Application Of Smiles Rearrangement For The Synthesis Of Thiazine Derivatives And Thiazepine Derivatives

Since1931Samuel Smiles and Warren documented that "iso-β-naphthol sulfide" when heated in aqueous sodium hydroxide solution, undergoes rearrangement to hydroxy mercaptane. Smiles rearrangement reaction has been eliciting widespread interest in the organic chemists. Smiles rearrangement is an intramolecular nucleophilic aromatic substitution reaction. And the most important feature in the modern development of the Smiles rearrangement is its application to heterocyclic chemistry. Various heterocyclic compounds have been approached with the intended or with "unexpected" rearrangement.Though Computer-Aided Drug Design(CADD) is playing an increasingly important role in the discovery of new drugs and pharmaceutical industry, traditional organic synthesis still plays an irreplaceable cornerstone role in drug research and development. Meanwhile, with environmental problems revealing especially day-by-day, developing new synthetic methods to reduce the pollution of the environment is not only highly needed but also particularly urgent. Moreover, with environmental problems revealing especially day-by-day, developing new synthetic method to reduce the pollution of the environment is not only highly needed but also particularly urgent.This thesis studies on the synthesis of nitrogen-and sulfur-containing heterocyclic compounds with biological activities via Smiles rearrangement. The thesis is divided into four chapters:In the first chapter, the synthetic application of Smiles rearrangement reaction and some related series reactions are briefly reviewed. And the second, third and fourth chapters are a description of my work during my Master’s study. They are summarized as follows: (1) A One-Pot Synthesis of benzo[1,4]thiazin-3(4H)-ones and Theoretical Study on S-N Type Smiles Rearrangement Mechanism(2) A Facile Method for the Synthesis of Pyridazino[4,5-b][1,4]thiazine-diones via Smiles Rearrangement(3) One pot Regioselective Synthesis of a Small Library of Dibenzo [bnf][1,4] thiazepin-11(10H)-ones via Smiles Rearrangement...