Dramatic Enhancement of Superacid-Catalyzed Polyhydroxyalkylation Reactions

Autor:	Serguei Fomine, Maria T. Guzmán-Gutiérrez, Mikhail G. Zolotukhin, Edward S. Wilks, Daniel Nieto, Hans R. Kricheldorf, Salvador López Morales, M. Carmen G. Hernandez
Rok vydání:	2010
Předmět:	Reaction mechanism Polymers and Plastics Chemistry Organic Chemistry Protonation Photochemistry Inorganic Chemistry Electrophilic substitution Acid catalysis chemistry.chemical_compound Nucleophile Electrophile Materials Chemistry Reactivity (chemistry) Superacid
Zdroj:	Macromolecules. 44:194-202
ISSN:	1520-5835 0024-9297
DOI:	10.1021/ma102267f
Popis:	Complementary theoretical and experimental studies of the consecutive steps of superacid catalyzed polyhydroxyalkylation reactions have been carried out. Calculations for the superacid catalyzed polyhydroxyalkylation of trifluoroacetone and trifluoroacetophenone with aromatic hydrocarbons explained a number of experimental facts within a single theoretical framework of monoprotonation. The principal factors affecting kinetics of superacid mediated hydroxyalkylation were shown to be as follows: (i) the acidity of the superacid affecting protonation energy of carbonyl components; (ii) the electrophilicity of carbonyl components; and (iii) the nucleophilicity of aromatic components. The modification of those factors allows for tuning of the reactivity of carbonyl and aromatic components; thereby, reaction kinetics are controlled. The conclusions were confirmed by the experiments. Theoretically predicted stoichiometrically imbalanced polymerizations of trifluoroacetone, trifluoroacetophenone, octafluoroacetop...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::599e1d4f721ff896ac2bb8e720484ad2 https://doi.org/10.1021/ma102267f Zobrazit plný text záznamu