3-(4-(dibenzylamino)phenyl)-4-hydroxycyclobut-3-ene-1,2-dione | 116966-12-2

• 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: 3-(4-(dibenzylamino)phenyl)-4-hydroxycyclobut-3-ene-1,2-dione
• 英文别名: 3-[4-(dibenzylamino)phenyl]-4-hydroxycyclobut-3-ene-1,2-dione
• CAS: 116966-12-2
• 化学式: C₂₄H₁₉NO₃
• 分子量: 369.42
• InChiKey: GSQXFRUGZKZZLZ-UHFFFAOYSA-N

物化性质

• 熔点：
  >140 °C
• 沸点：
  595.3±60.0 °C(predicted)
• 密度：
  1.349±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.86
• 重原子数：
  28.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  57.61
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  N,N-bis(pyridin-2-ylmethyl)aniline 、 3-(4-(dibenzylamino)phenyl)-4-hydroxycyclobut-3-ene-1,2-dione 在 原甲酸三正丁基酯 作用下， 以 异丙醇 为溶剂， 反应 12.0h， 以9%的产率得到
  参考文献：
  名称：

  Using the Rotaxane Mechanical Bond to Enhance Chemical Reactivity

  摘要：

  Rates of cycloreversion for squaraine rotaxane mono(endoperoxides) were enhanced by structural modifications that increased cross-component steric destabilization of the inward directed 9,10-anthracene endoperoxide group. The largest rate enhancements were obtained when the surrounding macrocycle contained two 2,6-pyridine dicarboxamide bridging units, which induced a cavity contraction effect. The precursor fluorescent, near-IR, squaraine rotaxanes are effectively photostable because the mono(endoperoxide) products, formed by reaction with photogenerated singlet oxygen, rapidly cyclorevert back to the original squaraine rotaxane.

  DOI：

  10.1021/ol102132x
• 作为产物：
  描述：

  3-chloro-4-[4-(dibenzylamino)phenyl]cyclobut-3-ene-1,2-dione 生成 3-(4-(dibenzylamino)phenyl)-4-hydroxycyclobut-3-ene-1,2-dione
  参考文献：
  名称：

  AKASAKI, YUTAKA;TSUNEHDA, AKIXIKO;SAEHKI, SATORU;TORIGOEH, KAORU;IMAI, AK+

  摘要：

  DOI：

文献信息

• Thermally-activated chemiluminescent squaraine rotaxane endoperoxide with green emission
  作者：Carleton G. Collins、Jeffrey M. Baumes、Bradley D. Smith

  DOI：10.1039/c1cc15550d

  日期：——

  A squaraine rotaxane endoperoxide with a truncated squaraine chromophore undergoes a cycloreversion reaction and emits green light that can be transferred to red acceptor dyes. The results demonstrate that chemiluminescence emission for squaraine rotaxane endoperoxides comes from the excited squaraine inside the rotaxane.

  一种具有截短色素的方酸轮烷过氧化物经历环反向反应，并发射可转移到红色受体染料的绿光。结果表明，方酸轮烷过氧化物的化学发光发射源自于轮烷内激发态的方酸。
• Fluorescent Thienothiophene-Containing Squaraine Dyes and Threaded Supramolecular Complexes with Tunable Wavelengths between 600–800 nm
  作者：Wenqi Liu、Hannah McGarraugh、Bradley Smith

  DOI：10.3390/molecules23092229

  日期：——

  stability, increased fluorescence quantum yield, and decreased fluorescence quenching upon dye self-aggregation. Energy transfer within the supramolecular complex permitted multiplex emission. That is, two separate dyes with fluorescence emission bands that match the popular Cy5 and Cy7 channels, could be simultaneously excited with a beam of 375 nm light. A broad range of practical applications is envisioned

  描述了一个新的含荧光噻吩和噻吩并噻吩的方酸菁染料家族，其可调波长覆盖了600-800 nm的吸收/发射范围。深红色和近红外荧光化合物易于通过简单的合成和纯化方法制备。光谱研究表明，每个方酸均被四内酰胺大环快速包封，在水中具有纳摩尔亲和力，以产生具有高化学稳定性，增加的荧光量子产率和减少的染料自聚集荧光猝灭的带螺纹的超分子复合物。超分子复合物中的能量转移允许多重发射。也就是说，可以用375 nm的光束同时激发具有独立于流行的Cy5和Cy7通道的荧光发射带的两种染料。
• Squaraine Rotaxanes with Boat Conformation Macrocycles
  作者：Na Fu、Jeffrey M. Baumes、Easwaran Arunkumar、Bruce C. Noll、Bradley D. Smith

  DOI：10.1021/jo901298n

  日期：2009.9.4

  central C4O2 core, is less electrophilic than the extended bis(anilino)squaraine analogue, but it is still susceptible to chemical and photochemical bleaching. Its stability is greatly enhanced when it is encapsulated as an interlocked squaraine rotaxane. An X-ray crystal structure of this truncated squaraine rotaxane shows the macrocycle in a boat conformation, and NMR studies indicate that the boat is

  荧光、深红色双（苯胺基）方酸染料在 Leigh 型四内酰胺大环内的机械封装产生互锁的方酸轮烷。周围的大环是灵活的，可以在溶液中快速交换椅子和船的构象。一系列 X 射线晶体结构显示了轮烷共构象交换过程如何涉及大环围绕封装的方酸线中心的同步横向振荡。具有 1,4-亚苯基侧壁和 2,6-吡啶二甲酰胺桥接单元的轮烷大环比具有含间苯二甲酰胺大环的类似方酸环烷轮烷系统更可能采用固态船型构象。一种截短的方酸染料，仲胺直接连接到中央 C 4 O2核的亲电子性低于扩展的双（苯胺基）方酸类似物，但它仍然容易受到化学和光化学漂白的影响。当它被封装为一个互锁的方酸环烷轮烷时，它的稳定性大大增强。这种截短的方酸环烷轮烷的 X 射线晶体结构显示大环呈船形，核磁共振研究表明船保持在溶液中。封装为轮烷可使染料的亮度增加 6 倍。封装过程似乎限制了染料并减少了发色团因平面性而变形。这项研究展示了如何将机械包封作为轮烷用作合
• Internal and External Stereoisomers of Squaraine Rotaxane Endoperoxide: Synthesis, Chemical Differences, and Structural Revision
  作者：Carleton G. Collins、Joshua M. Lee、Allen G. Oliver、Olaf Wiest、Bradley D. Smith

  DOI：10.1021/jo402564k

  日期：2014.2.7

  Photooxygenation of permanently interlocked squaraine rotaxanes with anthracene-containing macrocydes produces the corresponding squaraine rotaxane endoperoxides (SREPs) quantitatively. SREPs are stored at low temperature, and upon warming, they undergo clean cycloreversion, releasing singlet oxygen and emitting light. The structural elucidation in 2010 assigned the structure as the SREP-int stereoisomer, with the endoperoxide unit directed inside the macrocycle cavity. New experimental and computational evidence reported here proves that the initial, kinetic photooxygenation product is the less stable SREP-ext stereoisomer with the endoperoxide unit directed outside the macrocycle. The photophysical properties and subsequent reactivity of mechanically strained SREP-ext depend on the size of the end groups of the encapsulated squaraine dye. If the end groups are sufficiently large to prevent dissociation of the interlocked components, the strained SREP-ext stereoisomer undergoes clean, thermal cycloreversion. However, smaller squaraine end groups allow transient dissociation, resulting in a pseudorotaxane dissociation/association process that produces SREP-int as the thermodynamic stereoisomer that does not cyclorevert. The large difference in endoperoxide reactivity for the two SREP stereoisomers illustrates the power of the mechanical bond to induce cross-component steric strain and selective enhancement of a specific reaction pathway. The new insight enabled synthetic development of triptycene-containing squaraine rotaxanes with high fluorescence quantum yields and large Stokes shifts.
• Self-Assembly of Fluorescent Inclusion Complexes in Competitive Media Including the Interior of Living Cells
  作者：Jeremiah J. Gassensmith、Easwaran Arunkumar、Lorna Barr、Jeffrey M. Baumes、Kristy M. DiVittorio、James R. Johnson、Bruce C. Noll、Bradley D. Smith

  DOI：10.1021/ja075567v

  日期：2007.12.1

  Anthracene-containing tetralactam macrocycles are prepared and found to have an extremely high affinity for squaraine dyes in chloroform (log K-a = 5.2). Simply mixing the two components produces highly fluorescent, near-infrared inclusion complexes in quantitative yield. An X-ray crystal structure shows the expected hydrogen bonding between the squaraine oxygens and the macrocycle amide NH residues, and a high degree of cofacial aromatic stacking. The kinetics and thermodynamics of the assembly process are very sensitive to small structural changes in the binding partners. For example, a macrocycle containing two isophthalamide units associates with the squaraine dye in chloroform 400 000 times faster than an analogous macrocycle containing two 2,6-dicarboxamidopyridine units. Squaraine encapsulation also occurs in highly competitive media such as mixed aqueous/organic solutions, vesicle membranes, and the organelles within living cells. The highly fluorescent inclusion complexes possess emergent properties; that is, as compared to the building blocks, the complexes have improved chemical stabilities, red-shifted absorption/emission maxima, and different cell localization propensities. These are useful properties for new classes of near-infrared fluorescent imaging probes.