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

1四氮杂[14]环烯及其配合物的合成——以1,2-二氨基苯、2,4-戊二酮和四水合乙酸镍（II）为原料合成镍（II）配合物（1- ni）。以配合物（1- ni）为原料，经盐酸气体处理制得无金属化合物(1)。以化合物(1)和醋酸铜（II）水合物为原料，制备了铜（II）配合物（1- cu）尖栅四氮杂[14]环烯配合物的合成-配合物（1-Ni）或（1-Cu）与各种对取代苯甲酰氯(2)或对取代苯溴(3)反应，得到相应的7,16-二苯甲酰配合物（2- ni, 2- cu）或7,16-二苯甲酰配合物（3- ni）。以3-羟基苯甲酸和各种二溴化物（Br-R-Br）为原料，在氢氧化钠的存在下合成了带基团二苯甲酸。二苯甲酸与亚硫酰氯回流得到二酰基氯化物(4)。4带链四氮杂[14]环烯配合物的合成——带链四氮杂[14]环烯镍（II）配合物（5-Ni）是在含有过量三乙胺的大量甲苯储层中，用二酰基氯化物(4)将配合物（1-Ni）回流生成的。用上述方法得到无金属化合物(5)及其铜（II）配合物（5- cu）具有宿主功能的带链四氮杂环烯配合物的分子识别-带链配合物（5-Ni, 5-Cu）具有相当大的空腔，其中包含一些有机化合物。由于配合物（5-Ni, 5-Cu）与有机化合物之间氢键的形成对生成的包合物的稳定性至关重要，因此空腔需要桥接基中的空灵氧。

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.