mono-[6-(m-toluidinyl)-6-deoxy]-β-cyclodextrin

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: mono-[6-(m-toluidinyl)-6-deoxy]-β-cyclodextrin
• 英文别名: (1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-5,10,15,20,25,30-hexakis(hydroxymethyl)-35-[(3-methylanilino)methyl]-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecol
• 化学式: C₄₉H₇₇NO₃₄
• 分子量: 1224.14
• InChiKey: QQFNZGJQWUDSMX-XISQNVKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -12.3
• 重原子数：
  84
• 可旋转键数：
  9
• 环数：
  22.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  546
• 氢给体数：
  21
• 氢受体数：
  35

反应信息

• 作为产物：
  描述：

  3-甲基苯胺 、 mono-6-deoxy-6-(p-toluenesulfonyl)-β-cyclodextrin 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以45%的产率得到mono-[6-(m-toluidinyl)-6-deoxy]-β-cyclodextrin
  参考文献：
  名称：

  Molecular Recognition Study on a Supramolecular System. 10.¹ Inclusion Complexation of Modified β-Cyclodextrins with Amino Acids:  Enhanced Enantioselectivity for l/d-Leucine

  摘要：

  The novel beta-cyclodextrin (beta-CD) derivatives bearing a m-toluidinyl or (9-fluorenyl)alkylamino moiety have been synthesized by a convenient method in 45% and 66% yields, respectively. The stability constants (K-s) and Gibbs free energy changes (-Delta G) for inclusion complexation of mono-[6-(m-toluidinyl)-6- deoxy]-beta-cyclodextrin 1 and mono-[6-[(9-fluorenyl)alkylamino]-6-deoxy]-beta-cyclodextrin 2 with various L/D-amino acids have been examined by the fluorescence spectrum method in buffered aqueous solution (pH = 7.20) at 20-23 degrees C. The modified beta-cyclodextrins, possessing a toluidinyl or fluorenyl moiety as fluorescent probe, can recognize not only the size and shape but also the chirality of L/D-amino acids, giving fairly good enantioselectivity up to 33 for L/D-leucine. beta-Cyclodextrin derivative 1 gave the highest K-s far L-leucine and the lowest for D-leucine among the amino acid series, eventually showing the highest enantioselectivity for L/D-amino acids. The molecular recognition ability and enantioselectivity for amino acids of the modified beta-cyclodextrins 1 and 2 are discussed from the viewpoint of the size/shape-fit relationship between the host cavity and the guest molecules.

  DOI：

  10.1021/jo961625b

文献信息

• Molecular Recognition Study on Supramolecular System. 14.¹ Synthesis of Modified Cyclodextrins and Their Inclusion Complexation Thermodynamics with <scp>l</scp>-Tryptophan and Some Naphthalene Derivatives
  作者：Yu Liu、Bao-Hang Han、Bin Li、Yi-Min Zhang、Peng Zhao、Yun-Ti Chen、Takehiko Wada、Yoshihisa Inoue

  DOI：10.1021/jo971466b

  日期：1998.3.1

  A series of beta-cyclodextrin derivatives, carrying pyridinio (4-6), phosphonyl (7, 8), seleno (9-11), m-and p-picolinyl (12, 13), o-chloroanilino (16), 8-quinolyl. (17), furfuryl (18), and 9-fluorenyl (19) moieties in the side chain, were newly synthesized, and their complexation behavior was assessed and discussed thermodynamically, using L-tryptophan and a few naphthalene derivatives as representative guests. Calorimetric titrations have been performed at 25.0 degrees C in buffered aqueous solution (pH 7.20) to give the complex stability constants and thermodynamic parameters for the 1:1 inclusion complexation of these guests with the native and modified alpha-, beta-, and/or gamma-cyclodextrins (1-20). All of the chemical modifications to the primary side of cyclodextrins examined led to significant changes in complex stability and thermodynamic parameters, which are elucidated in terms of the conformational, electrostatic, hydrogen-bonding, and hydration effects. Thermodynamically, the inclusion complexation is mainly enthalpy-driven with a negative or minor positive entropic contribution, which in some cases determines the complex stability. The induced circular dichroism spectral analyses of these cyclodextrin derivatives indicated that the aromatic moiety in modified beta-cyclodextrins (4-6, 9-19) only shallowly penetrates into the hydrophobic cavity of beta-cyclodextrin, while the phenyl phosphate and fluorenyl moieties in 7 and 20 are embedded into the hydrophobic cavity of beta-cyclodextrin because of the longer linking chain. Using all the thermodynamic data for a wide variety of cyclodextrin derivatives obtained in this and previous studies, the entropy changes (T Delta S) were plotted against the enthalpy changes (Delta H) to give an excellent linear relationship. The slope (alpha) of 1.02 and an intercept (T Delta S-o) of 4.3 of the regression line indicate substantial conformational changes and extensive desolvation caused upon complexation,respectively.