Esters reaction

The reaction of ketones with peroxy acids is both novel and synthetically useful An oxygen from the peroxy acid is inserted between the carbonyl group and one of the attached car bons of the ketone to give an ester Reactions of this type were first described by Adolf von Baeyer and Victor Vilhger m 1899 and are known as Baeyer—Villiger oxidations... 

The primary and secondary alcohol functionahties have different reactivities, as exemplified by the slower reaction rate for secondary hydroxyls in the formation of esters from acids and alcohols (8). 1,2-Propylene glycol undergoes most of the typical alcohol reactions, such as reaction with a free acid, acyl hahde, or acid anhydride to form an ester reaction with alkaU metal hydroxide to form metal salts and reaction with aldehydes or ketones to form acetals and ketals (9,10). The most important commercial appHcation of propylene glycol is in the manufacture of polyesters by reaction with a dibasic or polybasic acid. 

Alternatively, weak acids and certain salts have been found to extend the lifetimes of inherently rapid reactions which occur with highly reactive esters, such as bis(2,4-dinitrophenyl) oxalate (95). A chemiluminescent demonstration based on the oxaUc ester reaction has been described (96) and the reaction has been developed iato a practical lighting system. 

A modified oxalic ester reaction that is activated by air rather than hydrogen peroxide has been provided by combining a 9,10-dihydroxyanthracene or ben2oin with the ester and fluorescer (259). Oxygen from air is converted to hydrogen peroxide by the dihydroxyanthracene. 

Sulfated Acids, Amides, and Esters. Reaction with sulfuric acid may be carried out on fatty acids, alkanolamides, and short-chain esters of fatty acids. The disodium salt of sulfated oleic acid is a textile additive and an effective lime soap dispersant. A typical sulfated alkanolamide stmcture is CiiH23C0NHCH2CH20S03Na. Others include the sulfates of mono and diethanolamides of fatty acids in the detergent range. The presence of... 

H-Benzimidazole, 2,2-pentamethylene-reduction, 5, 423 Benzimidazole-2-carbaldehyde oximes, 5, 436 Benzimidazolecarbaldehydes oxidation, 5, 437 Benzimidazole-2-carbamates 5-substituted as anthelmintics, 1, 202 Benzimidazole-1-carboxylic acid, 2-amino-methyl ester reactions, 5, 453... 

Furan-2-carbonyl chloride, 5-alkyl-3,4-dichloro-synthesis, 4, 690 Furancarboxamides rotational isomerism, 4, 543 Furan-2-carboxylic acid, 5-acetylamino-ethyl ester reactions, 4, 647 Furan-2-carboxylic acid, amino-properties, 4, 708 Furan-2-carboxylic acid, 5-bromo-nitration, 4, 603, 711 Furan-2-carboxylic acid, 3-methyl-methyl ester bromination, 4, 604 Furan-2-carboxylic acid, 5-methyl-nitration, 4, 602... 

IsoxazoIidine-3,3-dicarboxylic acid, 2-methoxy-dimethyl ester reaction with bases, 6, 47 Isoxazolidine-3,5-diones synthesis, 6, 112, 113 Isoxazoli dines conformation, 6, 10 3,5-disubstituted synthesis, 6, 109 oxidation, 6, 45-46 PE spectra, 6, 5 photolysis, 6, 46 pyrolysis, 6, 46 reactions, 6, 45-47 with acetone, 6, 47 with bases, 6, 47 reduction, 6, 45 ring fission, S, 80 spectroscopy, 6, 6 synthesis, 6, 3, 108-112 thermochemistry, 6, 10 Isoxazolidin-3-ol synthesis, 6, 111 Isoxazolidin-5-oI synthesis, 6, 111... 

Introduction of the two-carbon fragment is a cornerstone of synthetic methodology and many of the condensation reactions frequently used have been known for decades, if not for a century. Examples include the malonic ester and acetoacetic ester reactions, the Perkin condensation, and the Doebner-... 

Contents Introduction and Principles. - The Reaction of Dichlorocarbene With Olefins. - Reactions of Dichlorocarbene With Non-Olefinic Substrates. -Dibromocarbene and Other Carbenes. - Synthesis of Ethers. - Synthesis of Esters. - Reactions of Cyanide Ion. - Reactions of Superoxide Ions. - Reactions of Other Nucleophiles. - Alkylation Reactions. - Oxidation Reactions. - Reduction Techniques. - Preparation and Reactions of Sulfur Containing Substrates. -Ylids. - Altered Reactivity. - Addendum Recent Developments in Phase Transfer Catalysis. 

Discussion of acid and ester reaction mechanisms is often carried out in terms of the classification in Table 1-1. This specifies the type of bond fission (Ac or... 

Reaction with water to yield a carboxylic acid Reaction with an alcohol to yield an ester Reaction with ammonia or an amine to yield an amide Reaction with a hydride reducing agent to yield an aldehyde or an alcohol... 

Transesterifications, also termed ester exchange or ester interchange reactions, include hydroxy-ester, carboxy-ester, and ester-ester reactions. Hydroxy-ester reaction is the most important one and is used for many aromatic-aliphatic and wholly aromatic polyester syntheses. Carboxy-ester interchange is restricted to the synthesis of wholly aromatic polyesters while the ester-ester route is rarely used for polyester preparation due to slow kinetics. All these reactions may take place in comparable experimental conditions and can be catalyzed by similar classes of compounds. 

The use of (TMSlsSiH with acyl selenides can also yield new C-C bond formation, as shown with the a,/l-unsaturated lactam ester (Reaction 67). The resulting ketone can be envisaged as potentially useful for the synthesis of 2-acylindole alkaloids. Both the effects of H-donating ability and steric hindrance by the silicon hydride are evident. 

Though we and others (27-29) have demonstrated the utility and the improved sensitivity of the peroxyoxalate chemiluminescence method for analyte detection in RP-HPLC separations for appropriate substrates, a substantial area for Improvement and refinement of the technique remains. We have shown that the reactions of hydrogen peroxide and oxalate esters yield a very complex array of reactive intermediates, some of which activate the fluorophor to its fluorescent state. The mechanism for the ester reaction as well as the process for conversion of the chemical potential energy into electronic (excited state) energy remain to be detailed. Finally, the refinement of the technique for routine application of this sensitive method, including the optimization of the effi-ciencies for each of the contributing factors, is currently a major effort in the Center for Bioanalytical Research. 

Thiol protection, 59, 190 Thiono esters, reaction with ethyl isocyanoacetate, 59,187 Thionyl chloride, 55, 27 Thiophenol, 55, 122 58, 144 Thorium dodecanedioate, 56,110 Toluene, 56, 86 58,125 p-Toluenesulfonates, reaction with organo-cuprates, 55,112 p-Toluenesulfonic acid, 58, 57, 63 p-Toluenesulfonic acid, monohydrate, 56,44... 

In other ester reactions, there may be concern that the reaction might be concerted, bypassing the tetrahedral intermediate. We will return to this question later. If the properties of Nu or Lv can be varied so that the relative leaving group... 

A number of these alkylation reactions are illustrated in Scheme 9.2. Entries 1 and 2 are typical examples of a-halo ester reactions. Entry 3 is a modification in which the highly hindered base potassium 2,6-di-f-butylphenoxide is used. Similar reaction conditions can be used with a-halo ketones (Entries 4 and 5) and nitriles (Entry 6). Entries 7 to 9 illustrate the use of diazo esters and diazo ketones. Entry 10 shows an application of the reaction to the synthesis of an amide. 

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