meso-tetraphenyl-2-oxa-3-oxoporphyrinato zinc(II) | 873077-87-3

• 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: meso-tetraphenyl-2-oxa-3-oxoporphyrinato zinc(II)
• 英文别名: [tetraphenyl-2-oxa-3-oxo-porphyrinato]Zn(II)；ZINC;2,7,12,17-tetraphenyl-4-oxa-22,24-diaza-21,23-diazanidapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(20),2,6(24),7,9,11,13(22),14,16,18-decaen-5-one；zinc;2,7,12,17-tetraphenyl-4-oxa-22,24-diaza-21,23-diazanidapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(20),2,6(24),7,9,11,13(22),14,16,18-decaen-5-one
• CAS: 873077-87-3
• 化学式: C₄₃H₂₆N₄O₂Zn
• 分子量: 696.095
• InChiKey: XOUGEYPZQPDRHC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  50
• 可旋转键数：
  4
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  74.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  meso-tetraphenyl-2-oxa-3-oxoporphyrinato zinc(II) 在 盐酸 、 三乙基硅烷 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成 meso-tetraphenyl-2-oxa-3-isopropylchlorin
  参考文献：
  名称：

  meso-Aryl-3-alkyl-2-oxachlorins

  摘要：

  The formal replacement of a pyrrole moiety of meso-tetraarylporphyrin 1 by an oxazole moiety is described. The key step is the conversion of porpholactones 4 (prepared by a known two-step oxidation procedure from 1) by addition of alkyl Grignard reagent to form meso-tetraaryl-3-alkyl-2-oxachlorins 9 (alkyloxazolochlorins.; alkyl = Me, Et, iPr). Hemiacetal 9 can be converted to an acetal, reduced to an ether, or converted to bis-alkyloxazolochlorins 11. The optical properties (UV-visible and fluorescence spectroscopy) are described. The chlorin-like optical properties of the alkyloxazolochlorins are compared to regular chlorins, such as 2,3-dihydroxychlorins and nonalkylated oxazolochlorins made by reduction from porpholactone 4. The conformations of the mono- and bis-alkylated 2-oxachlorins, as determined by single crystal X-ray diffractometry, are essentially planar, thus proving that their optical properties are largely due to their intrinsic electronic properties and not affected by conformational effects. The mono- and bis-3-alkyl-2-oxachlorins are a class of readily prepared and oxidatively stable chlorins.

  DOI：

  10.1021/jo300964v
• 作为产物：
  描述：

  tetraphenylporphyrin 在 2,2'-联吡啶 、 ruthenium trichloride 、 Oxone 、 sodium hydroxide 作用下， 以 乙醇 、 氯仿 、 水 、 1,2-二氯乙烷 为溶剂， 反应 2.0h， 生成 meso-tetraphenyl-2-oxa-3-oxoporphyrinato zinc(II)
  参考文献：
  名称：

  调整自组装笼中的卟啉构件用于丙烯的支链选择性加氢甲酰化

  摘要：

  通过将铑络合物嵌入超分子组装体L2中，在丙烯加氢甲酰化中对支化醛产物实现了前所未有的区域选择性，超分子组装体 L2 是由三（间吡啶基）膦和锌（II）卟啉内酯的配位驱动自组装形成的。笼L2的设计基于配体模板方法，其中配体充当笼形成的模板。此前，曾报道过第一代笼L1，其中使用锌(II)卟啉单元代替卟啉内酯。结合研究表明，第二代笼L2形成的缔合常数比L1高出近一个数量级。这种强化的结合使笼L2在极性和工业相关溶剂中保持完整。因此，通过使用第二代组装，可以在极性和配位溶剂中保持支化醛产物前所未有的区域选择性。

  DOI：

  10.1002/chem.201702113

文献信息

• <i>meso</i>-Arylporpholactones and their Reduction Products
  作者：Christian Brückner、Junichi Ogikubo、Jason R. McCarthy、Joshua Akhigbe、Michael A. Hyland、Pedro Daddario、Jill L. Worlinsky、Matthias Zeller、James T. Engle、Christopher J. Ziegler、Matthew J. Ranaghan、Megan N. Sandberg、Robert R. Birge

  DOI：10.1021/jo300963m

  日期：2012.8.3

  chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2-oxachlorin (11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles

  详细介绍了内消旋四芳基-3-氧代-2-氧杂卟啉5（称为卟啉内酯）的合理合成，通过 MnO 4 –介导的相应内消旋四芳基-2,3-二羟基二氢卟酚 ( 7 ) 的氧化作用进行了详细说明。由于二氢卟酚7是由母体卟啉1制备的，这相当于用恶唑酮部分对1中的吡咯部分进行 2 步置换。卟啉内酯5的逐步还原导致形成二氢卟酚类似物、内消旋-tetraaryl-3-hydroxy-2-oxachlorin ( 11 ) 和内消旋四芳基-2-oxachlorin (12 )。描述了11与 O-、N-和 S-亲核试剂亲核取代的反应性。用恶唑酮（类卟啉发色团）或（取代的）恶唑部分（二氢卟酚类发色团，对于母体恶唑并绿素12，红移 Q x）正式取代吡咯的深刻光物理后果具有增强的振荡器强度的波段）在 SAC-CI 和 MNDO-PSDCI 分子轨道理论计算的基础上进行了详细和合理化。卟啉内酯的单晶 X 射线结构指向羰基氧
• Oxazolochlorins 21. Most Efficient Access to meso-Tetraphenyl- and meso-Tetrakis(pentafluorophenyl)porpholactones, and Their Zinc(II) and Platinum(II) Complexes
  作者：Damaris Thuita、Dinusha Damunupola、Christian Brückner

  DOI：10.3390/molecules25184351

  日期：——

  specific derivative. We report here on what we experimentally evaluated to be the most efficient pathways to generate the six key compounds from the commercially available porphyrins, meso-tetraphenylporphyrin (TPP) and meso-tetrakis(pentafluorophenyl)porphyrin (TFPP): free base meso-tetraphenylporpholactone (TPL) and meso-tetrakis(pentafluorophenyl)porpholactone (TFPL), and their platinum(II) and zinc(II)

  内消旋苯基和内消旋五氟苯基卟内酯、它们的金属络合物以及直接衍生自它们的类卟啉可用于许多技术和生物医学应用，并且预计会发现更多用途。报道了大约十几种合成它们的竞争和互补途径。这些方法的适用性随着内消旋芳基以及是否寻求游离碱或金属衍生物而变化。这些情况使得合成卟啉化学领域之外的任何人都很难确定哪种途径最适合生产哪种特定衍生物。我们在这里报告了我们通过实验评估的从市售卟啉、内消旋四苯基卟啉（TPP）和内消旋四（五氟苯基）卟啉（TFPP）生成六种关键化合物的最有效途径：游离碱内消旋四苯基卟啉（ TPL）和内消旋四（五氟苯基）卟内酯（TFPL），以及它们的铂（II）和锌（II）络合物分别为TPLPt、TFPLPt、TPLZn和TFPLZn。提供了详细的程序，使这些有趣的分子更容易用于进一步研究。
• Catalysts and processes for producing aldehydes
  申请人：Eastman Chemical Company

  公开号：US09649625B1

  公开（公告）日：2017-05-16

  Use of a unique supramolecular assembly of a tris-pyridylphosphine ligand and a metal centered porphyrin complex modified with a lactone functional group was shown to have improved selectivities to branched aldehydes via rhodium catalyzed hydroformylation of unsubstituted linear alpha olefins such as propylene and 1-octene. The addition of potassium salts was also shown to increase the activity of the lactone modified porphyrin-based catalyst while maintaining similar branched aldehyde selectivities for propylene hydroformylation.

  通过使用一种独特的三吡啶膦配体和一个带有内酯功能基团改性的金属中心卟啉复合物的超分子组装，改进了通过铑催化的未取代线性α-烯烃（如丙烯和1-辛烯）的水合甲醛反应对支链醛的选择性。同时，添加钾盐也显示出增加内酯改性卟啉基催化剂活性的效果，同时保持对丙烯水合甲醛反应的类似支链醛选择性。
• Tunable <i>meso</i>-Tetraphenyl-alkyloxazolo-chlorins and -bacteriochlorins†Oxazolochlorins <b>4</b>. Oxazolochlorins <b>3</b>: Khalil, G. E.; Daddario, P.; Lau, K. S. F.; Imtiaz, S.; King, M.; Gouterman, M.; Sidelev, A.; Ghandehari, M.; Brückner, C. <i>Analyst</i><b>2010</b>, <i>135</i>, 2125−2131.
  作者：Junichi Ogikubo、Christian Brückner

  DOI：10.1021/ol2006264

  日期：2011.5.6

  Alkyl-Grignard addition to meso-tetraphenylporpholactone generates monoalkyl- and gem-bis-alkyloxazolochlorins. Together with compounds made by further synthetic manipulations of these derivatives, a series of chlorin-type chromophores with modulated optical properties is generated. Furthermore, their OsO4-mediated dihydroxylations and subsequent functional group transformations generate a family of bacteriochlorins that possess substituent-dependent optical properties. Thus, the formal replacement of a pyrrolidine moiety in chlorins and bacteriochlorins by variously substituted oxazoles is a flexible methodology to generate novel and stable chromophores that are tunable over a considerable range of the optical spectrum.