- Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups
-
Abstract (±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed.
- Husar, Branislav,Moszner, Norbert,Lukac, Ivan
-
supporting information; experimental part
p. 337 - 343
(2012/05/19)
-
- Action of Red Light on Solid (+)-10-Bromo-2-chloro-2-nitrosocamphane: (i) Nuclear and Electron Paramagnetic Resonance Studies; (ii) Reaction Products; (iii) Solid-state Photolysis Reaction Mechanisms
-
Photolysis of blue, solid (+)-10-bromo-2-chloro-2-nitrosocamphane (1) with red light produces two nitroxide radicals (2) and (3), 10-bromocamphor (4), a 10-bromo-2-chloro-2-nitrocamphane (5), a 2-chloro-5,5-dimethyl-1,2-dinitrobicyclooctane (6a), and a corresponding 1-nitrato-analogue (6b).E.p.r. spectra of (2) and (3) are described and interpreted.Analyses of the 1H n.m.r. spectra of compounds (1) and (5) show that n.m.r. method can be used to determine configurations at active XCCl (X = NO or NO2) centres of gem-chloronitroso and gem-chloronitro derivatives of the terpenes.The combination of chemical and spectroscopic evidence enables some of the steps involved in the solid-state red photolysis reaction of (1) to be unravelled.
- Majeed, Nesreen N.,Porte, Andrew L.
-
p. 1139 - 1146
(2007/10/02)
-