Carboxylic, generally

Methods of synthesis for carboxylic acids include (1) oxidation of alkyl-benzenes, (2) oxidative cleavage of alkenes, (3) oxidation of primary alcohols or aldehydes, (4) hydrolysis of nitriles, and (5) reaction of Grignard reagents with CO2 (carboxylation). General reactions of carboxylic acids include (1) loss of the acidic proton, (2) nucleophilic acyl substitution at the carbonyl group, (3) substitution on the a carbon, and (4) reduction. 

Carboxylates (9.4, where R is the long-chain hydrophobe and X the cation) represent the oldest type of surfactants, since they could be obtained from naturally occurring fats and oils long before the advent of the petrochemical industry sodium heptadecanoate (9.5), for example, incorporates the cetyl group as hydrophobe. Sodium stearate, sodium palmitate and sodium oleate are the simplest carboxylates generally used as surfactants. Alkylaryl compounds (9.6) are also known. 

Cleavage of allyl carboxylates (general procedure) f To a solution of NaHTe (prepared in situ from tellurium powder (1.30 g, 1.0 mmol) and NaBH4 (0.90 g, 2.4 mmol) in EtOH (20 mL) buffered with deoxygenated HOAc (1.2 mL in 5 mL EtOH)) is added the allyl carboxylate (0.005 mol). The mixture is refluxed under N2 for 2 h, then filtered, the filtrate... 

The method used by Peligot can be extended to carboxylates generally (equation 16). Since the complexes with n > 1 were dried in vacuum at 100 °C before analysis, their degree of hydration has not been established. All have low magnetic moments (jueff = 0.7 BM) so it is likely that they have the acetate structure.157... 

In the crystalline state, triorganotin carboxylates generally adopt either a polymeric structure with a five-coordinated tin atom (type 383) or a monomeric structure varying from a purely tetrahedral four-coordinate geometry (type 384) to a similar one with a weak additional intramolecular coordination from the carbonyl oxygen to the tin atom (type 385)107,266,778.779... 

The reactions of alkyl sulfonates with sodium, potassium or tetraalkylammonium carboxylates generally proceed with inversion of configuration. In the case of f-alkyl sulfonates, however, a varied amount of elimination products is invariably formed. Of all metal carboxylates, cesium salts (Scheme 43) have proved vastly superior with respect to reactivity and the suppression of undesirable side reactions. ... 

Methyl 6 -Oxospiro(cyclopropane-l,8 -tricyclo 3.2.1.0 octane-r-carboxylate) General Procedure ... 

While palladium carboxylates generally decompose in a CO atmoshere to give metal, the compounds [Pd(02CR)(C0)]-nRC02H (n = 0, 0.5 R = Me, CDs, Et or Ph) have been prepared from the corresponding Pd acetate in carboxylic acid-benzene solution. A crystallographic study on the acetate complex showed it to have the tetrameric structure (20). The compound consists of two dimeric palladium(I) units linked by acetate bridges. 

Contrary to aryl carobxylates, benzyl carboxylates generally undergo type a scission. However, the pyridinomethyl esters also effectively guide the bond cleavage of type b probably via intramolecular coordination (Scheme 3.35) [67]. Since decarbonylation from the resulting acyl group rapidly occurs in this system, catalytic decarboxylation takes place in the presence of ammonium formate as a hydride source. 

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