N,N',N'',N'''-tetramethyl-2,11,20,29-tetraaza<3.3.3.3>paracyclophane | 33920-65-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N',N'',N'''-tetramethyl-2,11,20,29-tetraaza<3.3.3.3>paracyclophane
• 英文别名: Agn-PC-0LP8KX；3,10,17,24-tetramethyl-3,10,17,24-tetrazapentacyclo[24.2.2.25,8.212,15.219,22]hexatriaconta-1(29),5,7,12,14,19(32),20,22(31),26(30),27,33,35-dodecaene
• CAS: 33920-65-9
• 化学式: C₃₆H₄₄N₄
• 分子量: 532.772
• InChiKey: ZZYRHMOVFSBQCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  40
• 可旋转键数：
  0
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N',N'',N'''-tetramethyl-2,11,20,29-tetraaza<3.3.3.3>paracyclophane 、 trimethoxonium tetrafluoroborate 以 二氯甲烷 为溶剂， 反应 2.0h， 以40%的产率得到N,N,N',N',N'',N'',N''',N'''-octamethyl-2,11,20,29-tetraaza<3.3.3.3>paracyclophanetetrammonium tetrafluoroborate
  参考文献：
  名称：

  Substrate specificity in ester hydrolysis by a new water-soluble heterocyclophane

  摘要：

  DOI：

  10.1021/ja00411a037
• 作为产物：
  描述：

  N,N',N'',N'''-tetramethyl-1,12,19,30-tetraoxo-2,11,20,29-tetraaza<3.3.3.3>paracyclophane 在 lithium aluminium tetrahydride 作用下， 以 1,4-二氧六环 为溶剂， 反应 12.0h， 以17%的产率得到N,N',N'',N'''-tetramethyl-2,11,20,29-tetraaza<3.3.3.3>paracyclophane
  参考文献：
  名称：

  Substrate specificity in ester hydrolysis by a new water-soluble heterocyclophane

  摘要：

  DOI：

  10.1021/ja00411a037

文献信息

• A Simple Synthetic Method for Tetraaza[3.3.3.3]meta- and paracyclopanes by Alkylation of<i>N</i>-Substituted Trifluoroacetamide
  作者：Teruo Shinmyozu、Nobuhiko Shibakawa、Ken'ichi Sugimoto、Hiroko Sakane、Hiroyuki Takemura、Katsuya Sako、Takahiko Inazu

  DOI：10.1055/s-1993-26038

  日期：——

  A simple and practical synthesis of the title compounds 1b and 2b is described. Alkylation of N-substituted trifluoroacetamides (5a and b) with appropriate dibromides (6 and 9) in the presence of sodium hydride in N,N-dimethylformamide at 100°C, or powdered potassium hydroxide in refluxing acetone, followed by removal of the trifluoroacetyl group and N-methylation of the resultant amines provides the desired 1b and 2b in 21 and 19 % overall yields, respectively, along with their lower and higher homologs.

  标题化合物1b和2b的一种简便实用的合成方法如下所述。在100°C下，在N,N-二甲基甲酰胺中，使用氢化钠，或将粉状氢氧化钾加入回流的丙酮中，使N-取代的三氟乙酰胺（5a和5b）与适当的二溴化物（6和9）进行烷基化反应，随后去除三氟乙酰基并使所得胺进行N-甲基化，分别以21%和19%的总产率得到了所需的1b和2b，同时还生成了其低级和高级同系物。
• Syntheses of macrocyclic enzyme models. 8. Conformational mobility and molecular recognition by the internal cage of kyuphane
  作者：Yukito Murakami、Junichi Kikuchi、Teruhisa Ohno、Takayuki Hirayama、Yoshio Hisaeda、Hiroshi Nishimura、James P. Snyder、Kosta Steliou

  DOI：10.1021/ja00022a006

  日期：1991.10

  Temperature-dependent H-1 NMR measurements in CDCl3-CS2 (3:7 v/v) and DMF-d7 in concert with MM2 conformational analysis reveal that the molecular framework of "Kyuphane" (1), a cage-type cubical molecule with six faces each consisting of a 2,11,20,29-tetraaza[3.3.3.3]paracyclophane ring, is significantly more rigid than the corresponding noncage host (2), but still conformationally flexible. A slow rate of interconversion among degenerated conformers of the lowest energy C(i) conformation accounts for the observed NMR line broadening. Hosts 1 and 2 are soluble in acidic aqueous media below pH 4 and behave as polycationic species. Electrostatic field solvation analysis of the tetraprotonated salt of Kyuphane suggests a square-planar proton placement (11a) to predominate in solution. Line broadening for the tetracation appears to arise from both conformer interconversion and proton exchange. Guest recognition behavior of these hosts under acidic conditions was studied by means of H-1 NMR and fluorescence spectroscopy. Kyuphane demonstrates a pH-dependent guest-binding ability due to changes in the specific microenvironmental polarity of its three-dimensional cavity upon variable protonation of the nitrogen atoms. The host also shows size-sensitive and regioselective molecular discrimination originating from the semirigid geometry of the hydrophobic cavity and the specific protonation geometry. The specific molecular discrimination evidenced by 1 was analyzed by MM2 molecular mechanics and applied to selective transport of hydrophobic molecules between organic phases across an aqueous phase in which 1 was present as a carrier. It is noteworthy that the proton NMR signals of guest molecules naphthalene-2,6-disulfonate, 8-anilinonaphthalene-1-sulfonate, and 6-p-toluidinonaphthalene-2-sulfonate completely disappear upon complexation with Kyuphane, whereas the identical guest naphthalene-2,6-disulfonate shows normal upfield shifts of its NMR proton signals upon complexation with 2.
• TABUSHI, IWAO;YAMAMURA, KAZUO;NONOGUCHI, HIROSHI;HIROTSU, KEN;HIGUCHI, TA+, HETEROCYCLES, 1984, 21, N 2, 760
  作者：TABUSHI, IWAO、YAMAMURA, KAZUO、NONOGUCHI, HIROSHI、HIROTSU, KEN、HIGUCHI, TA+

  DOI：——

  日期：——
• Substrate specificity in ester hydrolysis by a new water-soluble heterocyclophane
  作者：Iwao Tabushi、Yoshio Kimura、Kazuo Yamamura

  DOI：10.1021/ja00411a037

  日期：1981.10