The Synthesis And Crystal Structure Research Of The Novel Acylthiourea And Its Functional Complexes

This paper includes three chapters:Chapter One. This chapter is a brief review for the synthetic methods of acylthioueas The crystal structure of acylthiouea complexes are briefly summarized. Then the research and application values of acylthioueas and their metal complexes in the fields of pesticide, superamolecular anion recognition, superamolecular self-assembly have been reviewed.Chapter Two. Ethyl chloroformate was treated with potassium thiocyanate in ethyl acetate in the presence of a catalysis N, N, N', N'-tetramethylethylenediamine to produce the ethoxycarbonylisothiocyanate. This compound can directly react with aryl-amines without isolation to afford N-benzoyl-N'-arylthioureas and N-ethoxycar bonyl-N'-arylthioureas. In conclusion, this method is an efficient and convenient method for the synthesis of N-aryl-N'-acylthioureas. Moreover, a series of N-aryl-N'-ethoxycarbonyl thioureas and arene (or polymethylene)-bis-ethoxycarbonylthiourea derivatives have been synthesized in good to excellent yields under the TMEDA catalyzed conditions at room temperature. The twenty-two metal acylthiouea complexes were synthesized by the eight acylthiourea ligands and Hg(II),Cu(II). All compounds were characterized by IR, ¹H NMR and EA.Chapter Three. The single crystal structure of N-ethoxycarbonyl-N'-(3-pyridyl) thiourea and four complexes were analyzed by X-ray diffraction. In conclusion There are hydrogen bonging andÏ€staking superamolecular interactions in N-ethoxycarbonyl-N'-(3-pyridyl) thiourea crystal. The compound was self-assembled to one-dimensional linear 1 netlike superamoleculer structure.The complex bis{(μ-chloro)-chloro-[N-benzoyl-N'-(2-hydroxyethyl)thiourea] mercury(II)} was prepared by the reaction of HgCl₂ with N-benzoyl-N'-(2-hydroxyethyl) thiourea.This complex is a binuclear complex with two Hg(II) ions tetrahedrally coordinated by a terminal chloride ion, two bridging chloride ions and a HL molecule. The Hg(II) ion is coordinated with HL via S(l) atom.A novel copper(II) complex, CuL₂(HL=N-ethoxycarbonyl-O-ethyl-N'-(2,4,6-trichlorophenyl)-isourea), derived from the desulfurated hydrogen of N-(2,4,6-trichorophenyl)-N'-ethoxycarbonyl-thiourea has been synthesized and crystallographically characterized. The metal ion in the (2:1) complex of HL with copper(II) is coordinated by the two N atoms and the two carbonyl O atoms of two ligands molecules resulting in two six membered chelate rings. This procedure provide a new way to synthesize isourea.We provide a new way to synthesize amionbenzothiazole. The ethyl 4,6-dibromobenzothiazol-2-ylcarbamate was formed in the reaction. The reason for this was presumably due to the fact that electrons of copper (II) transferred into the vacant p orbital of bromine atom and the delocalization of p orbital andÏ€system were weakened by this electrons transferredThe compound (CuL)6 (L=N-ethoxycarbonyl-N'-(4-fluorophenyl)-thiourea) was synthesized from L and Cu(NO₃)₂·3H₂O in ethanol, and characterized by Elemental analysis, IR, ¹H NMR, thermogravimetry and differential thermal analysis with its crystal structure determined by X-ray single crystal diffraction. The crystal of compound belongs to triclinic system.This compund is cage shaped metal cluster to consist of six copper (II) and six thiourea ligands.