Carboxylic acids conjugates

Vinyl carboxylic acids (conjugated acids) were shown to react with NBS and lithium acetate in aqueous acetonitrile, to give the corresponding vinyl bromide (C=C COOH C=C Br), using microwave irradiation." A similar reaction was reported using Na2Mo04, KBr and aqueous hydrogen peroxide... 

The aldehyde group is expected to be oxidized to the corresponding carboxylic acid, conjugated and subsequently excreted. 

Also, bis-1,3-dienes incorporate carbon dioxide in the presence of Ni(acac) and a diorganozinc reagent to afford cyclic carboxylic acids °. Conjugated dienemagnesium reagents react with acetone at -78 °C, followed by carbon dioxide at 0°C to form the spiro-y-lactone 34 in 68 % yield. ... 

The intramolecular reaction oF allcenes with various O and N functional groups offers useful synthetic methods for heterocycles[13,14,166]. The reaction of unsaturated carboxylic acids affords lactones by either exo- or endo-cyclization depending on the positions of the double bond. The reaction of sodium salts of the 3-alkenoic acid 143 and 4-alkenoic acid 144 with Li2PdCl4 affords mostly five-membcrcd lactones in 30-40% yields[167]. Both 5-hexe-noic acid (145) and 4-hexenoic acid (146) are converted to five- or six-mem-bered lactones depending on the solvents and bases[168]. Conjugated 2,4-pentadienoic acid (147) is cyclized with Li2PdCl4 to give 2-pyrone (148) in water[i69]. 

The reaction of alkenyl mercurials with alkenes forms 7r-allylpalladium intermediates by the rearrangement of Pd via the elimination of H—Pd—Cl and its reverse readdition. Further transformations such as trapping with nucleophiles or elimination form conjugated dienes[379]. The 7r-allylpalladium intermediate 418 formed from 3-butenoic acid reacts intramolecularly with carboxylic acid to yield the 7-vinyl-7-laCtone 4I9[380], The /i,7-titisaturated amide 421 is obtained by the reaction of 4-vinyl-2-azetidinone (420) with an organomercur-ial. Similarly homoallylic alcohols are obtained from vinylic oxetanes[381]. 

Neutral Lewis bases such as water alcohols and carboxylic acids are much weaker nucleophiles than their conjugate bases When comparing species that have the same nucleophilic atom a negatively charged nucleophile is more reactive than a neutral one... 

In most biochemical reactions the pH of the medium is close to 7 At this pH car boxylic acids are nearly completely converted to their conjugate bases Thus it is common practice m biological chemistry to specify the derived carboxylate anion rather than the carboxylic acid itself For example we say that glycolysis leads to lactate by way of pyruvate... 

Homer-Emmons reagents react with trifluoromethyl ketones to form tnfluo romethylated olefins, however, the double bond can isomerize out of conjugation with the carboxylic acid group with the product olefin that bears a y-proton [37] (equation 30)... 

Bile acids, which exist mainly as bile salts, are polar carboxylic acid derivatives of cholesterol that are important in the digestion of food, especially the solubilization of ingested fats. The Na and salts of glycocholic acid and tauro-cholic acid are the principal bile salts (Ligure 25.41). Glycocholate and tauro-cholate are conjugates of cholic acid with glycine and taurine, respectively. 

In these papers, the carboxylic acid to be protected was a stable, unsubstituted compound. Harsh conditions were acceptable for both formation and cleavage of the amide. Typically, a simple secondary amide is very difficult to cleave. As the pKa of the conjugate acid of an amide decreases, the rate of hydrolysis of amides derived from these amines increases. The dimethylamide of a cephalosporin was prepared as follows using 2,2 -dipyridyl disulfide. ... 

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