Synthesis and molecular recognition for strapped tetraaza [14] annulenes and their complexes with hostly function

1四氮杂[14]轮烯及其配合物的合成--以1，2-二氨基苯、2，4-戊二酮和四水合醋酸镍为原料合成了镍(II)配合物(1-Ni)。以络合物(1-Ni)为原料，经盐酸处理制得不含金属的化合物(1)。从化合物(1)和醋酸铜(II)水合物中制备铜(II)配合物(1-铜)。2四氮杂四氮杂[14]轮烯配合物的合成--配合物(1-Ni)或(1-铜)与各种对取代苯甲酰氯(2)或各种对取代溴化苄基(3)反应生成相应的7，16-二苯甲酰化配合物(2-Ni，3在氢氧化钠存在下，以3-羟基苯甲酸和不同的二溴(溴-R-溴)为原料合成了带基二苯甲酸。4四氮杂[14]环烯类络合物的合成--四氮杂[14]轮烯镍(II)络合物(5-Ni)是在一个含有过量三乙胺的大型甲苯储存库中回流得到的。通过上述步骤得到了无金属的带状化合物(5)和它们的铜(II)配合物(5-Cu)。5具有强烈功能的带状四氮杂[14]轮烯配合物的分子识别-带状配合物(5-Ni，5-Cu)具有相当大的空穴，其中包括一些有机化合物。由于络合物(5-Ni，5-Cu)与有机化合物之间形成氢键对包合物的稳定性具有重要意义，所以空腔需要桥基上的醚氧。

1 Synthesis of Tetraaza [14] annulene and its Complexes-The nickel (II) complex (1-Ni) was synthesized from 1,2-diaminobenzene, 2,4-pentanedione and nickel (II) acetate tetrahydrate. The metal-free compound (1) was prepared from complex (1-Ni) by treatment of hydrochloric acid gas. The copper (II) complex (1-Cu) was prepared from compound (1) and copper (II) acetate hydrate.2 Synthesis of Picket-Fence Tetraaza [14] annulene Complexes-The reaction of complex (1-Ni) or (1-Cu) with various para-substituted benzoyl chlorides (2) or various para-substituted benzyl bromides (3) led to the corresponding 7,16-dibenzoylated complexes (2-Ni, 2-Cu) or 7,16-dibenzylated complexes (3-Ni) .3 Synthesis of Strapped Group-Dibenzoic acids were synthesized from 3-hydroxybenzoic acid and various dibromides (Br-R-Br) in the presence of sodium hydroxide. Refluxing the dibenzoic acids with thionyl chloride gave diacyl chlorides (4) .4 Synthesis of Strapped Tetraaza [14] annulene Complexes-The strapped tetraaza [14] annulene nickel (II) complexes (5-Ni) were produced by refluxing complex (1-Ni) with diacyl chlorides (4) in a large reservoir of toluene containing an excess of triethylamine. The strapped metal-free compounds (5) and their copper (II) complexes (5-Cu) were obtained following the above procedure.5 Molecular Recognition of Strapped Tetraaza [14] annulene Complexes with Hostly Function-The strapped complexes (5-Ni, 5-Cu) have the sizeable cavities which include some organic compounds. The cavity needs the ethereal oxygen in the bridging group since the formation of hydrogen bond between complexes (5-Ni, 5-Cu) and the organic compounds is of a great importance for the stability of resulting inclusion compounds.