Carbonyl, from carboxyl

The chemistry of the carbonyl group is probably the single most important aspect of organic chemical reactivity Classes of compounds that contain the carbonyl group include many derived from carboxylic acids (acyl chlorides acid anhydrides esters and amides) as well as the two related classes discussed m this chapter aldehydes and ketones... 

Participation of fluorocarbocations, derived from carboxylic acids and from halo acetones, in reactions of carbonyl compounds with sulfur tetrafluoride has been directly evidenced by trapping them with aromatic hydrocarbons [207, 20S],... 

Interactive to use a web-based palette to predict products from a variety of halogenation reactions of carbonyls and carboxylic acids. 

Carbonyl compounds are more acidic than alkanes for the same reason that carboxylic acids are more acidic than alcohols (Section 20.2). In both cases, the anions are stabilized by resonance. Enolate ions differ from carboxylate ions, however, in that their two resonance forms are not equivalent—the form with the negative charge on oxygen is lower in energy than the form with the charge on carbon. Nevertheless, the principle behind resonance stabilization is the same in both cases. 

Fig. 13. The binding sites of calcium in (a) parvalbumin (41a), (b) annexin (41) and (c) calmodulin (42). The drawings show two bidentate carboxylates coordinated to Ca2 in the EF-hand site of parvalbumin, and one bidentate carboxylate coordinated to Ca2 in annexin and calmodulin. All the donor atoms coordinated to the calciums are oxygen donor atoms from carboxylates of asp = aspartate, or glu = glutamate, or else peptide carbonyl oxygens from gly = glycine or met = methionine. Redrawn after Refs. (41-42).

Page 276, line 10 from bottom. For carbonyl read carboxyl. ... 

The total emission In the commercial heat treatment of 5 to 8 hours at 170 to 160°C varied from 0.4 to 1.2% for CO2 and 0.05 to 0.2% for CO and 0.04 to 0.1% for total acids based on dry board. Some of this emission might emanate from pyrolysis of higher molecular weight material condensed and deposited on the walls of the heat treatment chamber. The heat of formation of this CO2 and CO Is about half the total heat release measured. Part of the oxidation products might remain in the solid phase within the board material, e.g. as bound carbonyl and carboxylic groups, partly followed by heat consuming dehydration reaction. 

Enzymes which catalyze proton abstraction from a carbon activated by carbonyl or carboxyl group adjacent to the carbon have been of great interest to experimentalists and theoreticians... 

Arachidic acid monolayers were prepared from a benzene solution on the water subphase of pH5.8(pure water) and 12.6(adjusted by addition of NaOH) at Tsp of 303 K below Tm(=328 K) of the monolayer [31]. The ionic dissociation state of hydrophilic group was estimated on the basis of the stretching vibrations of carbonyl and carboxylate groups by Fourier transform-infrared attenuated total reflection, FT-IR ATR measurements. 70 arachidic acid monolayers were transferred on germanium ATR prism, resulting in the formation of the multi-layered film. Transfer on the prism was carried out at surface pressures of 25 or 28 mN-nr1. Infrared absorption measurements revealed that almost carboxylic groups of arachidic acid molecules did not dissociate on the water subphase of pH5.8, whereas all carboxylic groups dissociated as carboxylate ions on the water subphase of pH 12.6. 

The a-hydrogens of carboxylic acid derivatives show enhanced acidity, as do those of aldehydes and ketones, and for the same reasons, that the carbonyl group stabilizes the conjugate base. Thus, we can generate enolate anions from carboxylic acid derivatives and use these as nucleophiles in much the same way as we have already seen with enolate anions from aldehydes and ketones. 

There is ample evidence in the literature for conversion of reactive hydrocarbons to carbonyl compounds by autoxidation. In coals, the final products of autoxidation under the conditions used in the present study could be a mixture of carbonyl and carboxylic acid surface groups. Under mild oxidation conditions, a different set of functional groups such as ethers as proposed by Liotta et al. or epoxides as suggested in Scheme V could be formed. There are numerous examples of alkoxy radicals rearranging to epoxides . Choi and Stock have shown that ethers can be produced from benzhydrol structures, which are invoked as intermediates in Scheme IV. At higher temperatures, the epoxides and ethers are unstable and may rearrange to carbonyl compounds. 

Lithium homoenolates derived from carboxylic acids were generated from the corresponding /3-chloro acids by means of an arene-catalyzed lithiation. Chloro acids 186 were deprotonated with n-butyllithium and lithiated in situ with lithium and a catalytic amount of DTBB (5%) in the presence of different carbonyl compounds to yield, after hydrolysis, the expected hydroxy acids (187). Since the purification of these products is difficult, they were cyclized without isolation upon treatment with p-toluenesulfonic acid (PTSA) under benzene reflux, into substituted y-lactones 188 (Scheme 64) . 

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