Hydrocarbons relative acidity

Our experience to this point has been that C—H bonds are not very acidic Com pared with most hydrocarbons however aldehydes and ketones have relatively acidic protons on their a carbon atoms pA s for enolate formation from simple aldehydes and ketones are m the 16 to 20 range... 

Another example of the effect of resonance is in the relative acidity of carboxylic acids as compared to alcohols. Carboxylic acids derived from saturated hydrocarbons have ipK values near 5, whereas saturated alcohols have pA values in the range 16-18. This implies that the carboxylate anion can accept negative charge more readily than an oxygen on a saturated carbon chain. This can be explained in terms of stabilization of the negative charge by resonance, ... 

In the discussion of the relative acidity of carboxylic acids in Chapter 1, the thermodynamic acidity, expressed as the acid dissociation constant, was taken as the measure of acidity. It is straightforward to determine dissociation constants of such adds in aqueous solution by measurement of the titration curve with a pH-sensitive electrode (pH meter). Determination of the acidity of carbon acids is more difficult. Because most are very weak acids, very strong bases are required to cause deprotonation. Water and alcohols are far more acidic than most hydrocarbons and are unsuitable solvents for generation of hydrocarbon anions. Any strong base will deprotonate the solvent rather than the hydrocarbon. For synthetic purposes, aprotic solvents such as ether, tetrahydrofuran (THF), and dimethoxyethane (DME) are used, but for equilibrium measurements solvents that promote dissociation of ion pairs and ion clusters are preferred. Weakly acidic solvents such as DMSO and cyclohexylamine are used in the preparation of strongly basic carbanions. The high polarity and cation-solvating ability of DMSO facilitate dissociation... 

An extensive series of hydrocarbons has been studied in cyclohexylamine, with the use of cesium cyclohexylamide as base. For many of the compounds studied, spectroscopic measurements were used to determine the relative extent of deprotonation of two hydrocarbons and thus establish relative acidity. For other hydrocarbons, the acidity was derived by kinetic measurements. It was shown that the rate of tritium exchange for a series of related hydrocarbons is linearly related to the equilibrium acidities of these hydrocarbons in the solvent system. This method was used to extend the scale to hydrocarbons such as toluene for which the exchange rate, but not equilibrium data, can be obtained. Representative values of some hydrocarbons withpAT values ranging from 16 to above 40 are given in Table 7.2. 

The order of basicities of anions is opposite that of the relative acidities of the hydrocarbons. 

Fractionation of mycobacteria resulted in the identification of two cellular immunostimulatory components, namely TDM and MDPs. Both are normally found in association with the mycobacterial cell wall. TDM is composed of a molecule of trehalose (a disaccharide consisting of two molecules of a-D-glucose linked via an a 1-1 glycosidic bond), linked to two molecules of my-colic acid (a long-chain aliphatic hydrocarbon-based acid) found almost exclusively in association with mycobacteria. TDM, although retaining its adjuvanticity, is relatively non-toxic. 

Fraser and coworkers116 measured the relative acidities of 15 weakly acidic hydrocarbons in THF using 13C NMR spectroscopy. However, as the experiments were... 

Alkylation generates relatively low volumes of wastewater, primarily from water washing of the liquid reactor products. Wastewater is also generated from steam strippers, depropanizers, and debutanizers, and can be contaminated with oil and other impurities. Liquid process waters (hydrocarbons and acid) originate from minor undesirable side reactions and from feed contaminants, and usually exit as a bottoms stream from the acid regeneration column. The bottoms stream is an acid-water mixture that is sent to the neutralizing drum. The acid in this liquid eventually ends up as insoluble calcium fluoride. 

Kilpatrick, M. and Luborsky, l.E. (1953) The base strengths of aromatic hydrocarbons relative to hydrofluoric acid in anhydrous hydrofluoric acid as the solvent./. Am. Chem. Soc., 75, 577. 

Standard organolithium reagents such as butyllithium, ec-butyllithium or tert-butyllithium deprotonate rapidly, if not instantaneously, the relatively acidic hydrocarbons of the 1,4-diene, diaryhnethane, triarylmethane, fluorene, indene and cyclopentadiene families and all terminal acetylenes (1-alkynes) as well. Butyllithium alone is ineffective toward toluene but its coordination complex with A/ ,A/ ,iV, iV-tetramethylethylenediamine does produce benzyllithium in high yield when heated to 80 To introduce metal into less reactive hydrocarbons one has either to rely on neighboring group-assistance or to employ so-called superbases. 

In addition to stable cations, triarylmethyl compounds form stable carbanions. Because of this the corresponding hydrocarbons are relatively acidic compared to simple alkanes. They react readily with strong bases such as sodium amide, and the resulting carbanions, like the cations, are intensely colored ... 

Students of chemistry must learn to perform simple analyses, to study hydrocarbons, alcohols, acids, and so forth, so that in the final year they may deal effectively with water analysis, constituents and relative values of different foods, the chemical changes of ferments, preservation and deterioration of food, purity of milk, and so forth.19... 

Carbon Acidity of Strained Hydrocarbons The difference in the formal hybridization at carbon accounts for the relative acidities of alkanes versus alkenes versus akynes. The greater the s-character of the carbon of Ihe C-H bond of interest, the more acidic is that proton. Of interest here is extension of this idea to strained compounds, which may employ greater or lesser s-character to accommodate the unusual geometries. Will these compounds have acidities that reflect their hybridization Are strained hydrocarbons more acidic than their unstrained analogs ... 

In making all operating and design decisions. It Is Important to keep in mind the definition of the true reaction zone. Fundamentally, this Is the Interfaclal area between the immiscible hydrocarbon and acid catalyst liquid phases in the reactor. Reactants and products flow across this boundary. The olefins In the feed stream react Instantaneously with the sulfuric acid catalyst and combine with the relatively small amount of isobutane present In solution In the acid catalyst to form alkylate. Alkylate passes out through the Interfaclal surface reaction boundary into the hydrocarbon phase while Isobutane passes in to resaturate the catalyst. To suppress undesirable polymerization and other reactions It Is necessary to ... 

A rough correlation between the relative rates of deprotonation and the Jq h for the bridgehead protons in the series 7, 8 and 9, was observed by Gloss and Larrabee. Taking the C-H coupling constant as a measure of the acidity of hydrocarbons, the acidity of the proton in bicyclobutane is expected to be between that of acetylene and ethylene (Jq-h values for acetylene, ethylene and bicyclobutane are 248,156 and 205 Hz respectively). 

These are equilibria whose positions depend on the relative acidities of the proton sources. The more acidic compound provides the greater amount of organolithium and so the greater the difference in the acidity, the larger the equilibrium constant. However, kinetic acidities must be considered as well as thermodynamic (pK values) e.g., PhH (pKj 37) is not metallated by alkyllithiums [pK of alkanes > 40 in tetrahydrofuran (THF)], despite large difference in pK values. The more reactive RLi-TMED (tetra-methylethylenediamine) complexes, however, provide PhLi. The equilibrium can be driven to the product side by removing the product hydrocarbon or precipitating the RLi. 

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