Insight into the Mechanism of Reversible Ring-Opening of 1,3-Benzoxazine with Thiols.
The reversible ring-opening addition and fragmentation reaction of p-cresol-based N-phenylbenzoxazine with aliphatic and aromatic thiols was investigated in solvent-mediated and solvent-free reactions. Independently of the used thiol, N-phenylbenzoxazine and the thiols reacted to equilibrium with comparable amounts of reactants and products in aprotic solvent, whereas in protic solvent almost full conversions were reached. In contrast, thiol reactivity was a crucial factor in solvent-free reactions yielding fast and complete conversions for a more acidic thiol and balanced equilibrium concentrations in case of thiols with high pKavalues. The strong influence of thiols with low pKavalues emphasizes the relevance of the protonation step in the ring-opening reactions of 1,3-benzoxazines with thiols in absence of solvents where acidity predominates nucleophilicity. The reverse reactions, namely adduct dissociation and benzoxazine recovery, were successfully conducted at elevated temperatures and reduced pressure facilitated by the removal of the formed thiols yielding up to 95% recovered 1,3-benzoxazine. These results provide deeper understanding of the reversible ring-opening reaction mechanism of 1,3-benzoxazine with thiols.
Fraunhofer Institute for Manufacturing Technology and Advanced Materials (IFAM) , Wiener Strasse 12, D-28359 Bremen, Germany.|Institute for Organic and Analytical Chemistry, University of Bremen , Leobener Strasse NW2C, D-28359 Bremen, Germany.
Tobias
T
Urbaniak
Fraunhofer Institute for Manufacturing Technology and Advanced Materials (IFAM) , Wiener Strasse 12, D-28359 Bremen, Germany.
Marc
0000-0002-3939-0486
M
Soto
Max Planck Institute for Marine Microbiology , Celsiusstrasse 1, D-28359 Bremen, Germany.
Manuel
M
Liebeke
Fraunhofer Institute for Manufacturing Technology and Advanced Materials (IFAM) , Wiener Strasse 12, D-28359 Bremen, Germany.
Katharina
0000-0001-7398-3528
K
Koschek