Mechanisms acid anhydrides

A mixture of an acid anhydride and a ketone is saturated with boron trifluoride this is followed by treatment with aqueous sodium acetate. The quantity of boron trifluoride absorbed usually amounts to 100 mol per cent, (based on total mola of ketone and anhydride). Catalytic amounts of the reagent do not give satisfactory results. This is in line with the observation that the p diketone is produced in the reaction mixture as the boron difluoride complex, some of which have been isolated. A reasonable mechanism of the reaction postulates the conversion of the anhydride into a carbonium ion, such as (I) the ketone into an enol type of complex, such as (II) followed by condensation of (I) and (II) to yield the boron difluoride complex of the p diketone (III) ... 

The mechanisms of the Fischer esterification and the reactions of alcohols with acyl chlorides and acid anhydrides will be discussed m detail m Chapters 19 and 20 after some fundamental principles of carbonyl group reactivity have been developed For the present it is sufficient to point out that most of the reactions that convert alcohols to esters leave the C—O bond of the alcohol intact... 

This reaction was also extended to other aromatic aldehydes for the preparation of a,P unsaturated carboxyUc acids. Several mechanisms of the reaction have been proposed (45). The most accepted mechanism iavolves the reaction of the aldehyde with the enol form of the acid anhydride which is promoted by the presence of the sodium salt or of another base. The resulting reaction product is then dehydrated iato an unsaturated carboxyUc acid. 

In addition to the proteins discussed above, a large number of reactive chemicals used in industry can cause asthma and rhinitis. Hypersensitivity pneumonias have also been described. Isocyanates and acid anhydrides are industrial chemicals that cause occupational asthma. Acid anhydrides, such as phthalic anhydride, seem to cause mainly type I reactions, whereas the IgE-mediated mechanism explains only a part of the sensitizations to isocyanates. Several mechanisms have been suggested, but despite intensive research no models have been generally accepted. The situation is even more obscure for other sensitizing chemicals therefore, the term specific chemical hypersensitivity is often used for chemical allergies. This term should not be confused with multiple chemical sensitivity (MCS) syndrome, which is a controversial term referring to hypersusceptibility to very low levels of environmental chemicals. ... 

FIGURE 20.3 An acid catalyzes the hydrolysis of a carboxylic acid anhydride by increasing the rate of the first stage of the mechanism. The faster the tetrahedral intermediate is formed, the faster the rate of hydrolysis. 

Flavone formation is believed to proceed through a similar mechanism as the synthesis of chromones, albeit aromatic acid anhydrides and their corresponding salts are used. The first step is benzoylation of 12 to give the ester 14. Enolization and o-alkylation then affords the enolbenzoate 15. Enolbenzoate 15 then undergoes an acyl transfer to yield... 

Swarc,M. The Kinetics and Mechanism of N-carboxy-a-amino-acid Anhydride (NCA) Polymerization to Poly-amino Acids. Vol. 4, pp. 1—65. 

Similar additions have been successfully carried out with carboxylic acids, anhydrides, acyl halides, carboxylic esters, nitriles, and other types of compounds. These reactions are not successful when the alkene contains electron-withdrawing groups such as halo or carbonyl groups. A free-radical initiator is required, usually peroxides or UV light. The mechanism is illustrated for aldehydes but is similar for the other compounds ... 

In an alternate synthesis, the formation of thermoplastic vulcanizate (TPV) is accomplished with two polymers, wherein one polymer is grafted with a carboxylic acid anhydride, which then is reacted with an aminosilane, which reacts with the acid anhydride and then cross-links with moismre. The vulcanizates exhibit good mechanical properties and lower melt-flow index than the starting polymers. 

Sekiguchi H (1981) Mechanism of N-carboxy-alpha-amino acid anhydride (Nca) polymerization. Pure Appl Chem 53 1689-1714... 

Respiratory hypersensitivity is an adverse reaction in the respiratory tract driven by immune mechanisms such as IgE antibody mediated allergic responses. Other less well understood mechanisms that have an immune component are also involved in respiratory hypersensitivity. OA is one outcome of respiratory hypersensitivity. Respiratory hypersensitivity and OA to proteins are primarily mediated by IgE antibody with subsequent inflammatory cell infiltrates. This same mechanism is responsible for OA to specific LMW chemicals such as the acid anhydrides and platinum salts. However, the role for IgE mediated responses in OA to other LMW chemicals such as the isocyanates and plicatic acid is poorly defined and other mechanisms may be responsible. 

Most industrially desirahle oxidation processes target products of partial, not total oxidation. Well-investigated examples are the oxidation of propane or propene to acrolein, hutane to maleic acid anhydride, benzene to phenol, or the ammoxidation of propene to acrylonitrile. The mechanism of many reactions of this type is adequately described in terms of the Mars and van Krevelen modeE A molecule is chemisorbed at the surface of the oxide and reacts with one or more oxygen ions, lowering the electrochemical oxidation state of the metal ions in the process. After desorption of the product, the oxide reacts with O2, re-oxidizing the metal ions to their original oxidation state. The selectivity of the process is determined by the relative chances of... 

Benzenetetracarboxylic dianhydride (pyromellitic dianhydride) is a typical bifunctional acid anhydride, and it is a useful raw material for preparing many useful chemicals. Polyimides and polyimidazopyrrolons prepared from this dianhydride have excellent heat and chemical resistance, as well as excellent mechanical and electrical properties. Pyromellitic dianhydride is produced by the oxidation of 1,2,4,5-tetraalkylbenzenes such as 1,2,4,5-tetramethylbenzene (commonly known as durene) and 4,6-diisopro-pyl-l,3-dimethylbenzene. Durene, in particular, is a fundamental raw material for the production of the dianhydride 1-8). 

This process is similar to the formation of an ester by the action of an acid anhydride on an alcohol (described in the earlier section Acid anhydride plus an alcohol ). Half the acid anhydride forms the amide the other half is a leaving group. Ammonia, primary amines, and secondary amines react to produce amides. Figure 12-27 shows the industrial preparation of phenacetin by the reaction of an amine with an acid anhydride. The mechanism for this reaction is similar to the mechanism for the reaction of an acid chloride with an amine (refer to Figure 12-26). 

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