ISSN print edition: 0366-6352
ISSN electronic edition: 1336-9075
Registr. No.: MK SR 9/7
Mechanism of α-acetyl-γ-butyrolactone synthesis
Wei Wang, Sheng-Wan Zhang, Mei-Ping Li, and Ying-Yu Ren
School of Life Science, Shanxi University, Taiyuan, 030006, China
Abstract: The mechanism of α-acetyl-γ-butyrolactone (ABL) synthesis from γ-butyrolactone (GBL) and ethyl acetate (EtOAc) was explored by detecting the material changes involved and the enthalpies of formation of the synthons, products, and possible intermediates were calculated using the density functional theory. GBL forms a carbanion of γ-butyrolactone by losing an α-H under strongly alkaline conditions. ABL is then obtained via two reaction mechanisms. One of the reaction mechanisms involves direct reaction of the carbanion of GBL with EtOAc to produce ABL. The other involves the formation of a carbanion of α-(2-hydroxy-tetrahydrofuran-2-yl)-γ-butyrolactone through the reaction of two molecules of GBL, and the subsequent combination of this anion with EtOAc to produce ABL. ABL is thus formed through the above two kinds of competitive ester condensation reactions. It is unnecessary to take into account synthons’ local thickness, and their self-condensation under these conditions. Both reactions of the carbanion of GBL with EtOAc and GBL are exothermic, so the control of their reaction rate is the key to their security. Considering the reasons above, this work applied synthon as the solvent, and avoided environmental pollution by alkylbenzene; also, accidents such as red material and fire were avoided by specific surface area of sodium metal control. Effective isolation of the organic and aqueous phases was performed using the salting out method. Thus, an environmentally friendly, safe, simple, and efficient new method for the synthesis of ABL with the yield higher than 90 % has been established.
Keywords: mechanism – enthalpy of formation – α-acetyl-γ-butyrolactone – synthesis
Full paper is available at www.springerlink.com.
Chemical Papers 67 (6) 624–630 (2013)