Acid anhydrides of aliphatic carboxylic acids

ACID ANHYDRIDES OF ALIPHATIC CARBOXYLIC ACIDS Acid anhydrides of monobasic aliphatic acids may be prepared — 

By the reaction of the acid chloride with the corresponding sodium salt, for example  

Acetyl chloride Sodium acetate Acetic anhydride 

An equivalent result may be obtained by treating excess of sodium acetate with phosphorus oxychloride acetyl chloride is an intermediate product and the final result is  

By the action of keten, CHjCO, upon acida with acetic acid  

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Acetonitrile, 407 Acetophenone, 725,729,730 phenylhydrazone, 852 p-Acetotoluidide, 593, 605 Acetoxime, 343 Acetylacetone, 861, 862, 863 Acetylation, reductive, 749 Thiele, 749 Acetyl chloride, 367 2-Acetylcyciohexanone, 862, 864 Acetylene, 245, 897 reactions of, 245, 246 Acetylenic compounds, synthesis of, 467-469, 895-902 Acetylglycine, 909 Acetylmethylurea, 968, 969 Acetylsalicylio acid, 996 Acetyl-o-toluidide, 578 2-Acetylthiophene, 837 Acid anhydrides of aliphatic carboxylic acids, 371... 

Perkin reaction Condensation of aromatic aldehydes with the anhydrides of aliphatic carboxylic acids to afford a,P-unsaturated carboxylic acids. 338... 

The use of aliphatic carboxylic acid anhydrides in place of the corresponding acid chlorides offers many advantages these include ... 

The reaction of aliphatic carboxylate esters or ethers with carbon monoxide in the presence of nickel or a nickel derivative, iodine or an iodine compound, and an organic trivalent Group VA element compound and DBU under pressure gave carboxylic acid anhydrides (79GEP2844371). 

Regioselective functionalization of the N-3 of 125 with 1,2,4-oxadiazole as amide isostere using an IL-bound 125 with chloroacetonitrile afforded N-3 substituted 126 (Scheme 48). The nitrile group of 126 was transformed into amidoxime 127 with hydroxylamine hydrochloride. Addition of aliphatic carboxylic anhydrides or aromatic carboxylic acid to 127 furnished 129 via the 0-acylamidoxime intermediate 128, after cleavage from the IL (07TL1063) (Scheme 48). 

Manufacture of aliphatic carboxylic acids and their corresponding anhydrides by air oxidation of aldehydes in the presence of dissolved catalysts... 

In 2012 Ryu and his colleagues reported the iron-catalyzed decarbonylation of aliphatic carboxylic acids to a-olefins (Scheme 11.7) [32]. In their mechanism study, they found the formation of CO but not CO2. If the reaction was carried out under low or no pressure (0-5 bar) of carbon monoxide, internal an olefin was observed [33]. In the proposed reaction mechanism, the reaction starts from acid anhydride, which was produced from the reaction of substrate and AC2O. Then it reacts with the in situ-formed iron-carbonyl complex, which was generated by FeCl2, phosphine ligand, KI, and CO, and decarbonylation occurred under high temperatures. Notably, Fe2(CO)9, Fe3(CO)i2, [Fe(CO)2Cp]2 did not give the decarbonylation product. 

The sulfonation of aliphatic carboxylic acids has been extensively studied the action of chlorosulfonic acid or sulfuric acid on acetic acid yields sulfoacetic acid, and by treatment with sulfur trioxide at low temperature it was possible to isolate the intermediate mixed anhydride. Such intermediates are also postulated to form in the reaction of aromatic acids with chlorosulfonic acid (see Chapter 4, p 89). Several aliphatic carboxylic acids 87, containing at least one a-hydrogen atom, e.g. n-butanoic, isobutanoic, pentanoic and 3-methylbutanoic acids, have been converted into the corresponding a-sulfonic acids 88 by treatment with chlorosulfonic acid at < 0 °C (Equation 35). The sulfonation probably proceeds via the mixed anhydride 89, which on warming rearranges to give the sulfonic acid 88. 

Anhydrides, both aliphatic and aromatic, as well as mixed anhydrides of carboxylic and carbonic acids, have been reduced to aldehydes in moderate yields with disodium tetracarbonylferrate Na2Fe(CO)4. Heating a carboxylic acid, presumably to form the anhydride, and then reaction with Na/EtOH leads to the aldehyde. 

A dispersant that can be used in drilling fluids, spacer fluids, cement slurries, completion fluids, and mixtures of drilling fluids and cement slurries controls the rheologic properties of and enhances the filtrate control in these fluids. The dispersant consists of polymers derived from monomeric residues, including low-molecular-weight olefins that may be sulfonated or phosphonated, unsaturated dicarboxylic acids, ethylenically unsaturated anhydrides, unsaturated aliphatic monocarboxylic acids, vinyl alcohols and diols, and sulfonated or phosphonated styrene. The sulfonic acid, phosphonic acid, and carboxylic acid groups on the polymers may be present in neutralized form as alkali metal or ammonium salts [192,193]. 

By use of TV-(trifluoroacetyl)- or TV-(trichloroacetyl)-imidazoleare obtained symmetric aliphatic and aromatic anhydrides even from carboxylic acids that do not form insoluble salts in benzene, ether, or THF (Table 13—1). In this case the acid is treated with the imidazolide in a 2 1 molar ratio, and an insoluble imidazolium trifluoro- or tri-chloroacetate is formed. 

In another type of oxidative decarboxylation, arylacetic acids can be oxidized to aldehydes with one less carbon (ArCH2COOH — ArCHO) by tetrabutylammonium periodate. 23l< Simple aliphatic carboxylic acids were converted to nitriles with one less carbon (RCH2COOH — RC=N) by treatment with trifluoroacetic anhydride and NaNCU in FjCCOOH.239 See also 4-39. 

This reaction can be extended to saturated aliphatic carboxylic acids by addition of maleic anhydride to the catalytic system.2... 

Reaction XX. (e) Action of Aliphatic or Aromatic Carboxylic Acids or their Chlorides or Anhydrides on Phenolic Compounds in presence of Zinc Chloride to yield Phenolic Ketones (Nencki). 

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