Naslov
Thermal vs. photochemical reactivity of hydroxycycloalkylphenols

Autori
Nikola Cindro

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Skup
13th YoungChem

Mjesto i datum
Kraków, Poljska, 07.10.2015. - 11.10.2015

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
excited state proton transfer (ESPT); carbocations; zwitterions; DFT; laser flash photolysis; m-quinone methide

Sažetak
Hydroxyalkylphenols such as molecule 1 can undergo elimination reaction to form quinone- methides QM 2 and carbocations [1]. These reactions can be performed under photochemical or acid-catalyzed conditions both yielding the intermediates which further on react, usually with solvent, yielding appropriate adducts 3 as shown in figure 1. This type of reaction especially when photochemicaly induced could in principle serve as a way of binding tag molecule into living organisms or inducing apoptosis in a selected region (photodynamic therapy). It has been noticed that QM bearing adamantane moiety have longer lifetime which is probably due to steric hindering which is making it more difficult for a nucleophile to attack. In case of adamantyl derivatives where there is no vicinal methylene group attached to hydroxyl the reaction gives only the solvent adduct or in some cases the rearrangement products [2]. Herein we report on photochemical and thermal (acid catalyzed) reactions of compounds 4-6 bearing a vicinal methylene group which opens a new route to styrene derivatives. In this way there is a competition between addition, elimination and in case of 4 and 5 possible rearrangement. Especially interesting was reactivity of compound 4 which gives rearrangement products only in thermal solvolisys, while in photochemical methanolisys ether is formed as a major product with retention of configuration.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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