sym-(propyl)dibenzo-16-crown-5-oxyacetic acid

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: sym-(propyl)dibenzo-16-crown-5-oxyacetic acid
• 英文别名: 2-[(4-Propyl-2,6,13,16,19-pentaoxatricyclo[18.4.0.07,12]tetracosa-1(24),7,9,11,20,22-hexaen-4-yl)oxy]acetic acid
• 化学式: C₂₄H₃₀O₈
• 分子量: 446.497
• InChiKey: DRLXXZHCAFWLEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  sym-(propyl)dibenzo-16-crown-5-oxyacetic acid 在 草酰氯 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 (4-Propyl-2,6,13,16,19-pentaoxa-tricyclo[18.4.0.07,12]tetracosa-1(24),7(12),8,10,20,22-hexaen-4-yloxy)-acetyl chloride
  参考文献：
  名称：

  新的套索状醚羧酸和异羟肟酸：合成和镧系元素离子络合

  摘要：

  合成了基于二苯并-13-冠-4，二苯并-14-冠-4，二苯并-16-冠-5和二苯并-19-冠-6环系的二十六个新的套索状醚羧酸和异羟肟酸，并且固体确定了二苯并-19-冠-6套索状醚异羟肟酸的α-态结构。这些质子可电离的套索状醚将镧系元素离子萃取到氯仿中的效率和选择性受冠醚环的大小，亲脂性基团连接位点和酸性官能团的强烈影响。通常，套索状醚异羟肟酸比相应的套索状醚羧酸更有效和更具选择性的镧系元素离子萃取剂。在1H nmr和ir结合研究表明，大环聚醚单元和质子可电离基团均参与镧系元素离子的络合。

  DOI：

  10.1002/jhet.5570350416

文献信息

• Synthesis of dibenzo-16-crown-5 compounds with pendant ester and ether groups
  作者：David A. Babb、Richard A. Bartsch、James J. Collier、Dhimant H. Desai、Sadik Elshania、Mi-Ja Goo、Johnny L. Hallman、Gwi Suk Heo、Xiaowu Huang、Vincent J. Huber、Hong-Sik Hwang、Russell J. Johnson、Yung Liu、Michael J. Pugia、Qiang Zhao

  DOI：10.1002/jhet.5570410503

  日期：2004.9

  related dibenzo-16-crown-5 lariat ethers with pendant ester and ether groups are prepared. Structural variations within the series of alkyl lariat ether esters include changes in the O-alkyl group, attachment site and nature of the lipophilic group, and length of the spacer, which connects the ester group to the polyether framework. Also synthesized are bis(crown ether) diesters with two dibenzo-16-crown-5

  制备具有侧酯和醚基的结构相关的二苯并-16-冠-5套索状醚。烷基套索状醚酯系列中的结构变化包括O-烷基的变化，亲脂基团的连接位点和性质以及将酯基团连接至聚醚骨架的间隔基的长度。还合成了具有两个二苯并基-16-冠-5或两个二环己基-16-冠-5单元和两个酯基的双（冠醚）二酯，所述两个酯基通过不同长度的接头彼此连接。描述了制备具有侧链含酯和醚侧链的套索状醚的合成策略。
• New lariat ether carboxylic and hydroxamic acids: Synthesis and lanthanide ion complexation
  作者：Sadik Elshani、Randal Noriyuki、Chien M. Wai、N. R. Natale、Richard A. Bartsch

  DOI：10.1002/jhet.5570350416

  日期：1998.7

  group attachment site and identity of the acidic function. In general, the lariat ether hydroxamic acids were more efficient and selective lanthanide ion extractants than the corresponding lariat ether carboxylic acids. The 1H nmr and ir binding studies indicate that both the macrocyclic polyether unit and the proton-ionizable group are involved in lanthanide ion complexation.

  合成了基于二苯并-13-冠-4，二苯并-14-冠-4，二苯并-16-冠-5和二苯并-19-冠-6环系的二十六个新的套索状醚羧酸和异羟肟酸，并且固体确定了二苯并-19-冠-6套索状醚异羟肟酸的α-态结构。这些质子可电离的套索状醚将镧系元素离子萃取到氯仿中的效率和选择性受冠醚环的大小，亲脂性基团连接位点和酸性官能团的强烈影响。通常，套索状醚异羟肟酸比相应的套索状醚羧酸更有效和更具选择性的镧系元素离子萃取剂。在1H nmr和ir结合研究表明，大环聚醚单元和质子可电离基团均参与镧系元素离子的络合。
• Structurally-selective gas-phase ion-molecule reactions of dibenzo-16-crown-5 compounds
  作者：Chien-Chung Liou、John Isbell、Hui-Fen Wu、Jennifer S. Brodbelt、Richard A. Bartsch、Jong Chan Lee、Johnny L. Hallman

  DOI：10.1002/jms.1190300408

  日期：1995.4

  Steric and substituent effects can play large roles in influencing the outcomes of organic reactions. In this work, the use of ion-molecule reactions of dibenzo-16-crown-5 compounds (lariat ethers) by tandem mass spectrometry to probe the influence of the pendant groups on the selectivity of their gas-phase reactions was evaluated. Lariat ethers are macrocyclic ethers with pendant substituents that have been developed as new types of hosts for molecular recognition. Dimethyl ether (DME) was the reactant chosen because of its well characterized reactivity with various organic substrates possessing different functional groups. Only those dibenzo-16-crown-5 compounds with no or at most one substituent at the center carbon of the three-carbon bridge form the diagnostic [M + 13]+ product ion through a methylene substitution process. Dibenzo-16-crown-5 compounds with geminal substituents on the center carbon of the three-carbon bridge form the [M + 45]+ ion, but not the characteristic [M + 13]+ ion. Causative factors may be steric blocking of the reaction pathway by the geminal groups or a requirement for the presence of at least one hydrogen on the center carbon of the three-center bridge for formation of the [M + 13]+ ion. CAD, deuterium labelling, molecular orbital calculations and comparisons with model compounds provide additional information about the reaction pathways.

  位阻效应和取代基效应在影响有机反应的结果方面发挥着重要作用。在这项工作中，通过串联质谱法利用二苯并-16-冠-5 化合物（套索醚）的离子-分子反应来探讨侧基对其气相反应选择性的影响。套索醚是带有侧取代基的大环醚，已被开发为分子识别的新型主体。选择二甲醚（DME）作为反应物是因为它与具有不同官能团的各种有机底物具有良好的反应活性。只有那些在三碳桥的中心碳上没有取代基或最多有一个取代基的二苯并-16-冠-5 化合物才能通过亚甲基取代过程形成诊断性[M + 13]+ 产物离子。在三碳桥的中心碳上具有偕取代基的二苯并-16-冠-5化合物形成[M+45]+离子，但不是特征性[M+13]+离子。致病因素可能是孪生基团对反应路径的空间阻碍，或者需要在三中心桥的中心碳上存在至少一个氢以形成[M+13]+离子。 CAD、氘标记、分子轨道计算以及与模型化合物的比较提供了有关反应途径的更多信息。
• Sodium Ion-Selective Electrodes Based on Dibenzo-16-crown-5 Compounds with Pendent Ester Groups
  作者：Akira. Ohki、Jian Ping. Lu、Johnny L. Hallman、Xiaowu. Huang、Richard A. Bartsch

  DOI：10.1021/ac00110a013

  日期：1995.7.15

  Selectivities of 21 dibenzo-16-crown-5 compounds with pendent ester groups for alkali metal, alkaline earth metal, and ammonium ions have been determined in solvent polymeric membrane electrodes. The ionophores include alkyl sym-R-dibenzo-16-crown-5-oxyacetates with R = hydrogen, linear alkyl, branched alkyl, fluoroalkyl, alkenyl, alkynyl, and phenyl groups. For lariat ethers with a hydrogen, linear alkyl group, or branched alkyl group attached to the ring carbon that bears the ester-containing side arm, the Na+/K+ selectivity increases as the bulkiness of the geminal substituent is enhanced; whereas the Na+/Li+ selectivity exhibits a weaker inverse relationship to the size of R. On the other hand, the Na+/K+ and Na+/Li+ selectivities are insensitive to variations in the size and shape of the ester alkyl groups. For eight of the lariat ether ester ionophores, very high Na+/Li+ selectivities of 10(3.8)-10(3.9) are observed.
• Kasprzyk, Stanislaw P.; Bartsch, Richard A., Journal of Heterocyclic Chemistry, 1993, vol. 30, # 1, p. 119 - 123
  作者：Kasprzyk, Stanislaw P.、Bartsch, Richard A.

  DOI：——

  日期：——