Oxidative esterification reaction

Pincer-ligated iridium complexes have been used as homogeneous catalysts for the dehydrogenation of aliphatic polyalkenes to give partially unsaturated polymers. The catalyst appears to be selective for dehydrogenation in branches as compared with the backbone of the polymer.56 The mechanism shown in Scheme 1 has been suggested for an [IrCl(cod)]2-catalysed oxidative esterification reaction of aliphatic aldehydes and olefinic alcohols.57... 

The oxidation of aldehydes to carboxylic acids has been most extensively investigated with horse liver alcohol dehydrogenases (65-67, 69, 73). There are two distinct reactions the direct oxidation of aldehydes as their hydrated gem-diol form [reaction (9)] and the oxidation of hemiacetals to esters [oxidative esterification, reaction (10)]. 

Figure 133 Reaction network in oxidative esterification reaction of methacrolein.

On the other hand, if the oxidative esterification reaction is considered as a general synthetic method for esters, it is quite significant that the Au-NiO, catalyst can almost completely suppress production of the ester by-product derived from oxidation of the alcohol reaction partner. As a general organic synthetic method for esters, it is not controlled by the equilibrium theory, and it is expected to develop as a green manufacturing method that does not require acid or alkali and does not proceed via organic acids. 

Our strategy for the synthesis of (+)-dactylolide (2.217) is outlined in Scheme 2.69. We envisioned that the 20-membered macrolactone in 2.332 could be constructed by intramolecular iV-heterocyclic carbene (NHC)-catalyzed oxidative macrolactonization of co-hydroxy aldehyde 2.333. Intramolecular NHC-catalyzed oxidative esterification reactions have been recognized as an attractive tool and rapidly growing area in the synthetic community. Indeed, several examples of these reactions have recently been reported [208-216], which clearly provide a new opportunity for the development of catalytic acyl transfer agents in macrolactonization reactions of co-hydroxy aldehydes in the presence of oxidants. The substrate for the macrolactonization reaction would be derived firom the cyanohydrin alkylation of 2,6-dr-tetrahydropyran enal 2.335 with dienyl chloride 2.334. 2,6 -di-tetrahydropyran enal would in turn be constructed by employing the 1,6-oxa conjugate addition reaction of co-hydroxy 2,4-dienal 2.336. Despite the... 

The oxidative esterification reaction of an aromatic carboxylic acid with a phenol in the presence of a phosphorous compound and a chlorocarbon, as illustrated below... 

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propjiene [115-07-1] yields isopropyl acetate [108-21-4], isobutjiene [115-11-7] gives tert-huty acetate [540-88-5]. Minute amounts of water inhibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. Eor example, ethylene-air-acetic acid passed over a palladium—Hthium acetate catalyst yields vinyl acetate. 

Another approach is to use an easily oxidized substance such as acetaldehyde or methylethyl ketone, which, under the reaction conditions, forms a hydroperoxide. These will accelerate the oxidation of the second methyl group. The DMT process encompasses four major processing steps oxidation, esterification, distillation, and crystallization. Figure 10-16 shows a typical p-xylene oxidation process to produce terephthalic acid or dimethyl terephthalate. The main use of TPA and DMT is to produce polyesters for synthetic fiber and film. 

Consider an equilibrium-limited esterification reaction. One way to drive the reaction to completion is to remove the water formed by the reaction selectively through a membrane. This can be an attractive strategy when higher temperatures are undesirable due to factors like colouration of the materials and formation of undesirable products even though these may be present at a low level. As another example, consider the air oxidation of cyclohexane or cyclododecane to cyclohexanone/-ol or cyclododecanone/-ol, where the product can undergo more facile oxidation to unwanted or much lower value products. Consequently, industrial processes operate at a level of less than 5% conversion. If a membrane can selectively remove cyclohexanone as it is formed, the problems mentioned above can be thwarted. However, selective polymeric membranes, which can work at oxidation temperature, have not yet been proved. 

Hydrotreating has been proposed by Arbokem Inc. in Canada as a means of converting Grade Tall Oil into biofuels and fuel additives. However, this process is a hydrogenation process which produces hydrocarbons rather than biodiesel. Recently a process for making biodiesel from crude tall oil has been proposed. It relies on the use of an acid catalysts or of an acyl halide for the esterification reaction, but no information is given on the properties of this fuel, particularly concerning the oxidative stability. 

The pore size of the catalyst plays an important role as the reactants and the products must be able to lit inside the catalyst to take full advantage of the total surface area available. The pore size of metal oxides are sufficiently large (>2 nm) to facihtate the mass transfer into and from the catalyst pores. This compensates for their lower acidity compared to other sohd acids. Table 33.1 gives an overview of the tested catalysts, showing their pros/cons with respect to the fatty acid esterification reaction. 

In current research work, mixed metal oxide based heterogeneous catalysts were prepared and employed for the triglyceride transesteriftcation as well as glycerol esterification reaction to produce triacetin and glycerol carbonate. 

Fig. 3.5 Oxidized carbon nanotubes undergoing amidation and esterification reactions.

Guizard et al. (1986), Cot, Guizard and Larbot (1988) and Larbot et al. (1989) used a sol-gel method to prepare zirconia membrane top layers on an alumina support. The water necessary for the hydrolysis of the Zr-alkoxide was obtained from an esterification reaction. The complete hydrolysis was done at room temperature and resulted in a hydrated oxide. The precipitate was peptized with nitric or hydrochloric acid at pH <1.1 and the final sol... 

Abstract Polyfunctionality of carbohydrates and their low solubility in conventional organic solvents make rather complex their conversion to higher value added chemicals. Therefore, innovative processes are now strongly needed in order to increase the selectivity of these reactions. Here, we report an overview of the different heterogeneously-catalyzed processes described in the literature. In particular, hydrolysis, dehydration, oxidation, esterification, and etherification of carbohydrates are presented. We shall discuss the main structural parameters that need to be controlled and that permit the conversion of carbohydrates to bioproducts with good selectivity. The conversion of monosaccharides and disaccharides over solid catalysts, as well as recent advances in the heterogeneously-catalyzed conversion of cellulose, will be presented. 

Here we report an overview of the different heterogeneously-catalyzed pathways designed for the selective conversion of carbohydrates. On the basis of these results, we shall try to determine the key parameters allowing a better control of the reaction selectivity. Water being commonly used as solvent in carbohydrate chemistry, we will also discuss the stability of solid catalysts in the aqueous phase. In this review, heterogeneously-catalyzed hydrolysis, dehydration, oxidation, esterification, and etherification of monosaccharides and polysaccharides are reported. 

In addition to transesterification reactions, solid base catalysts, including both simple oxides and zeolitic materials, have been used to carry out esterification reactions of fatty acids. These studies have mainly focused on the... 

In many instances the reactivity of the primary alcohol group is greater than that of a secondary alcohol group. Certain oxidation reactions, tritylation, tosylation, and some acid catalyzed esterification reactions are those which exhibit this selectivity. The greater steric availability of this necessarily terminal function may be a factor. 

Alternative reactions employ coupling reagents such as DCC (Steglich Esterification), preformed esters (transesterification), carboxylic acid chlorides or anhydrides. These reactions avoid the production of water. Another pathway for the production of esters is the formation of a carboxylate anion, which then reacts as a nucleophile with an electrophile (similar reactions can be found here). Esters may also be produced by oxidations, namely by the Baeyer-Villiger oxidation and oxidative esterifications. 

P,S -Unsaturated alcohols undergo an oxidative esterification with aliphatic aldehydes in the presence of an iridium(I) catalyst and potassium carbonate.330 Precoordination of the ene-alkoxide with iridium is proposed, followed by reaction with aldehyde. Although the ester yield is high, a mixture of unsaturated and saturated esters is typically obtained, except for secondary alcohols. 

The ethanol produced can be used to make other related chemicals, such as ethyl acetate, acetic acid and acetaldehyde by chemical reactions, e.g. oxidation, esterification. 

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