19,22-bis(1-methylethoxy)-4,5,9,10,14,15-hexakis[(4-propyloxy-4-oxo-1-butyl)thio]-23H,25H-benzo[b]porphyrazine

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 19,22-bis(1-methylethoxy)-4,5,9,10,14,15-hexakis[(4-propyloxy-4-oxo-1-butyl)thio]-23H,25H-benzo[b]porphyrazine
• 英文别名: Propyl 4-[[4,9,10,14,15-pentakis[(4-oxo-4-propoxybutyl)sulfanyl]-20,23-di(propan-2-yloxy)-2,7,12,17,25,26,27,28-octazahexacyclo[16.6.1.13,6.18,11.113,16.019,24]octacosa-1(25),2,4,6,8,10,12,14,16(26),17,19,21,23-tridecaen-5-yl]sulfanyl]butanoate
• 化学式: C₆₈H₉₆N₈O₁₄S₆
• 分子量: 1441.95
• InChiKey: AMAFSXWKADPHBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14
• 重原子数：
  96
• 可旋转键数：
  52
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  437
• 氢给体数：
  2
• 氢受体数：
  26

反应信息

• 作为反应物：
  描述：

  19,22-bis(1-methylethoxy)-4,5,9,10,14,15-hexakis[(4-propyloxy-4-oxo-1-butyl)thio]-23H,25H-benzo[b]porphyrazine 在 lithium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 以100%的产率得到19,22-bis(1-methylethoxy)-4,5,9,10,14,15-hexakis[(4-hydroxy-4-oxo-1-butyl)thio]-23H,25H-benzo[b]porphyrazine
  参考文献：
  名称：

  Synthesis of Near-IR Absorbing/Emitting Porphyrazine Derivatives with Tunable Solubility

  摘要：

  We report the synthesis of porphyrazines (pzs), or tetraazaporphyrins, of the form H(2)[pz(A(n;)B(4-n))], where A is [S(CH(2))(3)COOR](2) (R = n-Pr, H) and B is a fused beta,beta'-diisopropyloxybenzo group, including the compounds with n = 4 (6), n = 3 (7) and the trans compound with n = 2 (8) (Scheme 1). The synthesis employs Linstead crossover macrocyclization of dimethyl 6,7-dicyano-5,8-dithia-6(Z)dodecenedioate, MNT(C(4)O(2)Me)2 (2), with 1-imino-4,7-bis(1-methylethoxy)-1H-isoindole-3-amine (4). These pigments were characterized by (1)H NMR, 13C NMR, absorbance/fluorescence spectroscopy, mass spectrometry, and microanalysis. An X-ray crystal structure of 8 is presented. Of particular note, 6-8 display intense near-IR absorbance and dual UV-visible/near-IR emission which are very important in potential biomedical applications, both for cancer therapy (photodyanamic therapy, PDT) and cancer diagnosis (optical tumor imaging). For example, the trans-porphyrazine 8 has an intense long-wavelength absorption at ca. 800 nm (log epsilon = 4.18) and S1 fluorescence at similar to 820 nm, where mammalian tissue is effectively penetrated by light. Transformation of the ester group permits a wide range of functionality and solubility to be generated without change in optical properties. As an example, hydrolysis of these compounds by LiOH in THF/H(2)O gives the corresponding carboxylato-functionalized pigments 9-11, which are described. The last of these dissolves without aggregation in fetal calf serum.

  DOI：

  10.1021/jo001220y
• 作为产物：
  描述：

  丙醇 、 1-imino-4,7-bis(1-methylethoxy)-1H-isoindolin-3-amine 、 dimethyl 6,7-dicyano-5,8-dithia-6(Z)-dodecenedioate 在 magnesium n-propoxide 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以22%的产率得到2,3,7,8,12,13,17,18-octakis[(4-propyloxy-4-oxo-1-butyl)thio]-21H,23H-porphyrazine
  参考文献：
  名称：

  Synthesis of Near-IR Absorbing/Emitting Porphyrazine Derivatives with Tunable Solubility

  摘要：

  We report the synthesis of porphyrazines (pzs), or tetraazaporphyrins, of the form H(2)[pz(A(n;)B(4-n))], where A is [S(CH(2))(3)COOR](2) (R = n-Pr, H) and B is a fused beta,beta'-diisopropyloxybenzo group, including the compounds with n = 4 (6), n = 3 (7) and the trans compound with n = 2 (8) (Scheme 1). The synthesis employs Linstead crossover macrocyclization of dimethyl 6,7-dicyano-5,8-dithia-6(Z)dodecenedioate, MNT(C(4)O(2)Me)2 (2), with 1-imino-4,7-bis(1-methylethoxy)-1H-isoindole-3-amine (4). These pigments were characterized by (1)H NMR, 13C NMR, absorbance/fluorescence spectroscopy, mass spectrometry, and microanalysis. An X-ray crystal structure of 8 is presented. Of particular note, 6-8 display intense near-IR absorbance and dual UV-visible/near-IR emission which are very important in potential biomedical applications, both for cancer therapy (photodyanamic therapy, PDT) and cancer diagnosis (optical tumor imaging). For example, the trans-porphyrazine 8 has an intense long-wavelength absorption at ca. 800 nm (log epsilon = 4.18) and S1 fluorescence at similar to 820 nm, where mammalian tissue is effectively penetrated by light. Transformation of the ester group permits a wide range of functionality and solubility to be generated without change in optical properties. As an example, hydrolysis of these compounds by LiOH in THF/H(2)O gives the corresponding carboxylato-functionalized pigments 9-11, which are described. The last of these dissolves without aggregation in fetal calf serum.

  DOI：

  10.1021/jo001220y

文献信息

• Varying the Electrochemical Potential and Thickness of Porphyrazine SAMs by Molecular Design
  作者：Hong Zong、Peng Sun、Chad A. Mirkin、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/jp905762p

  日期：2009.11.12

  A series of multithiol-functionalized free-base and Zn-coordinated porphyrazines (pz's) have been prepared and characterized as self-assembled monolayers (SAMs) on Au. The synthetic flexibility of the pz's provides a unique opportunity to tune their electronic and chemical characteristics and to control the distance of the redox-active pz macrocycle from the Au surface. This allows us to study the reduction potentials of these surface-bound pz's as a function of film thickness and molecular charge distribution using angle-resolved X-ray photoelectron spectroscopy and cyclic voltammetry. Upon SAM formation, the reduction potentials of all pz's show a significant positive shift from their formal potentials when free in solution (up to similar to +1 V), with the magnitude of the shift inversely related to the Au-pz distance as determined from the film thickness of the pz SAM (thicknesses ranging from 3.5 to 11.8 angstrom). When the pz lies down oil the surface, in a SAM of thickness -3.5 angstrom, the charge distribution within a pz macrocycle also plays a role in determining the potential shift. These observations are consistent with our originally proposed mechanism for potential shifts upon binding to a metal surface based on image charge effects and with the analysis of Liu and Newton (J. Phys. Chem. 1994, 98, 7162).
• Synthesis of Near-IR Absorbing/Emitting Porphyrazine Derivatives with Tunable Solubility
  作者：Sangwan Lee、Andrew J. P. White、David J. Williams、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/jo001220y

  日期：2001.1.1

  We report the synthesis of porphyrazines (pzs), or tetraazaporphyrins, of the form H(2)[pz(A(n;)B(4-n))], where A is [S(CH(2))(3)COOR](2) (R = n-Pr, H) and B is a fused beta,beta'-diisopropyloxybenzo group, including the compounds with n = 4 (6), n = 3 (7) and the trans compound with n = 2 (8) (Scheme 1). The synthesis employs Linstead crossover macrocyclization of dimethyl 6,7-dicyano-5,8-dithia-6(Z)dodecenedioate, MNT(C(4)O(2)Me)2 (2), with 1-imino-4,7-bis(1-methylethoxy)-1H-isoindole-3-amine (4). These pigments were characterized by (1)H NMR, 13C NMR, absorbance/fluorescence spectroscopy, mass spectrometry, and microanalysis. An X-ray crystal structure of 8 is presented. Of particular note, 6-8 display intense near-IR absorbance and dual UV-visible/near-IR emission which are very important in potential biomedical applications, both for cancer therapy (photodyanamic therapy, PDT) and cancer diagnosis (optical tumor imaging). For example, the trans-porphyrazine 8 has an intense long-wavelength absorption at ca. 800 nm (log epsilon = 4.18) and S1 fluorescence at similar to 820 nm, where mammalian tissue is effectively penetrated by light. Transformation of the ester group permits a wide range of functionality and solubility to be generated without change in optical properties. As an example, hydrolysis of these compounds by LiOH in THF/H(2)O gives the corresponding carboxylato-functionalized pigments 9-11, which are described. The last of these dissolves without aggregation in fetal calf serum.