Synthesis and molecular recognition for tetraaza[14]annulenes and their complexes containing hydroxy groups

四氮杂[14]轮烯及其含羟基配合物的合成与分子识别

• 批准号: 10640548
• 负责人: SAKATA Kazunori
• 金额: $ 2.05万
• 依托单位: Kyushu Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640548/
• 关键词: Tetraaza[14]annulene; Template Reaction; Nickel(II) Complexes; Acyl Chlorides; Molecular Recognition; Hydroxy Groups; Hydrogen Bonds; Quinone; NMRスペクトル; IRスペクトル; 銅(II)錯体; ヒドロキシ安息香酸; サリチル酸メチル; 酸塩化物

1. Synthesis of Tetraaza[14]annulene and its Nickel(II) Complex-The nickel(II) complex (1-Ni) was prepared from 1,2-diaminobenzene, acetylacetone and nickel(II) acetate tetrahydrate. The metal-free compound (1) was prepared from complex (1-Ni) by treatment of hydrochloric acid gas.2. Synthesis of Acyl Chlorides-Benzyloxybenzoic acid were synthesized from hydroxybenzoic acid and benzylbromide in the presence of sodium hydroxide. Refluxing the benzyloxydibenzoic acids with thionyl chloride gave acyl chlorides (2).3. Synthesis of Tetraaza[14]annulene and its Nickel(II) Complex with hydroxy Groups-The reaction of compounds (1,1-Ni) with various benzyloxybenzoyl chlorides (2) led to the corresponding 7,16-dibenzoylated compound (3,3-Ni) in refluxing tolunene containing triethylamine. These compounds with hydroxy groups (4,4-Ni) were obtained in reduction of the compounds (3,3-Ni).4. Molecular(Recognition of Tetraaza[14]annulene and its Nickel(II) Complex with Hydroxy Groups-The compounds (4,4-Ni) have the sizeable cavities which include some quinone compounds. The cavity needs the hydroxy groups in the 7,16-positions because the formation of hydrogen bond between compounds (4,4-Ni) and quinone compounds is of a great importance for the stability of resulting inclusion compounds. Judging from the behavior of ィイD11ィエD1H NMR and IR spectra, the compounds (4,4-Ni) are presumed to exist in inclusion compounds.5. Discussion about Molecular Recognition Tetraaza[14]annulene and its nickel(II) Complex with Hydroxy Group-The results of IR and ィイD11ィエD1H NMR spectra show very week interaction between compounds (4,4-Ni) and quinone compounds with hydrogen bonds.

1.四氮杂[14]轮烯及其镍(II)配合物的合成--以1，2-二氨基苯、乙酰丙酮和醋酸镍(II)为原料合成了镍(II)配合物(1-Ni)。由络合物(1-Ni)经盐酸气体处理制得无金属化合物(1)。在氢氧化钠存在下，以对羟基苯甲酸和溴化苄为原料合成了酰氯-苯氧基苯甲酸。苯氧基二苯甲酸与亚硫酰氯回流得到酰氯(2)。四氮杂[14]轮烯及其含羟基镍(II)配合物的合成-化合物(1，1-Ni)与不同的苯氧基苯甲酰氯(2)反应，在含有三乙胺的甲苯中回流得到相应的7，16-二苯甲酰化化合物(3，3-Ni)。这些含羟基(4，4-Ni)的化合物是通过还原(3，3-Ni)得到的。分子(识别四氮杂[14]轮烯及其含羟基的镍(II)络合物)-化合物(4，4-Ni)具有相当大的空穴，其中包括一些醌化合物。空穴需要7，16位的羟基，因为化合物(4，4-Ni)与苯二酚化合物之间的氢键的形成对所得包合物的稳定性非常重要。从ィイ-D11-ィエ-D1H核磁共振和红外光谱的行为来看，化合物(4，4-Ni)可能存在于包合物中。四氮杂[14]轮烯及其含羟基镍(II)络合物的分子识别讨论--IR和ィイD11ィエD1HNMR谱的结果表明，化合物(4，4-Ni)与具有氢键的醌类化合物之间的相互作用非常弱。

项目成果

Zenglin Wang: "Syntheis, characterization and crystal structure of a 6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene yttrium(III) complex"Polyhedron. 17. 4451-4456 (1998)

王增林：“6,8,15,17-四甲基二苯并[b,i][1,4,8,11]四氮杂[14]轮烯钇(III)配合物的合成、表征和晶体结构”多面体。

Tetsuji Moriguchi: "Evalution of Transannular Interaction of [2.3]Metacyclophane-diazonium Tetrafluoroborate and its Dediazoniated Derivatives"J.Chem.Research(s). 1999(2). 78-79 (1999)

Tetsuji Moriguchi：“[2.3]Metacyclophane-重氮四氟硼酸盐及其去重氮化衍生物的跨环相互作用的评估”J.Chem.Research(s)。

Kazunori Sakata: "Preparation and Spectral properties of nickel(II) and copper(II) complexes with two isopmeric cyclohexylcyclams" Polyhedron. 17(9). 1463-1470 (1998)

Kazunori Sakata：“镍（II）和铜（II）与两种同分异构环己基环己酰胺配合物的制备和光谱特性” 多面体。

Zenglin Wang: "Syntheses, Characterization and Crystal Structure of Teramethyldibenzotetraaza[14]annulene Zinc(II) Complexes Containing an Axial Base"J. Coord. Chem.. 48(4). 541-554 (1999)

王增林：“含轴向碱基的四甲基二苯并四氮杂[14]轮烯锌(II)配合物的合成、表征及晶体结构”。

Kazunori Sakata: "Preparation and spectral properties of nickel(II) and copper(II) complexes with two isomeric cyclohexylcyclams"Polyhedron. 17. 1463-1470 (1998)

Kazunori Sakata：“具有两种异构环己基环己酰胺的镍（II）和铜（II）络合物的制备和光谱特性”多面体。