The Alkylation of Esters and Nitriles

Abstract

This chapter is concerned with the reactions of metal salts (enolates) of active methylene compounds with alkylating agents such as alkyl halides to produce allyl derivatives. The first example of this reaction is found in the literature when Geuther prepared ethyl alpha‐ethyl acetoacetate by the reaction of the sodium enolate of ethyl acetoacetate with ethyl iodide. The active methylene compounds considered in the chapter include malonic esters, cyanoacetic esters, malonitriles, monocarboxylic esters and mononitriles. These classes of compounds are characterized by the presence of one or more acidic hydrogen atoms attached to carbon. Only C‐alkylation has been observed with active methylene compounds and are discussed here. Several alternative methods for the preparation of alkyl and aryl derivatives of carboxylic esters and nitriles have been included.

Assessing the Downstream Contamination of Chemically Recycled Ethylene Feed Streams on the Kinetic Behavior of Ziegler‐Natta Catalysts and Microstructural Properties of HDPE and LLDPE

“…[ 39 ] Moreover, as metal alkyls like TEA readily react with functional groups, gas‐liquid phases can influence that, as liquid contaminants are in the same phase as the catalyst whereas gaseous contaminants depend on their solubility and saturation in the reaction solvent. [ 39 ]…”

“…[22,37] Potential alkylation of the n-BuCN nitrile group or the BzOEt ester group by TEA can destroy the activating power of the cocatalyst, which can explain the stronger influence on the catalyst activity, especially for P COCAT . [39] Moreover, as metal alkyls like TEA readily react with functional groups, gas-liquid phases can influence that, as liquid contaminants are in the same phase as the catalyst whereas gaseous contaminants depend on their solubility and saturation in the reaction solvent. [39] For kinetic analysis, Equation 4was applied as a model to gather insights into kinetic rate constants.…”

“…[39] Moreover, as metal alkyls like TEA readily react with functional groups, gas-liquid phases can influence that, as liquid contaminants are in the same phase as the catalyst whereas gaseous contaminants depend on their solubility and saturation in the reaction solvent. [39] For kinetic analysis, Equation 4was applied as a model to gather insights into kinetic rate constants. Figure 3 shows the obtained models and Table 4 shows the respective rate constants.…”

Synthesis of trialkyl 2-halogeno-1,1,1-ethanetricarboxylates

“…Diiodomethane reacts with 10 and the potassium or cesium carbonate in DMSO with yields comparable to dibromomethane, whereas dichloromethane, even in a closed vessel, only yields 1.3% of 17. The replacement of dichloromethane by chloroiodomethane that implies the change of the poor nucleofuge chloride by the effective iodide, 17 increases the yield of 17 to 89%.…”