A One-pot Synthesis Of Pyrrole From Ketone Via The Trofimov Reaction

Important biological properties of pyrrole derivatives stimulate the incessant search for new and improved methods of the pyrrole nucleus. Ketoximes with acetylene in superbasic media afford pyrroles and N-vinylpyrroles. This method is called the Trofimov reaction. Undergoing more than 30 years, it is concerned and studied until now. The estimates of feedstock resources show that oil and natural gas are exhausting rapidly, the return to a coal-based technology with reinforcing the acetylene branch in chemical industry seems to be probable. Here we report one-pot synthesis of pyrrole derivatives from ketone and acetylene. There are for parts in this thesis:Chapter 1: Reacent progress in the synsesis of pyrrole compounds is reviewed.Chapter 2: Study a one-pot synthesis of pyrrole via the Trofimov Reaction. 9 kinds of alkyl-, aryl- and hetaryl ketones after a one-pot oximation and treatment with acetylene are converted to 2-mono- and 2,3-disubstituted NH- and N-vinylpyrroles in good yields. The oximation is effected using a NH₂OH·HCl-NaHCO₃ system at room temperature. The reaction with acetylene is carried out in the presence of the KOH/DMSO superbase at 100℃ under atmospheric pressure.Chapter 3: The synthesis of paraphenyldiamine is improved by change the ratio of composition and improve the process of crystallization, purification and dry. The yield increase from 70% to 90%, the period of production decrease by one-half and the purity of product is more than 99.5%.Chapter 4: 7,7-Dichlorodicyclo[4,l,0]heptane is synthesized under phase-transfer catalysis condition. Different catalysts activity, quaternary ammonium salt, polyalcohol and polyether, is investigated in the addition of dichlorocarbene and cyclohexene. The optimum condition with polyethylene glycol catalyst is determined.