The Coupling Of Hydrazine With Thiol By Catalytic Metal Micelles

Organosulfur compounds exist widely in nature and play an important role in medicine,agriculture,food and biology.There had been a lot of research on synthesis of thioether compound.Regarding the synthesis of thioether compounds,the traditional method is to use halogenated compounds and organosulfur compounds to perform addition-elimination reactions in organic solvents through transition metal catalysis.For halogenated aromatic hydrocarbons with low activity,these reactions often require higher temperatures and longer reaction times.Some reactions use high-valent oxidants,which can easily cause product peroxidation.At the same time,the complex sulfur source causes many reaction by-products which brings inconvenience to the post-treatment.The reaction uses the high-boiling organic solvent,which is harmful to the environment.With the development of green chemistry,making full use of resources,reducing the discharge of chemical waste,and increasing the utilization rate of atoms have become crucial issues.Hydrazine,as an environmentally friendly arylation reagent,has attracted much attention,because its only by-products are nitrogen and water,which are pollution-free.Oxygen as an oxidant,is not only a renewable resource,but also mild,cheap and highly available.Compared with the traditional organic oxidant used commonly in existing technologies,oxygen as oxidant will avoid over-oxidation that produce a variety of byproducts.Water as an environment-friendly solvent is clean,safe,easy-to-handle which conforms to the concept of green chemistry.In this thesis,we designed a series of poly(ethylene glycol)-functionalized nitrogen ligands.The PEG chains were introduced into the aromatic rings of 1,10-phenanthroline and bipyridine to increase their water solubility.Copper and PEG-functionalized nitrogen ligands could form metallomicelles and catalyze the coupling reaction of thiols with hydrazine compounds.Catalysts,ligands,bases,temperatures and other reaction parameters were screened,and the optimal reaction condition was determined as follows:1 equiv.Hydrazine,1 equiv.thiol,5 mol % of Cu(NO)3·3H2O catalyst,5 mol % L1 ligand,1 equiv.Cs2CO3,2 ml water as solvent,100 oC,0.1 MPa O2.This condition is applicable to a wide range of substrates.37 organosulfides are obtained and characterized by melting point,low resolution mass spectrometry,high resolution mass spectrometry,1H NMR and 13 C NMR.In conclusion,an efficient and environment-friendly method to synthesize organosulfides with wide applicability had been established.