Ketones acid-base properties

Similar correlations between the acid-base properties of catalysts and activ-ity/selectivity were earlier observed in the rearrangement of simple oxiranes (refs. 5-8). In our case it seems reasonable to suppose that the observed changes are due to the different competing mechanisms discussed above. WO, with strong acidic sites in high concentration, is able to form the carbenium ion. Since the density and the strength of the basic sites on WO are low, formation of the double-bonded surface species depicted in Fig. 3 has only a low probability. The single-bonded open carbenium ion is then mainly transformed to ketone 3. In harmony with this, the isomers exhibit identical selectivity, a... 

The Michael addition of anions of C-acids, such as acetylacetone or hydrocyanic acid, to phenyl vinyl ketone follows a scheme similar to (7). In the cases studied it was possible to neglect the acid-base properties of the adduct and the reverse elimination reaction (Hrubcova, 1964). Equations analogous to (9) and (10) were used and the pH-dependence of the determined formal rate constant at a given analytical concentration of the C-acid follows a dissociation curve with an inflexion at the pKa value of the C-acid. 

The u.v. and i.r. spectra of NH3 and Cl2 codeposited in a N2 matrix at 20 K are consistent with the formation of a charge-transfer complex between these molecules.21 The formation of chloramine in high yield from Cl2 and NH3 in the presence of a ketone has been reported.22 Gas-phase as well as gas-liquid-phase reactions were investigated to assess the suitability of this reaction for the production of hydrazine. However, from a study of the acid-base properties of Br2 in liquid NH3 it has been deduced that BrNH2 does not exist in dilute solutions at low temperatures, owing to the stability of the solvated Br+ species.23... 

Mg-Al mixed oxides obtained by thermal decomposition of anionic clays of hydrotalcite structure, present acidic or basic surface properties depending on their chemical composition [1]. These materials contain the metal components in close interaction thereby promoting bifunctional reactions that are catalyzed by Bronsted base-Lewis acid pairs. Among others, hydrotalcite-derived mixed oxides promote aldol condensations [2], alkylations [3] and alcohol eliminations reactions [1]. In particular, we have reported that Mg-Al mixed oxides efficiently catalyze the gas-phase self-condensation of acetone to a,P-unsaturated ketones such as mesityl oxides and isophorone [4]. Unfortunately, in coupling reactions like aldol condensations, basic catalysts are often deactivated either by the presence of byproducts such as water in the gas phase or by coke build up through secondary side reactions. Deactivation has traditionally limited the potential of solid basic catalysts to replace environmentally problematic and corrosive liquid bases. However, few works in the literature deal with the deactivation of solid bases under reaction conditions. Studies relating the concerted and sequential pathways required in the deactivation mechanism with the acid-base properties of the catalyst surface are specially lacking. 

The MgyAlOx activity declines in the acetone oligomerization reaction due to a blockage of both basic and acid active sites by a carbonaceous residue formed by secondary aldol condensation reactions. The key intermediate species for coke formation are highly unsaturated linear trimers that are formed by aldol condensation of mesityl oxide with acetone and remain strongly bound to the catalyst surface. The catalyst surface acid-base properties determine the preferential formation of a given trimeric intermediate, which in turn defines the chemical nature of the carbon deposit. Aromatic hydrocarbons are the main component of coke formed on acidic Al-rich MgyAlOx samples whereas heavy a,P-unsaturated ketones preferentially form on basic Mg-rich catalysts. 

Rare earth oxides have been studied to a lesser extent than alkaline earth oxides. However, they show characteristic selectivity in the dehydration of alcohols. Secondary alcohols form 1-olefins, whereas the same reaction over an acid catalyst produces the thermodynamically more stable 2-olefin (312). An example of an industrially important rare earth oxide catalyst is Zr02. It has several applications, including the reduction of aromatic carboxylic acids with hydrogen to aldehydes (314), the dehydration of 1-cyclohexyl ethanol to vinyl cyclohexane (315), and the production of diisobutyl ketone from isobutyraldehyde (316). The extensive use of Zr02 is mainly due to its resistance to poisoning by H2O and CO2, and its inherent catalytic activity is a result of its bifunctional acid-base properties. It contains both weakly acidic and basic sites, neither of which is susceptible to poisoning. The acid-base functionality of Zr02 is displayed in the reaction of alkylamine to nitrile (278) (Fig. 33). To form nitriles from both secondary and tertiary amines, both acid and base sites are required. 

Br0nsted-Lowry acids and bases (Chapter 6, Sections 6.2-6.4) Lewis bases and Lewis acids (Chapter 6, Section 6.5) the acid-base properties of alcohols, alkenes, aldehydes, and ketones (Chapter 6, Sections 6.3-6.S)... 

The conversion of alcohols is a frequently used test reaction to study the acid-base properties of zeohtes (see Sects. 2.1.5 and 2.3.3). On acid sites alcohols are dehydrated to alkenes, while they dehydrogenate on basic sites to produce aldehydes or ketones (Scheme 13). 

On an acidic oxide, the allylic species exist as carbocations giving an unsaturated ketone R-CO-CH= CH2 or aldehyde R-CH= CH-CHO. Another possibility is that, the hydrocarbon is attacked by a Brpnsted acid site and forms an alkoxide intermediate, which gives a saturated ketone R-CO-CH2-CH3. It is clear that controlling the acid-base properties of the catalyst surface will affect the first C-H activation and first reaction intermediate, and thus the overall reaction scheme. 

A laser study of the prototropic equilibrium of triplet benzophenone (BP) has been reported [111]. Acid-base properties in the triplet state of aromatic ketones in HjO-CHjCN (4 1) mixtures have been studied by means of nanosecond laser flash photolysis. The acidity constants p /T) in the triplet state are determined by means of the T T, absorbance titration curve, the Ware plot, and the Rayner-Wyatt plot, whose values agree well among them, showing that the acid-base equilibrium in the... 

Chemical Properties. A combination of excellent chemical and mechanical properties at elevated temperatures result in high performance service in the chemical processing industry. Teflon PEA resins have been exposed to a variety of organic and inorganic compounds commonly encountered in chemical service (26). They are not attacked by inorganic acids, bases, halogens, metal salt solutions, organic acids, and anhydrides. Aromatic and ahphatic hydrocarbons, alcohols, aldehydes, ketones, ethers, amines, esters, chlorinated compounds, and other polymer solvents have Httle effect. However, like other perfluorinated polymers,they react with alkah metals and elemental fluorine. 

Both uncalcined and calcined LDHs have also been shown to be effective supports for noble metal catalysts [18-25]. For example, palladium supported on Cu/Mg/Al LDHs has been used in the liquid phase oxidation of limonene [24], and on calcined Mg/Al LDHs for the one-pot synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone and hydrogen at atmospheric pressure [25]. In the latter case, the performance depends on the interplay between the acid-base and hydrogenation properties. More recently. 

Several other natural products systems have been studied, some quite extensively, by NMR methodology, however space constraints prohibt detailed discussion of these systems therefore only important leading references will be given. Extensive NMR studies on amino acids and small peptides have been performed by Lauterwein and coworkers [116-119], by Fiat and coworkers [120-123] and others [124]. Several studies have used l O-enriched dioxygen and carbon monoxide to study by NMR techniques the interactions of these biochemically important small molecules with various proteins [125-128]. A number of investigators have explored the properties and interactions of nucleic acid bases [129,130], nucleosides [131,132], nucleotides [133-138] and one report has appeared in which NMR spectroscopy approaches were applied to the study of small molecule-DNA interactions [139]. A recent report describes the careful analysis of the effect of structure on NMR chemical shifts of over forty hydroxyterpenoids [140]. A study of the 1 0 NMR spectroscopy of over thirty steroid ketones, acids, esters and alcohols enriched with has recently appeared [141]. 

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