Solvent effects acids

Unfortunately, the number of mechanistic studies in this field stands in no proportion to its versatility" . Thermodynamic analysis revealed that the beneficial effect of Lewis-acids on the rate of the Diels-Alder reaction can be primarily ascribed to a reduction of the enthalpy of activation ( AAH = 30-50 kJ/mole) leaving the activation entropy essentially unchanged (TAAS = 0-10 kJ/mol)" . Solvent effects on Lewis-acid catalysed Diels-Alder reactions have received very little attention. A change in solvent affects mainly the coordination step rather than the actual Diels-Alder reaction. Donating solvents severely impede catalysis . This observation justifies the widespread use of inert solvents such as dichloromethane and chloroform for synthetic applications of Lewis-acid catalysed Diels-Alder reactions. 

Studies on solvent effects on the endo-exo selectivity of Diels-Alder reactions have revealed the importance of hydrogen bonding interactions besides the already mentioned solvophobic interactions and polarity effects. Further evidence of the significance of the former interactions comes from computer simulations" and the analogy with Lewis-acid catalysis which is known to enhance dramatically the endo-exo selectivity (Section 1.2.4). 

Several alternative attempts have been made to quantify Lewis-acid Lewis-base interaction. In view of the HSAB theory, the applicability of a scale which describes Lewis acidity with only one parameter will be unavoidably restricted to a narrow range of struchirally related Lewis bases. The use of more than one parameter results in relationships with a more general validity ". However, a quantitative prediction of the gas-phase stabilities of Lewis-acid Lewis-base complexes is still difficult. Hence the interpretation, not to mention the prediction, of solvent effects on Lewis-add Lewis-base interactions remains largely speculative. 

Donor strengths, taken from ref. 207b, based upon the solvent effect on the symmetric stretching frequency of the soft Lewis acid HgBr2. Gutmann s donor number taken from ref 207b, based upon AHr for the process of coordination of an isolated solvent molecule to the moderately hard SbCL molecule in dichioroethane. ° Bulk donor number calculated as described in ref 209 from the solvent effect on the adsorption spectrum of VO(acac)2. Taken from ref 58, based on the NMR chemical shift of triethylphosphine oxide in the respective pure solvent. Taken from ref 61, based on the solvatochromic shift of a pyridinium-A-phenoxide betaine dye. 

Clearly, complete understanding of solvent effects on the enantioselectivity of Lewis-acid catalysed Diels-Alder reactions has to await future studies. For a more detailed mechanistic understanding of the origins of enantioselectivity, extension of the set of solvents as well as quantitative assessment of the strength of arene - arene interactions in these solvent will be of great help. 

Interestingly, at very low concentrations of micellised Qi(DS)2, the rate of the reaction of 5.1a with 5.2 was observed to be zero-order in 5.1 a and only depending on the concentration of Cu(DS)2 and 5.2. This is akin to the turn-over and saturation kinetics exhibited by enzymes. The acceleration relative to the reaction in organic media in the absence of catalyst, also approaches enzyme-like magnitudes compared to the process in acetonitrile (Chapter 2), Cu(DS)2 micelles accelerate the Diels-Alder reaction between 5.1a and 5.2 by a factor of 1.8710 . This extremely high catalytic efficiency shows how a combination of a beneficial aqueous solvent effect, Lewis-acid catalysis and micellar catalysis can lead to tremendous accelerations. 

Solvent Effects on the Rate of Substitution by the S 2 Mechanism Polar solvents are required m typical bimolecular substitutions because ionic substances such as the sodium and potassium salts cited earlier m Table 8 1 are not sufficiently soluble m nonpolar solvents to give a high enough concentration of the nucleophile to allow the reaction to occur at a rapid rate Other than the requirement that the solvent be polar enough to dis solve ionic compounds however the effect of solvent polarity on the rate of 8 2 reactions IS small What is most important is whether or not the polar solvent is protic or aprotic Water (HOH) alcohols (ROH) and carboxylic acids (RCO2H) are classified as polar protic solvents they all have OH groups that allow them to form hydrogen bonds... 

Cold methanol has proven to be an effective solvent for acid gas removal. Cold methanol is nonselective in terms of hydrogen sulfide and carbon dioxide. The carbon dioxide is released from solution easily by reduction in pressure. Steam heating is required to release the hydrogen sulfide. A cold methanol process is Hcensed by Lurgi as Rectisol and by the Institute Francaise du Petrole (IFP) as IFPEXOL. 

Piperidin-4-one N-oxide, 2,2,6,6-tetramethyl-solvent effects, 2, 146 Piperidinones stability, 2, 159-161 synthesis, 2, 81, 95 from S-aminopentanoic acids, 2, 402 Piperidin-2-ones IR spectroscopy, 2, 130 synthesis... 

A prototype of such phenomena can be seen in even the simplest carboxylic acid, acetic acid (CH3CHOOH). Acidity is determined by the energy or free energy difference between the dissociated and nondissociated forms, whose energetics usually depend significantly on their conformation, e.g., the syn/anti conformational change of the carboxyl-ate group in the compound substantially affects the acid-base equilibrium. The coupled conformation and solvent effects on acidity is treated in Ref. 20. 

In this section, we review three studies on the coupled substimtion and solvent effects on basicity and acidity. 

Another example is the acidities of a series of carboxylic acids. It is known that the substitution effect on these compounds also depends on the environment. The behavior of the halo-substituted acetic acids is one of the prototype problems for the solvent effect on acidity The order in strength of the haloacetic acids in the gas phase is... 

The observed acidities in the gas phase are interpreted in terms of the negative induction effect of the halo substituents however, the microscopic picture of the solvent effects in addition to such induction effects of the solute have not been clarified. 

For a broad review of substituent and solvent effects on acidity and basicity, see R. W. Taft, Prog. Phys. Org. Chem. 14 247 (1983). 

A decisive solvent effect is also observed with other a,/ -epoxy ketones. Specifically, 3jS-hydroxy-16a,17a-epoxypregn-5-en-20-one and its acetate do not react with thiocyanic acid in ether or chloroform. However, the corresponding thiocyanatohydrins are formed by heating an acetic acid solution of the epoxide and potassium thiocyanate. As expected, the ring opening reaction is subject to steric hindrance. For example, 3j6-acetoxy-14f ,15f5-epoxy-5) -card-20(22)-enoIide is inert to thiocyanic acid in chloroform, whereas the 14a,15a-epoxide reacts readily under these conditions.Reactions of 14a,15a-epoxides in the cardenolide series yields isothiocyanatohydrins, e.g., (135), in addition to the normal thiocyanatohydrin, e.g., (134). 

The reactions of enamines as 1,3-dipolarophiles provide the most extensive examples of applications to heterocyclic syntheses. Thus the addition of aryl azides to a large number of cyclic (596-598) and acyclic (599-602) enamines has led to aminotriazolines which could be converted to triazoles with acid. Particular attention has been given to the direction of azide addition (601,603). While the observed products suggest a transition state in which the development of charges gives greater directional control than steric factors, kinetic data and solvent effects (604-606) speak against zwitterionic intermediates and support the usual 1,3-dipolar addition mechanism. 

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. 

Strong basic solutions are effective solvents for acid gases. However, these solutions are not normally used for treating large volumes of natural gas because the acid gases form stable salts, which are not easily regenerated. For example, carbon dioxide and hydrogen sulfide react with aqueous sodium hydroxide to yield sodium carbonate and sodium sulfide, respectively. 

Esters can also be synthesized by an acid-catalyzed nucleophilic acyl substitution reaction of a carboxylic acid with an alcohol, a process called the Fischer esterification reaction. Unfortunately, the need to use an excess of a liquid alcohol as solvent effectively limits the method to the synthesis of methyl, ethyl, propyl, and butyl esters. 

For sparingly soluble salts of a strong acid the effect of the addition of an acid will be similar to that of any other indifferent electrolyte but if the sparingly soluble salt MA is the salt of a weak acid HA, then acids will, in general, have a solvent effect upon it. If hydrochloric acid is added to an aqueous suspension of such a salt, the following equilibrium will be established ... 

Since, however, K2 is comparatively large, the solvent effect is relatively small this is why in the quantitative separation of barium sulphate, precipitation may be carried out in slightly acid solution in order to obtain a more easily filterable precipitate and to reduce co-precipitation (Section 11.5). 

The equilibrium in this reversible reaction will be greatly influenced by the nature of the acid and that of the solvent. Weak acids are normally used in the presence of strongly protophilic solvents as their acidic strengths are then enhanced and then become comparable to those of strong acids — this is referred to as the levelling effect . 

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