Synthesis and Specific Properties of Novel Allosteric Host Compounds

新型变构主体化合物的合成和特性

• 批准号: 07651027
• 负责人: YAMAMOTO Makoto
• 金额: $ 1.6万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651027/
• 关键词: allosteric host; diazacrown ether; metal ion transport; metal complex; molecular recognition; cryptand; hypervalent iodine compound; 金属錯化合物; エチニルアミン; アザクラウンエーテル

The author has studied by the above project, and foIIowing results were obtained.(1). Synthesis and its capturing of metal ion of host compounds bearing flexible cavity were carried out. Pd (II) ion was included at pyridine site of the host compound, but Pb (II), Cu(II) and Zn (II) ions were captured at beta-dicarbonyl site. Host (6) formed the Cu-complex (7) which is again included potassium cation in the newly formed cavity.(2). Synthesis and Metal ion transport were reported. Spiropyran (6), (7) and (8) transport Cu (lI) ion selectively through liquid membrane. Selective transport experiment of Cu (II) ion from the mixed metal ion solution also reported. Mechanism of this transport was proposed.(3). Various and direct aminations of acetylenic carbon by iodonium salt were carried out. Using alkylamines, diamines, hydroxylamines, aromatic amines, an amide and isocyanate reacted with phenylethynyliodonium tosylate to give corresponding ethynylamines in good yields. Synthesis were applied to crown-ether derivative and marcocyclic self-assembly compounds. Mechanism was also discussed.(4). Bis-azacrown ethers (ring size 15 and 18) and cryptands were synthesized. The interaction of these bis-azacrown ethers with dialkali metal salt of dicarboxylic acids in methanol were examined by C-NMR.Bis-azacrown ether (2b), for example, included with dipotassium malonate, 2,2-dibenzylmalonate and terephthalate in its cavity. The other dicarboxylate with bis-azacrown ethers were also examined.

笔者通过上述课题进行了研究，得到了以下结果： (1)．进行了具有柔性空腔的主体化合物的合成及其金属离子的捕获。 Pd (II) 离子包含在主体化合物的吡啶位点上，但 Pb (II)、Cu(II) 和 Zn (II) 离子被捕获在 β-二羰基位点上。主体（6）形成铜络合物（7），其在新形成的空腔中再次包含钾阳离子。（2）。报道了合成和金属离子传输。螺吡喃 (6)、(7) 和 (8) 选择性地通过液膜转运 Cu (lI) 离子。还报道了混合金属离子溶液中铜（II）离子的选择性传输实验。提出了这种运输机制。(3)．进行了碘鎓盐对炔属碳的各种直接胺化。使用烷基胺、二胺、羟胺、芳香胺、酰胺和异氰酸酯与苯乙炔碘鎓甲苯磺酸盐反应，以良好的收率得到相应的乙炔胺。合成应用于冠醚衍生物和大环自组装化合物。并对机理进行了探讨。(4)．合成了双氮杂冠醚（环尺寸15和18）和穴状配体。通过13C-NMR检测了这些双氮杂冠醚与二羧酸的二碱金属盐在甲醇中的相互作用。例如，双氮杂冠醚(2b)在其空腔中包含丙二酸二钾、2,2-丙二酸二苄酯和对苯二甲酸酯。还检查了其他具有双氮杂冠醚的二羧酸酯。

项目成果

山本忠、科野裕克、田中誠次、砂川博、岸川圭希、幸本重男: "ビス[(β-ケトエステル,β-エナミノン)ポリエーテル]誘導体の合成とそのイオン捕捉能" 日本化学会第69春季年会、講演予稿集I. 4F-536.

Tadashi Yamamoto、Hirokatsu Shinano、Seiji Tanaka、Hiroshi Sunakawa、Keiki Kishikawa、Shigeo Yukimoto：“双[(β-酮酯，β-烯胺酮)聚醚]衍生物的合成及其离子捕获能力”日本化学会第69届春季年会，会议记录 I. 4F-536。

山本忠、村山岳志、田中誠次、伊藤潔、岸川圭希、幸本重男: "置換エチニルヨードニウム塩と各種親核試薬との反応" 日本化学会第70春季年会、講演予稿集II. 1H-539.

Tadashi Yamamoto、Takeshi Murayama、Seiji Tanaka、Kiyoshi Ito、Keiki Kishikawa、Shigeo Yukimoto：“取代乙炔基碘鎓盐与各种亲核试剂的反应”日本化学学会第 70 届春季年会，会议记录 1H -539。

M.Yamamoto, M.Hirota, K.Kishikawa, S.Kohmoto andK.Yamada: "Oxidative Cyclization of 3-Hydroxy-5-tri(nbutyl)stannyl pentanoic Acids to Corresponding δ-Lactones" Synthesis. 1997年. 937-941 (1997)

M.Yamamoto、M.Hirota、K.Kishikawa、S.Kohmoto 和 K.Yamada：“3-羟基-5-三(正丁基)甲锡烷基戊酸氧化环化成相应的 δ-内酯”1997 年。937-941 ( 1997）

S. Irie, M. Yamamoto, K. Kishikawa, S. Kohmoto and K. Yamada: "Carbamoyloxa-Bridged Cyclophanes:Macrocycylization by Double Transesterification of Dimethyl-m-xylylenedicarbamate with α,w-Dihydroxy Compounds" Synthesis. 1179-1182 (1995)

S. Irie、M. Yamamoto、K. Kishikawa、S. Kohmoto 和 K. Yamada：“氨基甲酰氧桥环烷：间苯二甲甲酸二甲酯与 α,w-二羟基化合物的双酯交换大环化”合成 1179-1182（ 1995)

M.Yamamoto, M.Nakazawa, K.Kishikawa and S.Kohmoto: "Nibium Pentachloride-mediated Novel Homologation Reactions using α-Trialkylstannylmethyl-β-ketoesters" J.Chemical Society, Chemical Communications. 1996年. 2353-2354 (1996)

M. Yamamoto、M. Nakazawa、K. Kishikawa 和 S. Kohmoto：“使用 α-三烷基甲锡烷基甲基-β-酮酯进行五氯化铌介导的新型同系反应”J.Chemical Society，Chemical Communications 1996。2353-2354 (1996)。