene in these solvents is high enough to stabilize the active nickel species (Table 5.3-3), the nickel... 

As previously discussed, solvents that dissolve cellulose by derivatization may be employed for further functionahzation, e.g., esterification. Thus, cellulose has been dissolved in paraformaldehyde/DMSO and esterified, e.g., by acetic, butyric, and phthalic anhydride, as well as by unsaturated methacrylic and maleic anhydride, in the presence of pyridine, or an acetate catalyst. DS values from 0.2 to 2.0 were obtained, being higher, 2.5 for cellulose acetate. H and NMR spectroscopy have indicated that the hydroxyl group of the methy-lol chains are preferably esterified with the anhydrides. Treatment of celliflose with this solvent system, at 90 °C, with methylene diacetate or ethylene diacetate, in the presence of potassium acetate, led to cellulose acetate with a DS of 1.5. Interestingly, the reaction with acetyl chloride or activated acid is less convenient DMAc or DMF can be substituted for DMSO [215-219]. In another set of experiments, polymer with high o -celliflose content was esterified with trimethylacetic anhydride, 1,2,4-benzenetricarboylic anhydride, trimellitic anhydride, phthalic anhydride, and a pyridine catalyst. The esters were isolated after 8h of reaction at 80-100°C, or Ih at room temperature (trimellitic anhydride). These are versatile compounds with interesting elastomeric and thermoplastic properties, and can be cast as films and membranes [220]. 

The parameter Ho reflects the ability of the solvent system to donate protons, but it can be applied only to acidic solutions of high dielectric constant, mostly mixtures of water with acids such as nitric, sulfuric, perchloric, and so on. It is apparent that the Ho treatment is valid only when/i //hi+ is independent of the nature of the base (the indicator). Since this is so only when the bases are structurally similar, the treatment is limited. Even when similar bases are compared, many deviations are found. Other acidity scales have been set up, among them // for bases with a... 

Thiolates, generated in situ by the action of ammonium tetra-thiomolybdate on alkyl halides, thiocyanates, and disulfides, undergo conjugate addition to a, (1-unsaturatcd esters, nitriles, and ketones in water under neutral conditions (Eq. 10. II).29 Conjugate addition of thiols was also carried out in a hydrophobic ionic liquid [bmim]PF6/water-solvent system (2 1) in the absence of any acid catalyst to afford the corresponding Michael adducts in high to quantitative yields with excellent 1,4-selectivity under mild and neutral conditions (Eq. 10.12). The use of ionic liquids helps to avoid the use of either acid or base catalysts... 

Friestad and co-workers recently demonstrated that N-acyl hydrazones were excellent radical acceptors in the presence of a chiral Lewis acid [84], Valerolactam-derived hydrazone 117 proved to be the optimal substrate for enantioselective radical additions. Upon further optimization it was found that Cu(OTf )i and f-bulyl bisoxazoline ligand 96 gave the best yields and ee s (Scheme 31). Interestingly, a mixed solvent system (benzene dichloromethane in a 2 1 ratio, respectively) in the presence of molecular sieves (4 A) were necessary to achieve high yields and selectivities. 

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