Reactions acetylation

The acetylation reaction, [1], is carried out in pyridine to avoid the hydrolysis of acetic anhydride by water. After the acetylation is complete, water is added to convert the remaining acetic anhydride to acetic acid, [2]. 

Acetylation Reactions. Alcohols maybe acetylated without catalysts by using a large excess of acetic acid. 

Acetic anhydtide [108-24-7] (CH2C0)20, is a mobile, colorless liquid that has an acrid odor and is a more pierciag lacrimator than acetic acid [64-19-7]. It is the largest commercially produced carboxyUc acid anhydride U.S. production capacity is over 900,000 t yearly. Its chief iadustrial appHcation is for acetylation reactions it is also used ia many other appHcations ia organic synthesis, and it has some utility as a solvent ia chemical analysis. 

The manufacture of the highly pure ketene required for ketenization and acetylation reactions is based on the pyrolysis of diketene, a method which has been employed in industrial manufacture. Conversion of diketene to monomeric ketene is accompHshed on an industrial scale by passing diketene vapor through a tube heated to 350—600°C. Thus, a convenient and technically feasible process for producing ketene uncontaminated by methane, other hydrocarbons, and carbon oxides, is available. Based on the feasibiHty of this process, diketene can be considered a more stable form of the unstable ketene. 

A shippable but somewhat less reactive form of diketene is its acetone adduct, 2,2,6-trimethyl-4JT-l,3-dioxin-4-one (15) (103,104). Thermolysis of this safer to handle compound provides acetylketene, a reactive intermediate that can be used for acetoacetylation and cycloaddition reactions. The diketene—acetone adduct as weH as / fZ-butylaceto acetate [1694-31 -1] (also used for aceto acetylations by the trans aceto acetylation reaction) (130), are offered commercially. 

Detoxifica.tlon. Detoxification systems in the human body often involve reactions that utilize sulfur-containing compounds. For example, reactions in which sulfate esters of potentially toxic compounds are formed, rendering these less toxic or nontoxic, are common as are acetylation reactions involving acetyl—SCoA (45). Another important compound is. Vadenosylmethionine [29908-03-0] (SAM), the active form of methionine. SAM acts as a methylating agent, eg, in detoxification reactions such as the methylation of pyridine derivatives, and in the formation of choline (qv), creatine [60-27-5] carnitine [461-06-3] and epinephrine [329-65-7] (50). 

Acetates. Because of the significant interest in selective acetylation reactions of sucrose, the need for a convenient and unambiguous method of identification has been recognized (34,35). The position of an acetyl group in a partially acetylated sucrose derivative can be ascertained by comparison of its H-nmr acetyl methyl proton resonances after per-deuterioacetylation with those of the assigned octaacetate spectmm. The synthesis of partially acetylated sucroses has generally been achieved either by way of selectively protected derivatives such as trityl ethers and cychc acetals or by direct selective acetylation and deacetylation reactions. 

The acetylation reaction is stopped by the addition of water to destroy the excess anhydride, causing rapid hydrolysis of the combined sulfate acid ester (Eig. 7). This is followed by a much slower rate of hydrolysis of the acetyl ester groups. The rate of hydrolysis is controlled by temperature, catalyst concentration, and, to a lesser extent, by the amount of water. Higher temperatures and catalyst concentrations increase the rate of hydrolysis. Higher water content slightly iacreases the hydrolysis rate and helps minimize degradation (85). The amount of water also influences the ratio of primary to secondary... 

Benzimidazo[2,1 -a]isoquinolines synthesis, 5, 161 Benzimidazole, 1-acetyl-reactions... 

The aim of pretreatment is to open up the cellulosic matter in order to achieve more even substitution and to accelerate the main acetylation reaction. A large number of pretreatments have been described in the patent literature but in practice exposure to glacial acetic acid is that most commonly employed. 

Pantothenic acid is found in extracts from nearly all plants, bacteria, and animals, and the name derives from the Greek pantos, meaning everywhere. It is required in the diet of all vertebrates, but some microorganisms produce it in the rumens of animals such as cattle and sheep. This vitamin is widely distributed in foods common to the human diet, and deficiencies are only observed in cases of severe malnutrition. The eminent German-born biochemist Fritz Lipmann was the first to show that a coenzyme was required to facilitate biological acetylation reactions. (The A in... 

Using 1,2-dichloroethane as solvent, Brown et al. 16 have also studied the acetylation reaction, with acetyl chloride and aluminium chloride as reagents at 25 °C. The appropriate data for benzene are given in Table 111 and by comparison with Table 109 it appears that acetylation occurs some 300 times as fast as benzoylation. 

The acetylation reaction has been used by a number of workers for this purpose. Using acetyl chloride with aluminium chloride as catalyst in carbon disulphide or... 

Allcock, H, R., and Scopelianos, A. G., Sjmthesis of sugar-substituted cyclic and polymeric phosphazenes, and their oxidation, reduction, and acetylation reactions. Macromolecules. 36. 715, 1983. 

The GC/FID conditions were as follows column, 1.5% OV-17 (2 m x 3-mm i.d.) glass column N2 carrier gas flow rate, 45mLmin temperature of injection port, column and detector, 240,235 and 235 °C, respectively. The recoveries of these amino derivatives with fortification level ranging from 0.5 to lO.Omgkg" were 62-101% for chlornitrofen, 62-101% for nitrofen and 58-101% for chlomethoxyfen, and satisfactory recoveries from soil were obtained at high concentrations, but the recoveries at lower concentration averaged about 66% for the least recovered compound. Interference from other substances in the soil extracts derived from the acetylation reaction was negligible. 

Deprotection of X, and subsequent oxidation, reduction, and acetylation reactions can, with care, be carried out without decomposition of the inorganic backbone. Reactions of this type are of particular interest for the synthesis of bioactive or biocompatible polyphosphazenes. 

Compound 102 is used as the building block for the syntheses of PNU-86093 and its analogues, as described in Scheme 21. Namely, the Friedel-Crafts acetylation reaction of 102 under acetic anhydride, methanesulfonic acid, and methanesulfonyl anhydride [51,65] affords compound 103 (PNU-... 

It is possible that there will be differences in the reactivity of heartwood and sapwood, or between juvenile and mature wood in acetylation reactions. As a consequence, larger-dimension wood specimens containing both heartwood and sapwood, or mature and juvenile wood, could be liable to distortion when modified. Considering the importance of this to any commercial acetylation operation, it is surprising to see that there is, in fact, very little literature dealing with this issue. 

Direct evidence of the reaction of PAN with sulfhydryl compounds has since been obtained (PAN at 115 ppm for 1-10 min). - In the reaction with glutathione, the major products are oxidized glutathione (disulfide) and 5-acetylglutathione. Other sulfhydryl compounds (e.g., coenzyme A, lipoic acid, and cysteine) yield only oxidation products, with no evidence of 5-acetylation. However, acetylation reactions have been observed with alcohols and amines. Sulfur compounds other than thiols can undergo oxidation by PAN methionine is converted to methionine sulfoxide, and oxidized lipoic acid (disulfide) is converted to sulfoxide. 

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