10-(2-hydroxy-3-formyl-5-nitrobenzyl)-1,4,7-trioxa-10-azacyclododecane | 141620-24-8

• 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: 10-(2-hydroxy-3-formyl-5-nitrobenzyl)-1,4,7-trioxa-10-azacyclododecane
• 英文别名: 3-formyl-2-hydroxy-5-nitrobenzyl monoaza-12-crown-4；1-(3-formyl-2-hydroxy-5-nitrobenzyl)-monoaza-12-crown-4；2-Hydroxy-5-nitro-3-(1,4,7-trioxa-10-azacyclododec-10-ylmethyl)benzaldehyde
• CAS: 141620-24-8
• 化学式: C₁₆H₂₂N₂O₇
• 分子量: 354.36
• InChiKey: FQKDLDGETKEBQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  114
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  10-(2-hydroxy-3-formyl-5-nitrobenzyl)-1,4,7-trioxa-10-azacyclododecane 在 氢氧化钾 、 三乙胺 作用下， 以 乙醇 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 23.0h， 生成 5-nitro-2-sulfanyl-3-(1,4,7-trioxa-10-azacyclododec-10-ylmethyl)benzaldehyde
  参考文献：
  名称：

  冠状螺并噻吩并吡喃的合成和光致变色作用：通过冠醚和硫酚盐部分与金属离子的协同络合促进光致异构化。

  摘要：

  合成了带有单氮杂-12-冠-4，-15-冠-5，-18-冠-6和低聚氧乙烯部分的螺并苯并噻喃，并在乙腈中存在阳离子的情况下检查了它们的光致变色。与相应的螺并苯并吡喃衍生物不同，通过它们的冠醚部分进行的阳离子络合不能诱导热异构化为其相应的有色花菁形式。然而，冠醚部分的阳离子络合以及花青硫酚盐阴离子对金属离子的亲和力，尤其是在Li（+）和Ag（+）的存在下，促进了紫外线诱导的异构化。

  DOI：

  10.1021/jo000175r
• 作为产物：
  描述：

  3-氯甲基-5-硝基水杨醛 、 氮杂-12-冠醚-4 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以0.19 g的产率得到10-(2-hydroxy-3-formyl-5-nitrobenzyl)-1,4,7-trioxa-10-azacyclododecane
  参考文献：
  名称：

  带有羧基部分的加冠螺吡喃氟离子载体，可选择性检测锂离子†

  摘要：

  比较了含甲基-1-氮杂-12-皇冠-4，甲基-1-氮杂-15-皇冠-5，甲基-1-氮杂-18-皇冠-6部分的羧化螺吡喃的吸光度和荧光光谱。观察到在添加了Li +，Na +，K +和Cs +的碱金属盐后光谱的特征变化。观察到由金属阳离子的结合引起的色度随着吸光度和荧光的增加而增加。在这些金属阳离子中，Li +离子在所有三个螺吡喃系统中产生了最大的变化。在交替的352 nm紫外线和白光照射下，可以观察到螺吡喃-金属配合物的可逆光开关。这导致基于可逆的基于荧光的锂离子感测，具有在生物传感器装置中使用的潜力。

  DOI：

  10.1039/c6ob00468g

文献信息

• Cation-specific isomerization of crowned spirobenzopyrans
  作者：Keiichi Kimura、Takashi Yamashita、Masaaki Yokoyama

  DOI：10.1039/c39910000147

  日期：——

  Novel spirobenzopyran derivatives carrying monoazacrown moieties at the 8-position undergo selective complexation of alkali metal ions and thereby isomerization to their corresponding merocyanine form in the dark; the isomerization is enhanced especially by Li+ that is likely to interact with the phenolate anion intramolecularly when bound to the crown rings.

  新型螺并吡喃衍生物的 8 位含有单氮冠分子，在黑暗条件下会与碱金属离子发生选择性络合，从而异构化为相应的美拉德菁形式；异构化作用在 Li+ 的作用下尤其明显，因为 Li+ 与冠环结合时可能会与酚阴离子发生分子内相互作用。
• Potential photoresponse of membranes containing a lipophilic crowned spirobenzopyran
  作者：Keiichi Kimura、Shinpei Kado、Hidefumi Sakamoto、Akio Sakai、Masaaki Yokoyama、Mutsuo Tanaka

  DOI：10.1039/a904897i

  日期：——

  Potential response and its photoresponse for plasticized-poly(vinyl chloride) membranes containing a lipophilic crowned spirobenzopyran were surveyed and compared with those for membrane systems of a spirobenzopyran deriative not carrying any crown ether moiety. On UV-light irradiation, an intriguing type of time-course change was found with the membrane potential for the crowned spirobenzopyran system in the presence of alkali metal ions, i.e., the potential first increases and then decreases. The photoresponse profile for the crowned spirobenzopyran system was affected considerably by the sort of metal ions and the pH conditions of aqueous phases. This phenomenon is explained by an ion-exchange mechanism specific to crowned spirobenzopyran, that is, fast proton exchange followed by slow metal-ion exhange of its merocyanine form. The system for the corresponding spirobenzopyran without crown ether moiety exhibited a steady potential photoresponse that depends on the pH conditions of aqueous phases.

  研究了含有亲脂冠螺苯并吡喃的塑化聚（氯乙烯）膜的电位响应及其光响应，并将其与不含任何冠醚分子的螺苯并吡喃衍生物膜系统的电位响应及其光响应进行了比较。在紫外线照射下，发现在碱金属离子存在的情况下，冠螺苯并吡喃体系的膜电位发生了一种有趣的时间变化，即电位先升高后降低。冠螺苯并吡喃体系的光响应曲线受到金属离子种类和水相 pH 值条件的很大影响。这种现象可以用冠螺苯并吡喃特有的离子交换机制来解释，即先进行快速质子交换，然后再进行其美拉环形式的缓慢金属离子交换。相应的不含冠醚分子的螺并吡喃体系则表现出稳定的光响应电位，这取决于水相的 pH 值条件。
• Metal-ion stabilization of photoinduced open colored isomer in crowned spirobenzothiapyran
  作者：Mutsuo Tanaka、Kenji Kamada、Hisanori Ando、Takashi Kitagaki、Yasuhiko Shibutani、Setsuko Yajima、Hidefumi Sakamoto、Keiichi Kimura

  DOI：10.1039/a903877i

  日期：——

  A spirobenzothiapyran derivative bearing a monoaza-12-crown-4 moiety affords significant thermal stability enhancement in the UV light induced colored merocyanine form of its photochromic moiety by metal-ion complexation of its crown ether moiety, although the complexation hardly induces the isomerization without photoirradiation.

  通过冠醚分子的金属离子络合，一种具有单aza-12-冠-4分子的螺苯并噻喃衍生物在紫外光诱导下的光致变色美拉德菁形式的热稳定性显著增强，尽管这种络合在没有光辐射的情况下很难诱导异构化。
• Kimura, Keiichi; Yamashita, Takashi; Yokoyama, Masaaki, Journal of the Chemical Society. Perkin transactions II, 1992, # 4, p. 613 - 620
  作者：Kimura, Keiichi、Yamashita, Takashi、Yokoyama, Masaaki

  DOI：——

  日期：——
• Cation Complexation, Photochromism, and Photoresponsive Ion-Conducting Behavior of Crowned Spirobenzopyran Vinyl Polymers
  作者：Keiichi Kimura、Hidefumi Sakamoto、Ryoko M. Uda

  DOI：10.1021/ma035644g

  日期：2004.3.1

  Vinyl polymers incorporating a crowned spirobenzopyran moiety at the side chain were synthesized, and their alkali metal-ion complexation, photochromism, and photoresponsive ion-conducting behaviors were studied in comparison with similar polymers incorporating crown ether and spirobenzopyran moieties independently. The metal-ion complexation by their crown ether moiety significantly affected the photochromism of their spirobenzopyran moiety. The crowned spirobenzopyran polymers are similar to their corresponding monomeric analogue in their metal-ion complexing property and photochromism, with some difference induced by polymer effect. Almost no significant aggregation of the photoinduced merocyanine moiety was found in the crowned spirobenzopyran polymer, unlike the polymers carrying spirobenzopyran and crown ether moiety independently. The crowned spirobenzopyran polymers were applied successfully as components of photoresponsive ion-conducting materials.