4-硼酸新戊二醇酯三苯胺 | 408359-97-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 4-硼酸新戊二醇酯三苯胺
• 英文名称: [4-(5,5-dimethyl[1,3,2]dioxaborinan-2-yl)phenyl]diphenylamine
• 英文别名: 2,2-dimethyl-1,3-propanediol 4-(diphenylamino)phenylboronate；4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-N,N-diphenylaniline；4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)triphenylamine；4-(neopentylglycolatoboron)-N,N-diphenylaniline；Benzenamine, 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-N,N-diphenyl-
• CAS: 408359-97-7
• 化学式: C₂₃H₂₄BNO₂
• 分子量: 357.26
• InChiKey: VKRFLXKOJWGSOJ-UHFFFAOYSA-N

物化性质

• 沸点：
  501.9±33.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4'-溴-α,α,α''-三吡啶 、 4-硼酸新戊二醇酯三苯胺 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 乙二醇二甲醚 为溶剂， 以59%的产率得到4'-(4-N,N-diphenylaminophenyl)-2,2':6',2''-terpyridine
  参考文献：
  名称：

  The synthesis of 4′-aryl substituted terpyridines by Suzuki cross-coupling reactions: substituent effects on ligand fluorescence

  摘要：

  通过钯催化的交叉偶联反应，制备了几种4′-芳基取代的2,2′:6′,2″-三联吡啶（tpy-C6H4R），涉及4′-溴三联吡啶或4′-三氟甲磺酸酯三联吡啶（triflate = 三氟甲磺酰氧基）与芳基硼酸或硼酸酯的反应，RC6H4B(OR′)2（R = H, m-NH2, p-CHO, -NO2, -CN, -NMe2, -NPh2）。新配体4′-三甲基苯基三联吡啶（mesityl = 2,4,6-三甲基苯基）也通过相同方法制备。类似地，4′-溴苯基三联吡啶（tpy-Φ-Br）已与芳基卤化物交叉偶联，生成了几种新的双芳基取代三联吡啶（tpy-Φ-C6H4R，其中R = H, p-CN, NMe2, NPh2），以及两种含有3-或4-吡啶基侧链的相关化合物（tpy-Φ-C6H4-py）。对于选定的化合物，还研究了替代的偶联策略，即反应一个三联吡啶-4-硼酸酯或三联吡啶-4-苯基硼酸酯与适当的芳基卤化物（例如制备tpy-Φ-C6H4NO2），但通常发现效果较差。所有化合物在紫外区域都有荧光发射，双芳基取代的化合物相比于单芳基系统仅有轻微的红移，但其伴随质子化产生的进一步红移对前者更为显著。溶液中的荧光寿命在1~5纳秒范围内。氨基联苯取代化合物的发射光谱（tpy-Φ-C6H4NR″2，其中R″ = Me或Ph）随着溶剂极性的增加显示出较大的红移，表明存在分子内电荷转移态，这与先前报道的两种省略苯环的类似物（tpy-C6H4NR″2）一致。然而，与后者不同，氨基联苯化合物在质子化或与路易斯酸性金属离子结合时，其发射几乎完全淬灭。

  DOI：

  10.1039/b205330f
• 作为产物：
  描述：

  4-溴三苯胺 、 联硼酸新戊二醇酯 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 potassium acetate 作用下， 以 二甲基亚砜 为溶剂， 反应 5.5h， 以93%的产率得到4-硼酸新戊二醇酯三苯胺
  参考文献：
  名称：

  摘要：

  A sequence of three metal-catalysed aryl coupling reactions leads to the new ligand 4'-(4-N,N-diphenylaminophenyl) 2,2':6',2"-terpyridine, the intense ICT emission of which undergoes a large red-shift upon binding of zinc ions, providing a unique response over other common metal ions.

  DOI：

  10.1039/b108408a

文献信息

• Catalytic conjunctive cross-coupling enabled by metal-induced metallate rearrangement
  作者：Liang Zhang、Gabriel J. Lovinger、Emma K. Edelstein、Adam A. Szymaniak、Matteo P. Chierchia、James P. Morken

  DOI：10.1126/science.aad6080

  日期：2016.1

  Suzuki-Miyaura coupling. Specifically, we demonstrate that vinyl boronic ester ate complexes, prepared by combining organoboronates and organolithium reagents, engage in palladium-induced metallate rearrangement wherein 1,2-migration of an alkyl or aryl group from boron to the vinyl α-carbon occurs concomitantly with C–Pd σ-bond formation. This elementary reaction enables a powerful cross-coupling

  Suzuki 偶联的二合一扭曲 Suzuki-Miyaura 偶联反应是最广泛使用的制备碳-碳键的方法之一。本质上，钯催化剂激活一个碳碎片，然后将其与从硼中提取的第二个碎片连接起来。张等人。现在展示对传统途径的改变（参见 Fyfe 和 Watson 的观点）。在他们的系统中，钯最初将一个硼中心的两个碳碎片连接在一起。然后催化剂将第二个 CC 键缝合到第三个外部片段上。手性配体使反应具有高度的对映选择性。科学，这个问题 p。70; 另见第。26 钯在广泛使用的 Suzuki 偶联反应中催化硼上迁移性碳-碳键的形成。[另见 Fyfe 和 Watson 的观点] 过渡金属催化在当代有机合成中起着核心作用。考虑到非常广泛的过渡金属催化转化，值得注意的是基础元素反应步骤的数量相对较少。在这里，我们描述了许多金属催化反应中常见的有机金属金属转移步骤的替代方法，例如 Suzuki-Miyaura 偶联。
• Diphenylamine end-capped 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) derivatives with large two-photon absorption cross-sections and strong two-photon excitation red fluorescence
  作者：Er Qian Guo、Pei Hua Ren、Yan Li Zhang、Hai Chang Zhang、Wen Jun Yang

  DOI：10.1039/b911808j

  日期：——

  Novel donor–π-bridge–acceptor–π-bridge–donor (D–π–A–π–D)-type 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) derivatives with end-capping diphenylamine groups have been synthesized and shown to exhibit large two-photon absorption cross-sections over a wide range of wavelengths with strong two-photon excitation red fluorescence.

  新型供体-π桥-受体-π桥-供体（D-π-A-π-D）型 1,4-二酮-3,6-二苯基吡咯并[3,4-c]吡咯（DPP）衍生物已被合成，并显示其在宽波长范围内具有较大的双光子吸收截面，同时具有较强的双光子激发红色荧光。
• Singlet oxygen generation by two-photon excitation of porphyrin derivatives having two-photon-absorbing benzothiadiazole chromophores
  作者：Tsutomu Ishi-i、Yoshiki Taguri、Shin-ichiro Kato、Motoyuki Shigeiwa、Hideki Gorohmaru、Shuuichi Maeda、Shuntaro Mataka

  DOI：10.1039/b704499b

  日期：——

  Porphyrin derivatives with four two-photon absorbing 2,1,3-benzothiadiazole chromophores at the meso positions provide large two-photon absorption cross-sections up to 735 GM as well as large quantum yields of one-photon singlet oxygen sensitization of ca. 0.7, leading to generation of singlet oxygen by two-photon excitation of 800 nm. The two-photon singlet oxygen sensitization is discussed on the basis of a parameter of the normalized oxygen luminescence intensity obtained from the two-photon experiment.

  在中位具有四个双光子吸收 2,1,3-苯并噻二唑发色团的卟啉衍生物可提供高达 735 GM 的大双光子吸收截面，以及约 0.7 的大单光子单线态氧敏化量子产率，从而在 800 nm 的双光子激发下产生单线态氧。根据从双光子实验中获得的归一化氧发光强度参数，对双光子单线态氧敏化进行了讨论。
• Two-photon absorption and fluorescence fluoride-sensing properties of N-octyl-3,6-bis[4-(4-(diphenylamino)phenyl)phenyl]-1,4-diketo-pyrrolo[3,4-c]pyrrole
  作者：Yiping Li、Meng Zheng、Jianfeng Wang、Yangyang Gao、Baoliang Zhang、Wenjun Yang

  DOI：10.1016/j.dyepig.2013.12.031

  日期：2014.5

  red two-photon excitation fluorescence, but also could operate as one- and two-photon chemosensor selectively for fluoride anion. Interestingly, it is observed that both the detection sensitivity of TDP to fluoride anion and the ratiometric change in emission spectra upon two-photon induced by fluoride anion are higher than one-photon excitation, implying that TDP could serve better as two-photon fluorescence

  完全芳香的D–π–A–π–D型分子3,6-双[4-（4-（4-（二苯基氨基）-苯基）苯基] -N-辛基-1,4-二酮-吡咯并[3,4 - ç ]吡咯（TDP）合成，并在不存在或氟阴离子的存在下，单组分和双光子吸收和发射性能进行了研究。结果表明，TDP不仅表现出高达1030 GM的大的双光子吸收（2PA）横截面（δ）和强的红色双光子激发荧光，而且还可以选择性地用作氟离子的单光子和双光子化学传感器。 。有趣的是，观察到TDP的检测灵敏度氟离子对氟离子的诱导作用，且氟离子诱导的双光子发射光谱的比重变化高于单光子激发，说明TDP可以更好地用作氟离子的双光子荧光传感器。三苯胺端基促进的大δ和2PA红移带使TDP能够在更长的激发波长和更低的输入激光功率下感应氟离子。
• Two in One: Luminescence Imaging and 730 nm Continuous Wave Laser Driven Photodynamic Therapy of Iridium Complexes
  作者：Fengfeng Xue、Yang Lu、Zhiguo Zhou、Min Shi、Yuping Yan、Hong Yang、Shiping Yang

  DOI：10.1021/om500895y

  日期：2015.1.12

  A phosphorescent cationic iridium complex (1) with a donor-p-donor type unit as a N boolean AND N ligand and 2-phenylpyridine as a C boolean AND N ligand was synthesized and characterized. 1 exhibits an intense absorption peak centered at similar to 450 nm with a large molar extinction coefficient (e) of similar to 2.4 x 10(-4) M-1 cm1 and displays highly efficient orange-red phosphorescence located at 620 nm with a quantum efficiency of similar to 3% in PBS buffer solution at room temperature, which is beneficial for a luminescence probe in living cells excited by visible light. Importantly, the generation of singlet oxygen (1O(2)) by 1 was observed by 730 nm continuous wave (CW) laser irradiation owing to its reverse saturable absorption property, which was confirmed by the O-1(2) scavenger of 1,3-diphenylbenzo[c]furan (DPBF) and ESR spectra. The photodynamic therapy effect of 1 in vivo by a 730 nm CW laser was further assessed by histological examination and immunohistochemistry.