3,5-Dihydro-1H-thieno[3,4-c]pyrrolcarbonsaeure-benzylester | 218628-86-5

• 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: 3,5-Dihydro-1H-thieno[3,4-c]pyrrolcarbonsaeure-benzylester
• 英文别名: benzyl pyrrole-2-carboxylate；benzyl 2,2-dioxo-3,5-dihydro-1H-thieno[3,4-c]pyrrole-4-carboxylate
• CAS: 218628-86-5
• 化学式: C₁₄H₁₃NO₄S
• 分子量: 291.328
• InChiKey: NEVDGCJVGFSMHD-UHFFFAOYSA-N

物化性质

• 熔点：
  163-164 °C
• 沸点：
  619.1±55.0 °C(Predicted)
• 密度：
  1.442±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  84.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,5-Dihydro-1H-thieno[3,4-c]pyrrolcarbonsaeure-benzylester 在 氢气 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 反应 1.08h， 生成 3,5-dihydro-1H-thieno<3,4-c>pyrrole 2,2-dioxide
  参考文献：
  名称：

  摘要：

  The efficient preparation of the symmetric tetrasulfolenoporphyrin 1 is reported, which shows good solubility in a variety of solvents. In 1, four sulfone groups that symmetrically bridge the eight methylene groups in beta-position at the pyrrole rings provide four sulfolene (= 2,5-dihydrothiophene 1,1-dioxide) units which are prone to cleavage by thermally induced extrusion of sulfur dioxide. The tetrasulfolenoporphyrin, accordingly, is indicated to lend itself to specific and multiple refunctionalization by the replacement of the sulfone groups by other functionalities in SO(2) extrusion/cycloaddition sequences. The predicted reactivity and the potential of a zinc complex of the tetrasulfolenoporphyrin as a reactive porphyrin module (see 5b) is tested in exploratory experiments. To this end, thermolysis of the tetrasulfolenoporphyrinatozinc 5b in dichlorobenzene solution (at 140 degrees) and in the presence of [5,6]fullerene-C(60)-I(h) gives the (fullereno-porphyrinato)zinc 6 still having three sulfolene units and a 'diagonal' (difullerenoporphyrinato)zinc 7 that still has two sulfolene units, in 14 and in 43% yield, respectively.

  DOI：

  10.1002/(sici)1522-2675(20000315)83:3<583::aid-hlca583>3.0.co;2-a
• 作为产物：
  描述：

  benzyl 2-formamidoacetate 在 potassium tert-butylate 、 三乙胺 、 三氯氧磷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 3,5-Dihydro-1H-thieno[3,4-c]pyrrolcarbonsaeure-benzylester
  参考文献：
  名称：

  Eine einfache und flexible Synthese von Pyrrolen ausα,β-ungesättigten Sulfonen

  摘要：

  The addition of alkyl isocyanoacetates and isocyanoacetonitrile to alpha,beta-unsaturated sulfones affords a convenient and broad access to pyrroles with unusual substitution patterns (see Scheme 2). The alpha,beta-unsaturated sulfones required as starting materials are easily obtained from different olefines.

  DOI：

  10.1002/(sici)1522-2675(19981111)81:11<1978::aid-hlca1978>3.0.co;2-t

文献信息

• Porphodimethylidenes from porphyrin-fused 3-sulfolenes—versatile porphyrin dienes for cycloadditions
  作者：Maxwell J. Gunter、Hesheng Tang

  DOI：10.1039/a901446b

  日期：——

  A porphyrin with a β-fused 3-sulfolene on one of the pyrroles acts as a porphodimethylidene precusor which can be used for a variety of Diels–Alder cycloaddition reactions.

  卟啉中的一个吡咯上含有δ-融合的 3-亚硫基，可作为卟吩二甲叉前体，用于各种 DielsâAlder 环加成反应。
• Symmetrical tetra-β″-sulfoleno-<i>meso</i>-aryl-porphyrins — synthesis, spectroscopy and structural characterization
  作者：Srinivas Banala、Klaus Wurst、Bernhard Kräutler

  DOI：10.1142/s1088424613501204

  日期：2014.1

  We report here the preparation (in "one-pot") of a tetra-β″-sulfoleno-meso-aryl-porphyrin in about 80% yield by using an optimized modification of Lindsey's variant of the Adler–Longo approach. The Zn ( II )-, Cu ( II )- and Ni ( II )-complexes of the symmetrical porphyrin were prepared and characterized spectroscopically. Crystal structures of the fluorescent Zn ( II )- and of the non-fluorescent Ni ( II )-tetra-β″-sulfoleno-meso-aryl-porphyrinates showed the highly substituted porphyrin ligands to be nearly perfectly planar. The Zn ( II )-complex of this porphyrin has been used as a thermal precursor of a reactive diene, and — formally — of lateral and diagonal bis-dienes, of a tris-diene and of a tetra-diene, which all underwent [4 + 2]-cycloaddition reactions in situ with a range of dienophiles. Thus, the tetra-β″-sulfoleno-meso-aryl-porphyrin and its metal complexes represent reactive building blocks, "programmed" for the syntheses of symmetrical and highly functionalized porphyrins.

  我们在此报告，通过对 Lindsey 的 Adler-Longo 方法变体进行优化修改，以约 80% 的收率（"一锅 "法）制备了四-β″-亚磺酰基芳基卟啉。制备了对称卟啉的 Zn ( II )-、Cu ( II )- 和 Ni ( II )- 复合物，并对其进行了光谱学表征。荧光 Zn ( II )- 和非荧光 Ni ( II )- 四-β″-亚磺酰基芳基卟啉的晶体结构显示，高度取代的卟啉配体几乎是完全平面的。这种卟啉的 Zn ( II )-络合物已被用作活性二烯的热前体，并正式用作侧向和对角双二烯、三二烯和四二烯的热前体，它们都在原位与一系列二烯烃发生了[4 + 2]-环加成反应。因此，四-β″-亚磺酰基芳基卟啉及其金属复合物代表了活性构件，是合成对称和高功能化卟啉的 "程序化 "产物。
• <i>syn</i>-Diarylphthalimidoporphyrins: Effects of Symmetry Breaking on Two-Photon Absorption and Linear Photophysical Properties
  作者：Srinivasa Rao Allu、Luca Ravotto、Thomas Troxler、Sergei A. Vinogradov

  DOI：10.1021/acs.jpca.1c01652

  日期：2021.4.15

  Aromatically π-extended porphyrins possess exceptionally intense one-photon (1P) and sometimes two-photon (2P) absorption bands, presenting interest for construction of optical imaging probes and photodynamic agents. Here we investigated how breaking the molecular symmetry affects linear and 2PA properties of π-extended porphyrins. First, we developed the synthesis of porphyrins fused with two phthalimide

  芳香族 π 扩展卟啉具有异常强烈的单光子 (1P) 和有时双光子 (2P) 吸收带，这对构建光学成像探针和光动力剂具有重要意义。在这里，我们研究了破坏分子对称性如何影响 π 扩展卟啉的线性和 2PA 特性。首先，我们开发了与两个邻苯二甲酰亚胺片段融合的卟啉的合成，称为顺-二芳基邻苯二甲酰亚胺卟啉（DAIP）。二、H 2的光物理性质、Zn、Pd 和 Pt DAPIP 被测量并与完全对称的四芳基邻苯二甲酰亚胺卟啉 (TAIP) 的那些进行比较。使用 DFT/TDDFT 计算和状态总和 (SOS) 形式来解释数据。总体而言，2PA在DAPIP画面被发现类似，在中心对称的卟啉，表明破对称，即使显著由顺-phthalimido融合，引起相对小的扰动卟啉电子结构。总的来说，紧凑的尺寸、通用的合成、高 1PA 和 2PA 截面以及明亮的发光使 DAIP 成为构建成像探针和其他生物应用的有价值的发色团。
• Sulfolenoporphyrins: synthons for refunctionalization of porphyrins
  作者：Sang Hee Lee、Kevin M. Smith

  DOI：10.1016/j.tetlet.2005.01.154

  日期：2005.3

  Using sulfolenopyrroles (4) and (11) methods are developed for the synthesis of opp- (15,18,19) and adj- (25) bis-sulfolenoporphyrins,- such compounds are useful building blocks for the refunctionalization of the porphyrin system, and readily undergo Diels-Alder cycloaddition reactions. (C) 2005 Elsevier Ltd. All rights reserved.
• Montforts, Franz-Peter; Kutzki, Olaf, Angewandte Chemie - International Edition, 2000, vol. 39, # 3, p. 599 - 601
  作者：Montforts, Franz-Peter、Kutzki, Olaf

  DOI：——

  日期：——