Diethyl 3,3-bis(4-hydroxy-3,5-dimethylphenyl)pentanedioate | 116159-02-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Diethyl 3,3-bis(4-hydroxy-3,5-dimethylphenyl)pentanedioate
• CAS: 116159-02-5
• 化学式: C₂₅H₃₂O₆
• 分子量: 428.525
• InChiKey: BKXKVNWIGYKZAD-UHFFFAOYSA-N

物化性质

• 熔点：
  177-178 °C(Solv: nitromethane (75-52-5))
• 沸点：
  558.6±45.0 °C(Predicted)
• 密度：
  1.156±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  93.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Diethyl 3,3-bis(4-hydroxy-3,5-dimethylphenyl)pentanedioate 在 咪唑 、 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.0h， 生成 3,3-bis{4-[(tert-butyl)dimethylsilyloxy]-3,5-dimethylphenyl}pentane-1,5-diyl bis(methanesulfonate)
  参考文献：
  名称：

  Catalytic Dendrophanes as Enzyme Mimics: Synthesis, Binding Properties, Micropolarity Effect, and Catalytic Activity of Dendritic Thiazolio-cyclophanes

  摘要：

  Catalytic dendrophanes 9 and 10 were prepared as functional mimics of the thiamine-diphosphate-dependent enzyme pyruvate oxidase, and studied as catalysts in the oxidation of naphthalene-2-carbaldehyde (4) to methyl naphthalene-2-carboxylate (8) (Scheme 1). They are composed of a thiazolio-cyclophane initiator core with four generation-2 (G-2) poly(etheramide) dendrons attached. The two dendrophanes were synthesized by a convergent growth strategy by coupling dendrons 11 and 12, respectively (Scheme 2), with (chloromethyl)-cyclophane 42 (Scheme 5) and subsequent conversion with 4-methylthiaaole (Scheme 7). The X-ray crystal structures of cyclophane precursors 30 (Scheme 3), 37 and 38 (Scheme 5) on the way to dendrophanes were determined (Fig. I). The crystal-structure analysis of the benzene clathrate of 37 revealed the formation of channel-like stacks by the cyclophane which incorporate its morpholinomethyl side chain and the enclathrated benzene molecule (Fig. 2). The interactions of the enclathrated benzene molecule with the phenyl rings of the two adjacent cyclophane molecules in the stack closely resemble those between neighboring benzene molecules in crystalline benzene (Fig. 3). The characterization by MALDI-TOF-MS (Fig. 4) and H-1- and C-13-NMR spectroscopy (Fig. 5) proved the monodispersity of the G-2 dendrophanes 9 and 10 with molecular weights up to 11500 Da (Eor 10). H-1-NMR and fluorescence binding titrations in H2O and aqueous MeOH showed that 9 and 10 form stable 1:1 complexes with naphthalene-2-carbaldehyde (4) and 6-(p-toluidino)naphthalene-2-sulfonate (48, TNS) (Tables 1 and 2). The evaluation of the fluorescence-emission maxima of bound TNS revealed that the dendritic branching creates a microenvironment of distinctly reduced polarity at the cyclophane core by limiting its exposure to bulk solvent. Initial rate studies for the oxidation of naphthalene-2-carbaldehyde to methyl naphthalene-2-carboxylate in basic aqueous MeOH in the presence of flavin derivative 6 revealed only a weak catalytic activity of dendrophanes 9 and 10 (Table 3), despite the favorable micropolarity at the cyclophane active site. The low catalytic activity in the interior of the macromolecules was explained by steric hindrance of reaction transition states by the dendritic branches.

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<1066::aid-hlca1066>3.0.co;2-o
• 作为产物：
  描述：

  2,6-二甲基苯酚 、 1,3-丙酮二羧酸二乙酯 在 硫酸 作用下， 以75%的产率得到Diethyl 3,3-bis(4-hydroxy-3,5-dimethylphenyl)pentanedioate
  参考文献：
  名称：

  黄酮-主体在水溶液中的氧化还原依赖性络合能力

  摘要：

  描述了新的大环主体1的合成，该主体结合了异恶恶嗪部分作为黄酮酶活性位点的模型。在水溶液中分析了氧化的和还原的黄素-主体和芳族客体之间的络合物。

  DOI：

  10.1016/s0040-4039(00)95604-1

文献信息

• New Cyclophanes as Initiator Cores for the Construction of Dendritic Receptors: Host-guest complexation in aqueous solutions and structures of solid-state inclusion compounds
  作者：Peter Wallimann、Sebastiano Mattei、Paul Seiler、Fran�ois Diederich

  DOI：10.1002/hlca.19970800809

  日期：1997.12.15

  Cyclophanes in the crystal lattice. In the 1:2 inclusion compound 5c, two toluene molecules penetrate with their aromatic rings the macrocyclic cavity from opposite sides in an antiparallel fashion. On the other hand, p-xylene (= 1,4-dimethylbenzene) in the 1:1 compound 5d is sandwiched between the cyclophane molecules with its two Me groups penetrating the cavities of the two macrocycles. In the 1:2

  环芳3和4制备作为引发磁芯dendrophanes（建设树突cydophanes）1和2分别为，其中模拟物识别位点埋在球状蛋白。四-氧[6.1.6.1]对环环烷3通过短的三步路线（方案1）制备，并具有由两个二苯甲烷单元形成的空腔结合位点，适合于将平面芳族底物（如苯和萘衍生物）包括在内。通过在碱性D 2 O磷酸盐缓冲液中的1 H-NMR结合滴定显示了表1（表1）。较大的Cyclphane 4，由两个较宽的萘基（苯基）甲烷间隔基形成，是通过较长的十步合成法（方案2）制备的，其中包括作为关键中间体的四溴环烷5。在D 2 O / CD 3 OD的碱性硼酸盐缓冲液中的1 H-NMR结合研究表明4是有效的类固醇受体。在一系列类固醇中（表1），配合物强度随着底物极性的增加和极性取代基的数量的增加而降低；另外，宿主和客体的羧酸残基之间的静电排斥也强烈影响结合亲和力。构象柔性的四溴环烷5表现出明显的趋势，即
• Catalytic cyclophanes VII. Esterase activity of a bisimidazolyl-cyclophane
  作者：Ito Chao、François Diederich

  DOI：10.1002/recl.19931120605

  日期：——

  that shape the macrocyclic cavity. Four acetic acid residues diverge from the central carbon atoms of the two spacer units and ensure solubility of 3 in water and binary aqueous solvent mixtures. Cyclophane 3 forms stoichiometric inclusion complexes with nitronaphthyl acetates in aqueous phosphate buffers (pH 8) and catalyzes the hydrolysis of bound substrates under turnover conditions.

  我们报告了具有两个咪唑残基的新型四氧杂[6.1.6.1]对环环烷3的合成，该残基连接到形成大环腔的两个二苯甲烷间隔基之一的苯环上。四个乙酸残基与两个间隔单元的中心碳原子分开，并确保3在水和二元水性溶剂混合物中的溶解度。环戊烷3在含水磷酸盐缓冲液（pH 8）中与乙酸硝基萘酯形成化学计量的包合物，并在周转条件下催化结合的底物的水解。
• A new water soluble cyclophane host that is organized by calcium binding
  作者：Kathryn L. Cole、M. Angeles Farran、Kurt Deshayes

  DOI：10.1016/s0040-4039(00)92320-7

  日期：1992.1

  Two new water soluble cyclophanes1a and1b were synthesized. The allosteric regulation of the host-guest interactions was studied by fluorescence spectroscopy.

  合成了两个新的水溶性环烷1a和1b。通过荧光光谱研究了宿主-客体相互作用的变构调节。
• Redox-dependent binding ability of a flavin cyclophane in aqueous solution: hydrophobic stacking versus cavity-inclusion complexation
  作者：Eileen M. Seward、R. Bruce Hopkins、Wolfgang Sauerer、Suk Wah Tam、Francois Diederich

  DOI：10.1021/ja00161a020

  日期：1990.2
• SEWARD, EILEEN M.;HOPKINS, R. BRUCE;SAUERER, WOLFGANG;TAM, SUK-WAH;DIEDER+, J. AMER. CHEM. SOC., 112,(1990) N, C. 1783-1790
  作者：SEWARD, EILEEN M.、HOPKINS, R. BRUCE、SAUERER, WOLFGANG、TAM, SUK-WAH、DIEDER+

  DOI：——

  日期：——