Study On Synthesis,reaction And Properties Of Thiophene O-Aminonitriles

o-Aminohiophenonitriles,a class of electron rich skeleton heterocyclic compound with two functional groups,have received a great interest in the field of pharmaceuticals,pesti-cides,dyes,chemicals,polymer additives,photosensitive materials and wide biological activities such as anticancer,antimalarial,antiinflammatory,antiplasmodial,anticonvulsant,etc.As an eco-and atom-economy,efficient synthetic method of fused heterocycle,cyclocondensation of aromatic o-aminonitriles and carbonyl compounds via PDF reaction（discovered in the normal Friedl?nder quinoline synthesis by our group）led to a lot of different nitrogen-containing heterocyclic compounds such as dihydroquinazoline,benzo[f]pyrimidinone and pyrimido[4,5-d]pyrimidinone,and it has been proved that the PDF transformation is universal.But our previous studies are mainly concentrated on the cyclocondensation of carbonyl compounds with o-aminonitrile based on both all-carbon or nitrogen/oxygen-containning heterocyclic skeleton,and never related to the sulfer-containning heterocyclic skeleton.Additionally,the properties and applications of the products of PDF conversion and those relatived compounds have never been investigated.This paper will study the synthesis of o-aminothiophenonitriles as raw materials,both PDF conversion and Friedl?nder reaction of these synthesized o-aminohiophenonitriles with carbonyl compounds,their properties and application.The main results were summarized as follows:1.PDF conversion of o-aminothienonitrile and carbonyl compounds（Chapter 2）.Thienopyrimidinone derivatives 2.7 were afforded by the cyclocondensation of o-aminohio-phenonitriles with carbonyl compounds in the catalyst of sodium ethanol,and for the first time the unexpected tertiary hydroxyl thienopyrimidinone derivatives 2.8 were also accidentally discovery during the following PDF conversion with UV lamp irradiation.A series tests revealed that the synthesis of 2.8 was influenced by several factors such as dynamics,thermodynamics and steric effect of six membered ring.The controlled experiments including UV lamp irradiation time-real monitoring,running sets under the protection of argon and in the dark condition revealled that the possible mechanism of 2.8formation includes the PDF conversion and subsequent photo-catalytic oxygenation rearrangement.This synthetic strategy offers an alternative method for regioselective construction of tertiary hydroxylated thieno[2,3-d]pyrimidinone architectures with kinetic,thermodynamic control and six-member ring effect.The reaction was shown to have attractive features,including environmentally friendly conditions,simple,clean isolated processing and large scale production.In this section,35 compounds including 16unexpected tertiary hydroxyl thieno[2,3-d]thienopyrimidinone derivatives 2.8 were synthesized,the structure of compound 2.8a and 2.8b were confirmed by single crystal X-ray diffraction determination and the X-ray diffraction showed there were a tertiary hydroxyl group and at least one chiral center carbon atoms are existed in the two molecules.2.PDF conversion of 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile 3.1 with carbonyl compounds（Chapter 3）.Tetra-hydrothieno[2,3-b]thienopyrimidinone derivatives3.3 were synthesized via a novel,straightforward and efficient PDF tandem cycloconden-sation of symmetric o-amino-thieno[2,3-b]thiophenonitrile 3.1 and different ketones and aliphatic aldehyde in the present of base.Correspondingly,the unexpected thieno[2,3-b]thienopyrimidinone derivatives 3.4 were afforded through the similar condensation of 3.1with aromatic aldehydes in the same conditions,which were provided by the further oxidization of PDF product.15 PDF conversion products synthesized were new,and The structures of compounds 3.3a,3.3e and 3.4b were confirmed by single crystal X-ray diffraction.Coplanar comound 3.4b afford two-dimensional layered structure unit in"face to face"cross and arranged to form a tetrahedral structure byπ-πpacking interactions with the distance 3.769?of each layer and extended into 3D supramolecular framework by solvent DMF bridging.3.Friedl?nder reaction of 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile 3.1with ketones and the coordination complexes of the product 4.2（Chapter 4）.The Zn²⁺complexes 4.2a-Zn and 4.2d-Zn of thieno[2,3-b]thiophene fused pyridine derivatives 4.2（bithpy）not free amino-substituted 4.2,normal Friedl?nder condensation product,were fristly obtained by the the reaction of 3.1 with ketones in the catalyst of zinc chloride.4.2 is a kind of bidentate ligands of ortho-phenanthroline structure（bithpy）.The complex of4.2a-Zn and 4.2d-Zn were dealed with aqueous NaOH to release free amino-substituted4.2,and 6 Friedl?nder reaction products 4.2 of 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile 3.1 with ketones in the catalyst of zinc chloride.The determination of single crystal 4.2a-Zn and 4.2d-Zn:the fused pyridine,thiophene thiophene,and pyridine rings were coplanar,and zinc ion is chelated with two nitrogen atoms of bithpy.Its structure is very stability.In addition,4.2a also can be coordinated with transition metal ruthenium.4.Thermal properties,optical properties and applications of o-aminonitriles and some reaction products（Chapter 5）.The thermogravimetry of the conversion products of 3.1 with carbonyl compounds from TG,showed that the synthesized compounds 3.1,3.3,3.4,and4.2-Zn have good thermostability,and the melting point is up to 497 ^oC（melting point of covalent small molecules has not reached so high）.And the results of photoluminescence deteriment of 3.3,3.4,and 4.2-Zn showed they have good fluorescence properties.Furthermore,a series of multi donore-acceptor substituted symmetrical o-aminonitrile pyridine derivatives synthesed were thermally stable and possesed fluorescence exhibit aggregation-induced emission（AIE）in both aqueous solution and solid state due to the restricted intramolecular rotation as well.Moreover,the importance of dyes for heavy and transition metal ion species detection applications was demonstrated via the“turn off”detection of Au³⁺in aqueous solution with the simple synthetic approach and high selectivity and sensitivity.