Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst

Abstract

Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reaction of imides with oxiranes. In this article the kinetics of the reaction of cyclic monoimides: succinimide, phtalimide, and glutarimide, with ethylene and propylene oxides in presence of triethylamine in aprotic solvent was studied. The rate laws for those processes were established based upon on dilatometric measurements. I was said that cyclic monoimides react with oxiranes in presence of triethylamine to give N-(2-hydroxyalkyl)imides as major product. This product react further with oxiranes in consecutive reaction. The kinetics of the reaction of cyclic mono-imides with oxiranes obey the following rate law: V = k 1/2 . Based upon kinetic data the following orders of reactivity of imides and oxiranes were obtained: phtalimide ≥ succinimide > glutarimide and ethylene oxide > propylene oxide. The solvent (DMF, DMSO and dioxane) effect was also studied. From temperature dependences the thermodynamic parameters: activation energy, enthalpy and entropy from linear Eyring plots were obtained.

Hydroxyalkylation of Cyclic Imides with Oxiranes Part III. Mechanism of the Reaction in Presence of Sodium Hydroxide Catalyst

“…Kinetics of reaction was studied by dilatometry, i.e. by measuring volume contraction of reaction mixture, as it was described before [5]. Relative concentration of oxirane (b) was defined as…”

“…Hydroxyalkylation of cyclic monoimides has been exploited mostly for syntheses [1] [2] [3] [4]. Knowledge on the kinetics and mechanism of the reaction is limited to two publications [5] [6]. On the other hand the kinetics and mechanism of reaction of oxiranes with compounds containing acidic groups like alcohols, thiols, carboxylic acids, amides are well recognized [2] [7]- [13].…”

“…Encountered multifunctional cyclic imides are not suitable for monitoring the kinetics of reaction with oxiranes due to their low solubility in contrary to cyclic monoimides [5] [6]. The kinetics and mechanism of reaction between oxiranes (EO and PO) with SI, PI, and GI in presence of triethylamine (TEA) was studied in details and general rate low was found as [5]:…”

“…the reaction of N-(hydroxyalkyl)imides with oxiranes follow different mechanism than reaction of imide with oxirane. The oxirane-related order of consecutive reaction is 1 in comparison with ½ for reaction of imide with oxirane [5] [6]. In order to further understand the mechanism of these processes we have undertaken detailed study on kinetics of reaction between cyclic imides and oxiranes in presence of sodium hydroxide catalyst.…”

Hydroxyalkylation of Cyclic Imides with Oxiranes. Part II. The Mechanism of Reaction in Presence of Triethylamine

“…The reaction of cyclic monoimides with oxiranes in presence of triethylamine (TEA) leads to N-(hydroxy-alkyl) imides of the general formula (I): where R = (-CH 2 -) 2 , (-CH 2 -) 3 , -Ph R' = -H, -CH 3 As it was presented in [1] the reaction follows the rate law (2): 1 2 3 2 1 2 1 2 K AH B V k c c c  …”