dimethyl 4,5,6,7-tetrahydro-2H-isoindole-5,6-dicarboxylate | 334641-87-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: dimethyl 4,5,6,7-tetrahydro-2H-isoindole-5,6-dicarboxylate
• CAS: 334641-87-1
• 化学式: C₁₂H₁₅NO₄
• 分子量: 237.255
• InChiKey: UBTTVYVBXPKXIG-UHFFFAOYSA-N

物化性质

• 沸点：
  389.4±42.0 °C(Predicted)
• 密度：
  1.249±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  对硝基苯甲醛 、 dimethyl 4,5,6,7-tetrahydro-2H-isoindole-5,6-dicarboxylate 在 三氟化硼乙醚 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 2.17h， 以25%的产率得到
  参考文献：
  名称：

  新型通用合成取代的四苯并卟啉

  摘要：

  开发了一条新颖的合成路线，合成具有各种外围官能团的四芳基四苯并卟啉（Ar 4 TBP）。该程序包括（i）1-硝基-或1-苯基磺酰基环己烯与异氰基乙酸酯的Barton-Zard缩合;（ii）所得4,5,6,7-四氢异吲哚与芳香族醛的缩合，得到稠合的四芳基四环己烯基卟啉（Ar 4 TCHP），以及（iii）将Ar 4 TCHP的金属配合物芳构化为相应的Ar 4 TBP。将Ar 4 TBP的Cu和Zn络合物进一步脱金属，得到相应的Ar 4TBP游离碱。该序列的总产率为15％至40％，这使得该方法适合一次制备克量的Ar 4 TBP。讨论了方法的范围，外围取代基的选择，金属离子的选择及其对芳构化收率的影响。报告了新合成的Ar 4 TBP和Ar 4 TCHP的基本光谱性质以及NiAr 4 TBP配合物的第一个X射线晶体结构。

  DOI：

  10.1021/jo0350054
• 作为产物：
  描述：

  4-(Phenylsulfonyl)-4-cyclohexene-1,2-dicarboxylic acid dimethyl ester 在 palladium hydroxide - carbon potassium tert-butylate 、 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇 为溶剂， 反应 0.5h， 生成 dimethyl 4,5,6,7-tetrahydro-2H-isoindole-5,6-dicarboxylate
  参考文献：
  名称：

  Synthesis and Luminescence of Soluble meso-Unsubstituted Tetrabenzo- and Tetranaphtho[2,3]porphyrins

  摘要：

  Syntheses of soluble tetrabenzoporphyrins (TBP) and tetranaphtho[2,3]porphyrins (TNP), with multiple substituents in the conjugated aromatic rings but bearing no substituents in the mesopositions, is reported. Both types of porphyrins were obtained by direct aromatization of precursor porphyrins, annealed with either cyclohexene or dihydronaphthalene fragments. TBPs and TNPs possess powerful absorption bands in the near-infrared (lambda = 610-710 nm, is an element of = 100,000-300,000 M-1 cm(-1)) and exhibit strong luminescence. Free bases and Zn complexes fluoresce with quantum yields of up to 50%, whereas Pd and Pt complexes phosphoresce in solutions at ambient temperatures. Remarkably, the phosphorescence quantum yields of Pd and Pt TBPs reach as high as 20-50%, which places them among the brightest near-infrared phosphors known to date.

  DOI：

  10.1021/jo051580r

文献信息

• An expedient synthesis of substituted tetraaryltetrabenzoporphyrins
  作者：Olga Finikova、Andrei Cheprakov、Irina Beletskaya、Sergei Vinogradov

  DOI：10.1039/b008816l

  日期：——

  A simple route to tetraaryltetrabenzoporphyrins (Ar4TBPs) is developed; the procedure allows for the introduction of substituents on both benzo- and phenyl-rings and employs readily available, inexpensive components.

  一种合成四芳基四苯并卟啉（Ar4TBPs）的简单方法被开发出来；该方法允许在苯环和苯基上引入取代基，并使用容易获得且廉价的成分。
• Porphyrin and Tetrabenzoporphyrin Dendrimers:  Tunable Membrane-Impermeable Fluorescent pH Nanosensors
  作者：Olga Finikova、Alexander Galkin、Vladimir Rozhkov、Maria Cordero、Cecilia Hägerhäll、Sergei Vinogradov

  DOI：10.1021/ja0341687

  日期：2003.4.1

  The pH dependencies of the UV-vis and fluorescent spectra of new water-soluble dendritic porphyrins and tetrabenzoporphyrins were studied. Because of extended pi-conjugation and nonplanar distortion, the absorption and the emission bands of tetraaryltetrabenzoporphyrins (Ar4TBP) are red-shifted and do not overlap with those of regular tetraarylporphyrins (Ar4P). When encapsulated inside dendrimers with hydrophilic outer layers, Ar(4)Ps and Ar(4)TBPs become water soluble and can serve as pH indicators, with pKs adjustable by the peripheral charges on the dendrimers. Two new dendritic porphyrins, Gen 4 polyglutamic porphyrin dendrimer H2P-Glu(4)OH (1) with 64 peripheral carboxylates and Gen 1 poly(ester amide) Newkome-type tetrabenzoporphyrin dendrimer H2TBP-Nw(1)OH (2) with 36 peripheral carboxylates, were synthesized and characterized. The pKs of the encapsulated porphyrins (pK(H2P-Glu)(OH)(4) = 6.2 and pK(H2TBP)-Nw(1)OH = 6.3) were found to be strongly influenced by the dendrimers, revealing significant electrostatic shielding of the cores by the peripheral charges. The titration curves obtained by differential excitation using the mixtures of the dendrimers were shown to be identical to those determined for the dendrimers individually. Due to their peripheral carboxylates and nanometric molecular size, porphyrin dendrimers cannot penetrate through phospholipid membranes. Dendrimer 1 was captured inside phospholipid liposomes, which were suspended in a solution containing dendrimer 2. No response from 1 was detected upon pH changes in the bulk solution, while the response from 2 was predictably strong. When proton channels were created in the liposome walls, both compounds responded equally to the bulk pH changes. These results suggest that porphyrin dendrimers can be used as fluorescent pH indicators for proton gradient measurements.
• Novel Versatile Synthesis of Substituted Tetrabenzoporphyrins
  作者：Olga S. Finikova、Andrei V. Cheprakov、Irina P. Beletskaya、Patrick J. Carroll、Sergei A. Vinogradov

  DOI：10.1021/jo0350054

  日期：2004.1.1

  choice of the metal ions, and their influence on the yields of aromatization are discussed. The basic spectroscopic properties of newly synthesized Ar4TBP's and Ar4TCHP's are reported together with the first X-ray crystallographic structure of the NiAr4TBP complex.

  开发了一条新颖的合成路线，合成具有各种外围官能团的四芳基四苯并卟啉（Ar 4 TBP）。该程序包括（i）1-硝基-或1-苯基磺酰基环己烯与异氰基乙酸酯的Barton-Zard缩合;（ii）所得4,5,6,7-四氢异吲哚与芳香族醛的缩合，得到稠合的四芳基四环己烯基卟啉（Ar 4 TCHP），以及（iii）将Ar 4 TCHP的金属配合物芳构化为相应的Ar 4 TBP。将Ar 4 TBP的Cu和Zn络合物进一步脱金属，得到相应的Ar 4TBP游离碱。该序列的总产率为15％至40％，这使得该方法适合一次制备克量的Ar 4 TBP。讨论了方法的范围，外围取代基的选择，金属离子的选择及其对芳构化收率的影响。报告了新合成的Ar 4 TBP和Ar 4 TCHP的基本光谱性质以及NiAr 4 TBP配合物的第一个X射线晶体结构。
• Synthesis and Luminescence of Soluble <i>m</i><i>eso-</i>Unsubstituted Tetrabenzo- and Tetranaphtho[2,3]porphyrins
  作者：Olga S. Finikova、Andrei V. Cheprakov、Sergei A. Vinogradov

  DOI：10.1021/jo051580r

  日期：2005.11.1

  Syntheses of soluble tetrabenzoporphyrins (TBP) and tetranaphtho[2,3]porphyrins (TNP), with multiple substituents in the conjugated aromatic rings but bearing no substituents in the mesopositions, is reported. Both types of porphyrins were obtained by direct aromatization of precursor porphyrins, annealed with either cyclohexene or dihydronaphthalene fragments. TBPs and TNPs possess powerful absorption bands in the near-infrared (lambda = 610-710 nm, is an element of = 100,000-300,000 M-1 cm(-1)) and exhibit strong luminescence. Free bases and Zn complexes fluoresce with quantum yields of up to 50%, whereas Pd and Pt complexes phosphoresce in solutions at ambient temperatures. Remarkably, the phosphorescence quantum yields of Pd and Pt TBPs reach as high as 20-50%, which places them among the brightest near-infrared phosphors known to date.