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.

作者在上述项目中进行了研究，并获得了效果。（1）。进行了合成及其对带有柔性腔的宿主化合物的金属离子的捕获。 Pd（II）离子在宿主化合物的吡啶位点包括在内，但是在β-二氨基苯苯二甲酸杆菌位置捕获了Pb（ii），Cu（ii）和Zn（II）离子。主宿主（6）形成了Cu复合物（7），该复合物再次包括在新形成的腔中。（2）。据报道合成和金属离子运输。 Spiropyran（6），（7）和（8）通过液体选择性地运输Cu（Li）离子。还报道了来自混合金属离子溶液的Cu（II）离子的选择性转运实验。提出了这种运输的机制。（3）。碘盐对乙炔碳进行了各种直接氨水。使用烷基胺，二胺，羟胺，芳香胺，酰胺和异氰酸酯与苯甲酰胺甲苯二烯丙基反应，以良好的产率获得相应的乙尼胺。将合成应用于皇冠衍生物和莫克环状自组装化合物。还讨论了机制。（4）。合成了Bis-azcrown Ethers（环尺寸15和18）和密码。 C-Nmr.bis-rescrown-Ether（2B）检查了这些Bis-Zrakown醚与甲醇中二羧酸的Dialkali金属盐的相互作用（例如，2,2-甲酸二甲酸二甲酸二甲酸酯，2,2-二苯甲酸甲酸酯和treperphalate in cavity中。还检查了其他带有二羧酸盐的二羧酸盐。

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）

M.Yamamoto, K.Itoh, K.Kishikawa and S.Kohmoto: "A Highly Diastereoselective Synthesis of α-Substituted-β-hydoroxy Compounds from Corresponding β-Stanny1 Compounds" Chemistry Letters. 1997年. 1035-1036 (1997)

M.Yamamoto、K.Itoh、K.Kishikawa 和 S.Kohmoto：“从相应的 β-Stanny1 化合物中高度非对映选择性合成 α-取代的-β-羟基化合物”化学快报，1997 年。1035-1036 (1997)

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)。