ChemInform Abstract: AROMATIC KETO PEROXIDES ‐ PHOTOINITIATORS OF RADICAL REACTIONS. PREPARATION OF BENZOYL‐TERT‐BUTYLPEROXYMETHANOL BY THE REACTION OF PHENYLGLYOXAL WITH TERT‐BUTYL HYDROPEROXIDE

Abstract

Phenylglyoxal (I) addiert tert.‐Butylhydroperoxid (II) zur Titelverbindung (III) mit photolabiler Benzoyl‐ und thermolabiler Peroxidgruppe am selben C‐Atom.

Catalytic Oxidative Cleavage Reactions of Arylalkenes by tert-Butyl Hydroperoxide – A Mechanistic Assessment

“…tert -Butyl p -methylperbenzoate was investigated as a possible intermediate formed from hemiketal 6a produced by addition of TBHP, but this compound was not detected (<1%) in the reaction mixture, and the perester was determined to be stable under the reaction conditions. However, hemiketal peroxide 11a , which was determined by spectral and HRMS to be a reaction product from the oxidation of 6a by T-HYDRO in chloroform or cyclohexane at room temperature with Rh 2 (cap) 4 as the catalyst, was independently synthesized from phenylglyoxal . Treatment of 11a with T-HYDRO and catalyst gave the results as shown in Scheme .…”

“…2-Oxo-2-( p -tolyl)­acetaldehyde was prepared according to the reported procedure . 2-( tert -Butylperoxy)-2-hydroxy-1-( p -tolyl)­ethan-1-one 11a was prepared with modification from ref . T-HYDRO (510.0 μL, 3.6 mmol) was added dropwise to a 50.0 mL round-bottom flask of a 10.0 mL solution of water containing 2-oxo-2-( p -tolyl)­acetaldehyde (300.0 mg, 1.8 mmol), after which the reaction solution was stirred for 12 h at room temperature, and a white precipitate was formed.…”

“…However, hemiketal peroxide 11a, which was determined by spectral and HRMS to be a reaction product from the oxidation of 6a by T-HYDRO in chloroform or cyclohexane at room temperature with Rh 2 (cap) 4 as the catalyst, was independently synthesized from phenylglyoxal. 29 hemiketal peroxide 11a to p-toluic acid 10a in 94% yield, whereas no reaction occurred in CHCl 3 . Oxidation of 11a by TBHP in water with Rh 2 (cap) 4 as the catalyst at room temperature produced p-toluic acid in only 10% yield.…”

Curing of Divinyl Triethylene Glycol Bis-o-phthalate Films in the Presence of Photoinitiators

“…Much attention is given today to photopolymerization of oligomers containing double bonds, because of the possibility of combining the polymerization and curing in a single process cycle and of using such compounds in production of optical disks, in protective and adhesive coatings, in polygraphy, and in stomatology [1,2]. Promising photoinitiators (PIs) are transition metal b-diketonates because of their availability and high stability in storage [3].…”