Protonic acid

Base Conjugale Acid Proton Affinity (experimental, kcal/mol) Proton Affinity (AM1, kcal/mol)... 

The most acidic proton is that next to the ester and the halide ... 

These species are less stable than R88=C=8(Li)-XR in the presence of a sufficiently acidic proton donor, e.g. amtnonia or dicyclohexylamine, they are... 

As indicated in the general scheme below, butatrienes are the first products from base-induced 1,4-elinination of hydrogen and a suitable leaving group. The butatriene in general very readily undergoes isomerization into enynes, if sufficiently "acidic" protons are available (see Chapter 11 in Ref. 3a). In aprotic media cumulenic ethers are fixed as their lithio derivatives if an excess of alkyllithium is applied... 

A primary isotope effect /ch/ d of 6.4 (extrapolated for 35 C) is observed for the metalation and the methylation of 171b when the C-5 position is deuterated. This value is in excellent agreement with the primary isotope effect of 6.6 reported for the metalation of thiophene (392) and it confirms that the rate-determining step is the abstraction by the base of the acidic proton. 

In many acids the acidic proton is bonded to oxygen Such compounds can be con sidered as derivatives of water Among organic compounds the ones most closely related to water are alcohols Most alcohols are somewhat weaker acids than water methanol IS slightly stronger... 

Many compounds contain more than one functional group Prostaglandin Ei a hormone that regulates the relaxation of smooth muscles con tains two different kinds of carbonyl groups Classify each one (aldehyde ketone carboxylic acid ester amide acyl chloride or acid anhydride) Identify the most acidic proton in prostaglandin Ei and use Table 1 7 to estimate its pK ... 

The same anion is formed by loss of the most acidic proton from 1 methyl 1 3 cyclo pentadiene as from 5 methyl 1 3 cyclopentadiene Explain... 

Diphenylmethane is significantly more acidic than benzene and tnphenylmethane is more acidic than either Identify the most acidic proton in each compound and suggest a reason for the trend in 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... 

The most acidic proton is the one of the carboxylic acid group and should have a of approx imately 5... 

Care must be exercised in determining the number of reaction units associated with the acid and base. The number of reaction units for an acid, for instance, depends not on how many acidic protons are present, but on how many... 

Weak acids, of which aqueous acetic acid is one example, cannot completely donate their acidic protons to the solvent. Instead, most of the acid remains undissociated, with only a small fraction present as the conjugate base. 

Monoprotic weak acids, such as acetic acid, have only a single acidic proton and a single acid dissociation constant. Some acids, such as phosphoric acid, can donate more than one proton and are called polyprotic weak acids. Polyprotic acids are described by a series of acid dissociation steps, each characterized by it own acid dissociation constant. Phosphoric acid, for example, has three acid dissociation reactions and acid dissociation constants. 

Multiprotic weak acids can be used to prepare buffers at as many different pH s as there are acidic protons. For example, a diprotic weak acid can be used to prepare buffers at two pH s and a triprotic weak acid can be used to prepare three different buffers. The Henderson-Hasselbalch equation applies in each case. Thus, buffers of malonic acid (pKai = 2.85 and = 5.70) can be prepared for which... 

The purity of a pharmaceutical preparation of sulfanilamide, C6H4N2O2S, can be determined by oxidizing the sulfur to SO2 and bubbling the SO2 through H2O2 to produce H2SO4. The acid is then titrated with a standard solution of NaOH to the bromothymol blue end point, where both of sulfuric acid s acidic protons have been neutralized. Calculate the purity of the preparation, given that a 0.5136-g sample required 48.13 mL of 0.1251 M NaOH. 

The unshared pairs of electrons on hydroxyl oxygens seek electron deficient centers. Alkylphenols tend to be less nucleophiUc than aUphatic alcohols as a direct result of the attraction of the electron density by the aromatic nucleus. The reactivity of the hydroxyl group can be enhanced in spite of the attraction of the ring current by use of a basic catalyst which removes the acidic proton from the hydroxyl group leaving the more nucleophiUc alkylphenoxide. 

Reactions with Aldehydes and Ketones. An important use for alkylphenols is ia phenol—formaldehyde resias. These resias are classified as resoles or aovolaks (see Phenolic resins). Resoles are produced whea oae or more moles of formaldehyde react with oae mole of pheaol uader basic catalysis. These resias are thermosets. Novolaks are thermoplastic resias formed whea an excess of phenol reacts with formaldehyde under acidic conditions. The acid protonates formaldehyde to generate the alkylating electrophile (17). 

When DMSO is mixed with concentrated hydrochloric acid, protonated DMSO is in equiUbtium with the chlorodimethylsiilfonium ion. Pummerer reactions and subsequent reaction of the initial products give a complex mixture of products including formaldehyde, bis(methylthio)methane, methanethiol, dimethyl disulfide, dimethyl sulfide, and others. 

Poly(methyl vinyl ether) [34465-52-6] because of its water solubility, continues to generate commercial interest. It is soluble in all proportions and exhibits a well-defined cloud point of 33°C. Like other polybases, ie, polymers capable of accepting acidic protons, such as poly(ethylene oxide) and poly(vinyl pyrroHdone), each monomer unit can accept a proton in the presence of large anions, such as anionic surfactants, Hl, or polyacids, to form a wide variety of complexes. 

Proliferous Polymerization. Eady attempts to polymerize VP anionicaHy resulted in proliferous or "popcorn" polymerization (48). This was found to be a special form of free-radical addition polymerization, and not an example of anionic polymerization, as originally thought. VP contains a relatively acidic proton alpha to the pyrroHdinone carbonyl. In the presence of strong base such as sodium hydroxide, VP forms cross-linkers in situ probably by the following mechanism ... 

ACID DYES Commercial acid dyes contain one or more sulfonate groups, thereby providing solubility in aqueous media. These dyes are apphed in the presence of organic or mineral acids (pH 2—6). Such acids protonate any available cationic sites on the fiber, thereby making possible bonding between the fiber and the anionic dye molecule. Wool, an animal fiber, is an amphoteric coUoid, possessing both basic and acidic properties because of the amino and carboxylic groups of the protein stmcture. In order to dye such a system, coulombic interactions between the dye molecule and the fiber must take place ie, H2N" -wool-COO + H2N" -wool-COOH. The term acid dye is appHed to those that are capable of such interactions. Acid dyes... 

Pteridinetriones exist as anhydrous species because the tt-electron deficiency is largely compensated by the electron-releasing hydroxy groups. The acidic properties of the amide functions and the sequence of ionization of the acidic protons have been determined in most polyoxopteridines by measurements of the piTa values and comparison of spectral... 

Whenever possible, the chemical reactions involved in the fonnation of diastereomers and their- conversion to separate enantiomers are simple acid-base reactions. For example, naturally occurring (5)-(—)-malic acid is often used to resolve fflnines. One such amine that has been resolved in this way is 1-phenylethylarnine. Amines are bases, and malic acid is an acid. Proton transfer from (5)-(—)-malic acid to a racemic mixture of (/ )- and (5)-1-phenylethylarnine gives a mixture of diastereorneric salts. 

These isomerization processes may be dependent on the nature of the solvent. For example, the rotational barrier of the tetrazathiapentalenes 15.15 (ca. 16 kcal moF ) is influenced by the donor or acceptor ability of the substituents X and Y through the S N short contacts.Solvents with acidic protons increase the magnitude of the barrier, whereas solvents that are good Lewis bases decrease the size of the barrier, owing to solvation of the transition state. 

Table 4-1 lists some rate constants for acid-base reactions. A very simple yet powerful generalization can be made For normal acids, proton transfer in the thermodynamically favored direction is diffusion controlled. Normal acids are predominantly oxygen and nitrogen acids carbon acids do not fit this pattern. The thermodynamicEilly favored direction is that in which the conventionally written equilibrium constant is greater than unity this is readily established from the pK of the conjugate acid. Approximate values of rate constants in both directions can thus be estimated by assuming a typical diffusion-limited value in the favored direction (most reasonably by inspection of experimental results for closely related... 

---