Carboxylic acid anhydrides: aliphatic

The classes of compounds that are conveniently considered together as derivatives of carboxylic acids include the acyl chlorides, carboxylic acid anhydrides, esters, and amides. In the case of simple aliphatic and aromatic acids, synthetic transformations... 

Carboxylic acids, anhydrides, aromatic and aliphatic hydrocarbons, alcohols, aldehydes, ketones, esters, and chlorinated solvents have only a slight effect. 

Anilino-553 and the three 3-tolylaminobenzo[6]thiophenes554 undergo the Bernthsen reaction when heated with an aliphatic carboxylic acid anhydride and zinc chloride 1o yield polycyclic compounds (e.g., 181 from 3-m-tolylaminobenzo[6]thiophene and acetic anhydride), They give analogous arsenic derivatives (e.g., 182 from 3-p-tolylaminobenzo[6]thiophene) when heated with arsenic trichloride in o-dichlorobenzene.553,554... 

In connection with the elaboration of specific procedures for the manufacture of both of the isosorbide mononitrates, methods were developed to shift, with high regioselectivity, the course of the acylation reaction either towards the 5 (endo) or the 2 (exo) position, depending on the conditions applied.104-106 Thus, isosorbide 5-acylates are obtained in 70-85% yield when 3 is treated with the appropriate acid anhydride in the presence of lead(II) oxide or acetate for 20 to 40 h at room temperature. To avoid transesterifications to the appropriate 2-acylate, the workup procedures, especially during the distillation, have to be conducted under strictly neutral conditions. The contrary effect, a remarkable enrichment by the isosorbide 2-acylate (up to 90%) is realized by a transesterification process mediated by a small proportion of sodium or potassium carbonate, hydroxide, or meth-oxide, which are added to the acylation mixture from isosorbide at HOMO0, and subsequent removal of the 2-acylate by vacuum distillation.104 These two regioselective acylation methods may be used for aliphatic, as well as for aromatic, carboxylic acid anhydrides. 

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

In contrast to the broad variety of applications of 1 - 4 and 1 3 linked glucans after reaction with (C2 to C4) carboxylic acid anhydrides and chlorides [159], the use of dextran esters of short chain aliphatic acids such as acetates or propionates is rather limited. According to the present knowledge, the commonly applied acetylation of polysaccharides with the acetic acid anhydrides or acetyl chlorides in the presence of triethylamine or pyridine as base does not lead to pure and soluble dextran acetate with significant DS values. In contrast, dextran propionates [160] and butyrates [161] can be... 

A large number of stable /e-organo tellurocarboxylates were prepared from tellurolates and aliphatic1,2 or aromatic2 carboxylic acid chlorides or aliphatic carboxylic acid anhydrides . The tellurolates were obtained by reduction of diorgano ditelluriums with sodium borohydride. 

Diorgano tellurium dicarboxylates were prepared from dialkyl and diaryl tellurium derivatives. Aliphatic carboxylic acids, aromatic carboxylic acids, their sodium or silver salts, and carboxylic acid anhydrides were used as reagents. Dicarboxylic acids such as succinic acid and phthalic acid were reported to give monomeric carboxylates when... 

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). 

Ethylene-tetrafluoroethylene is inert to strong mineral acids, inorganic bases, halogens, and metal salt solutions. Even carboxylic acids, anhydrides, aromatic and aliphatic hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, chloro-carbons, and classic polymer solvents have little effect on ETFE. 

Classification Aliphatic carboxylic acid anhydride Empirical C4H2O3... 

Iodine triacylates (29) are readily obtained by ozonization of solutions of iodine in aliphatic carboxylic acid anhydrides thermolysis with mercuric oxide affords the symmetrical esters (30) in good yield. Mercuric iodate can perform the same transformation by direct reaction with the anhydride. 

A two-component epoxy system consists of a resin and a hardener, along with possible additives such as accelerators, reactive diluents, resin modifiers, plasticizers, and fillers. Typical hardeners include aliphatic polyamines, which cure at room temperature or at slightly elevated temperatures polyamides, which provide flexibility and are widely used aromatics, which are solid and anhydrides, which require elevated temperature cure and produce thermally stable but brittle adhesives. Low molecular weight epoxies are liquid and are usually cured by amines, carboxylic acid anhydrides, and Lewis acid and base catalyst. Higher molecular weight epoxies are cured through their hydroxyl groups. Cure of epoxies involves an exothermic reaction. 

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

However, certain additives can decrease the rate of thermal decomposition [28]. These additives include cyclic sulfates, sulfones, sultones, aliphatic and aromatic anhydrides, and polymers with pendant carboxylic acid functional groups. Most of these materials are latent acids, which decompose on heating in the presence of moisture to form a strong acid, as shown for cyclic sulfate, 9, in Eq. 5. 

Trifluoroacetic anhydride, which activates the polyesterification of 4-hy-droxybenzoic acid via the formation of a mixed anhydride,307 and 1,1 -carbonyldiimidazole308 were the first reported activating agents. The reaction between 1,1 -carbonyldiimidazolc and carboxylic acids proceeds through the formation of N-acylimidazolcs, which react with aliphatic diols in the presence of sodium ethoxide catalyst (Scheme 2.28). 

Isocyanates react with carboxylic acids to form amides, ureas, anhydrides, and carbon dioxide, depending on reaction conditions and the structure of the starting materials (Scheme 4.13). Aliphatic isocyanates more readily give amides. Aromatic isocyanates tend to react with carboxylic acids to first generate anhydrides and ureas, which at elevated temperatures (ca. 160°C) may further react to give amides. In practice, the isocyanate reaction with carboxylic acid is rarely utilized deliberately but can be an unwanted side reaction resulting from residual C02H functionality in polyester polyols. 

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. 

So do anhydrides and many compounds that enolize easily (e.g., malonic ester and aliphatic nitro compounds). The mechanism is usually regarded as proceeding through the enol as in 12-4. If chlorosulfuric acid (CISO2OH) is used as a catalyst, carboxylic acids can be ot-iodinated, as well as chlorinated or brominated. N-Bromosuccinimide in a mixture of sulfuric acid-trifluoroacetic acid can mono-brominate simple carboxylic acids. ... 

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