Acid-Catalyzed Aqueous Hydration

In general ketones are more stable than their enol precursors and are the products actually isolated when alkynes undergo acid catalyzed hydration The standard method for alkyne hydration employs aqueous sulfuric acid as the reaction medium and mer cury(II) sulfate or mercury(II) oxide as a catalyst... 

The synthesis of pyrazoles and isoxazoles from l-heterobut-l-en-3-ynes is performed, as a rule, in an aqueous acid medium, i.e., under conditions favoring the hydrolysis and hydration of the initial enyne. This circumstance impedes rationalization of the experimental results. Therefore, it is reasonable to consider in brief the protonation and behavior of l-heterobut-l-en-3-ynes under the conditions of acid-catalyzed hydrolysis. 

Rate-determining protonation to give a vinyl cation rather than 1,4 addition of water has been proposed as the most consistent mechanism (25) for the acid-catalyzed hydration of arylpropiolic acids in aqueous sulfuric acid. Hydration of arylpropiolic acid closely resembles the acid-catalyzed isomeriza-... 

Chiang, Y. Kresge, J. Zhu, Y. Flash photolytic generation of o-quinone a-phenylmethide and o-quinone oc-(p-anisyl)methide in aqueous solution and investigation of their reactions in that medium. Saturation of acid-catalyzed hydration. J. Am. Chem. Soc. 2002, 124, 717-722. 

Judging from these findings, the mechanism of Lewis acid catalysis in water (for example, aldol reactions of aldehydes with silyl enol ethers) can be assumed to be as follows. When metal compounds are added to water, the metals dissodate and hydration occurs immediatdy. At this stage, the intramolecular and intermolecular exchange reactions of water molecules frequently occur. If an aldehyde exists in the system, there is a chance that it will coordinate to the metal cations instead of the water molecules and the aldehyde is then activated. A silyl enol ether attacks this adivated aldehyde to produce the aldol adduct. According to this mechanism, it is expected that many Lewis acid-catalyzed reactions should be successful in aqueous solutions. Although the precise activity as Lewis acids in aqueous media cannot be predicted quantitatively... 

In aqueous solutions, aldehydes [RHC=0] undergo general acid-catalyzed addition of water to yield the hydrate [RHC(0H)2], and the equilibrium position lies in favor of the hydrate. Jencks summarized the most likely mechanism for the hydration reaction. 

An amino or hydroxy group facilitates 5-bromination even in aqueous solution. A -bromosuccinimide (NBS) and molecular bromine are the commonest reagents used. In uracils, cytosines, and barbituric acids, products of both addition and substitution can be identified in aqueous solution, and 5,5-dibromo products are common. In the bromination of uracils, addition products, including covalent hydrates, form rapidly, and the acid-catalyzed dehydration step to 5-bromouracils is much slower. Cytosine and related compounds behave similarly <1994HC(52)1, 1996CHEC-II(6)93>. 

When mixed-phase rutile pigments are used in special paint systems, (e.g., stoving or acid-catalyzed lacquers), inorganic surface treatment in an aqueous medium can improve the gloss and flocculation properties. For example, an aqueous pigment suspension is first treated with a surfactant, and then coated with metal hydroxides or oxide hydrates [3.93],... 

In so far as in aqueous solution dehydration of alcohols to form alkenes is normally disfavored thermodynamically, it is clear why the rate-determining step in the acid-catalyzed dehydration (or hydration of the alkenes) is normally proton transfer. Only when the double bond of the product is strongly stabilized, for example by forming part of an aromatic ring, does deprotonation become faster than carbocation formation. 

Mercuric Ion-Catalyzed Hydration Alkynes undergo acid-catalyzed addition of water across the triple bond in the presence of mercuric ion as a catalyst. A mixture of mercuric sulfate in aqueous sulfuric acid is commonly used as the reagent. The hydration of alkynes is similar to the hydration of alkenes, and it also goes with Markovnikov orientation. The products are not the alcohols we might expect, however. 

Protoporphyrin and its derivatives, because of their labile vinyl substituents, are susceptible to acid-catalyzed hydration. For this reason aqueous solutions should be avoided in the preparation of protoporphyrin dimethyl ester from protohemin, and subsequent reinsertion of the iron. Thus the direct esterification of protohemin under basic conditions appears to be the method of choice. More stable porphyrins such as H2oep are most conveniently prepared by the direct insertion of iron(lll) ion using the iron(III) chloride method5 the resultant Fe(IIl) (oep)Cl can be separated directly from the reaction medium as shining purple crystals. However, this method fails to give successful results with protoporphyrin derivatives. In general, the iron (II) sulfate method is the mildest and should be used for all prophyrins unless one is certain that the more rapid alternatives [boiling DMF with iron(II) chloride, or preferably the more stable iron(II) perchlorate] will have no ill effect on the peripheral substituents. 

In acid-catalyzed reactions, the distinction between single-species and complex catalysis is not always clear-cut. The actual catalyst is the solvated proton, H30+ in aqueous solution, and H20 (or a molecule of the nonaqueous solvent) may thus appear as a co-product in the first step and as a co-reactant in the step reconstituting the original solvated proton, possibly also in other additional steps, e.g., if the overall reaction is hydrolysis or hydration. Moreover, the acid added as catalyst may not be completely dissociated, and its dissociation equilibrium then affects the concentration of the solvated proton. At high concentrations this is true even for fairly strong acids such as sulfuric, particularly in solvents less polar than water. Such cases are better described as acid-base catalysis (see Section 8.2.1). 

Epoxide rings are cleaved by treatment with acid just as other ethers are. The major difference is that epoxides react under much milder condition-because of ring strain. Dilute aqueous acid at room temperature is sufficiem to cause the hydrolysis of epoxides to 1,2-diols, also called vicina/glycols.(Th word vicinal means adjacent," and a glycol is a diol.) More than 3 millK tons of ethylene glycol, most of it used for automobile antifreeze, are produci each year in the United States by acid-catalyzed hydration of ethylene oxid Note that the name ethylene glycol refers to the glycol derived from ethylen just as ethylene oxide refers to the epoxide derived from ethylene. 

Attempted peroxy acid epoxidation of the bicyclic ketone (31 equation 13) gave the lactone (33), instead of several possible rational alternatives. The epoxide (32) was implicated as an intermediate when it was independently synthesized from the epoxy alcohol, and shown to give (33) on treatment with aqueous acid.- A mechanism involving scission of the acyl bridgehead bond via the hydrated 1,1 -diol form of the ketone was proposed to account for the formation of this unexpected product. The rearrangement of the isolongifolene derivative (34 equation 14) appears to be mechanistically related. The product (35) is formed by brief treatment with dilute HCIO4 in dioxane as a mixture of isomers believed to arise by acid-catalyzed epimerization of the carbinol center. ... 

The cyclic vinyl ether 2,3-dihydro-1,4-dioxin is converted into its cyclic hemiacetal hydration product, tetrahydro-2-hydroxy-1,4-dioxin, in aqueous solution by an acid-catalyzed reaction <870K2746, 89JP043). Treatment of an alcohol with excess of 2,3-dihydro-1,4-dioxin at room temperature in the presence of copper(II) bromide in tetrahydrofuran leads to the corresponding acetal. This new protective group for alcohols, which is stable towards lithium aluminum hydride and organolithium reagents, can be removed by treatment with acidified aqueous methanol <85S806>. 

Acrophyllidine, C17H19NO4, appeared from its NMR spectrum to be the tertiary alcohol 170, and this was confirmed by conversion of acrophylline into acrophyllidine through acid-catalyzed hydration. Because aqueous acid was used in the isolation procedure, acrophyllidine may be an artifact. 

The volumes of activation for the acid-catalyzed hydration of propylene and isobutene in aqueous solution are respectively —9 6 l-0 cm mole- at 100°C and — ll-5 l-0 cm mole at 35 C (Baliga and Whalley, unpublished results). Thus well over half the volume of a water molecule is lost when the transition state is formed, and it seems... 

This reaction was first reported by Fittig and Schrohe in 1875 and subsequently extended by Kutscheroff in 1881. It is an acid-catalyzed hydration of alkynes into ketones. In this reaction, dilute sulfuric acid and mercuric salt are used as catalysts, and mercuric chloride can form a complex with acetylene in aqueous solution. This reaction has been used to prepare ketones from higher alkynes, such as propyne, and vinylacetylene as well as in commercial production of acetaldehyde from acetylene. ... 

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