Alkylation of Cyclododecanone with Allyl Acetate in the Presence of Solid Radical Initiators. Issue 24 (19th June 2018)

• Record Type: Journal Article
• Authors: Köckritz, Angela; Eckelt, Reinhard; Koch, Oskar; Esser, Peter; Panten, Johannes; Baumann, Wolfgang; Atia, Hanan
• Is Part Of: European journal of inorganic chemistry. Issue 24(2018)
• Page Start: 2776
• Page End: 2784
• Publication Date: 2018-06-19
• Subjects: Alkylation -- Radical reactions -- Metal oxide initiators -- Cycloalkanones -- Allyl acetate; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201800145
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The radical alkylation of cyclododecanone (CDD) with allyl acetate (AlAc) yielding 2‐[3‐(acetyloxy)propyl] cyclododecanone (CDDPA) in the presence of different inorganic radical initiators was investigated. The most useful initiator among other inorganic metal oxides was found to be CuO. The molar ratio of CDD and AlAc was varied between 10:1 and 3:1. CuO was characterized by using different analytical methods, such as N2 adsorption, powder X‐ray diffraction, temperature‐programmed reduction, scanning electron microscopy, and X‐ray photoelectron spectroscopy. The reaction was performed in a batch system, by adding all the reactants at once, and in a semibatch procedure by dosing AlAc over the whole time of the experiment. Different parameters that affected the selectivity of CDDPA were studied, such as the ratio of CDD/AlAc, reaction time, surface of CuO initiator, and reaction temperature. The best result was obtained with 21 % conversion of CDD and 77 % selectivity to CDDPA at a final molar ratio of CDD/AlAc = 4:1 in the semibatch procedure. Abstract : Radical alkylation of cyclododecanone (CDD) with allyl acetate (AlAc) by using CuO as a radical initiator is described for the first time. A selectivity for 2‐[3‐(acetyloxy)propyl] cyclododecanone (CDDPA) of 77 % was achieved after applying a semibatch procedure with slow continuous dosing of AlAc, structural optimization of CuO, and adjustment of the final AlAc/CDD molar ratio.