2-oxobenzo[d][1,3]dithiole-5-carbaldehyde | 256479-38-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-oxobenzo[d][1,3]dithiole-5-carbaldehyde
• 英文别名: 2-oxobenzo[d][1,3]dithiole-5-carbaldenyde；2-Oxo-1,3-benzodithiole-5-carbaldehyde
• CAS: 256479-38-6
• 化学式: C₈H₄O₂S₂
• 分子量: 196.251
• InChiKey: KHAYUPFDZZVSJH-UHFFFAOYSA-N

物化性质

• 沸点：
  415.5±47.0 °C(Predicted)
• 密度：
  1.561±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  84.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-oxobenzo[d][1,3]dithiole-5-carbaldehyde 在 Amberlyst 、 亚磷酸三乙酯 作用下， 生成 2-(5-Diethoxymethyl-benzo[1,3]dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine
  参考文献：
  名称：

  新合成2- [1,3-二硫醇-2-亚烷基] -5,6-二氢-1,3-二硫代[4,5- b ] [1,4]二硫联苯胺上具有甲酰基的化合物，[1 ，4]二硫氨酸或噻吩环

  摘要：

  作为新型的基于TTF的退火供体，带有甲酰基的2- [1,3-二硫醇-2-亚烷基] -5,6-二氢-1,3-二硫代[4,5- b ] [1,4]二硫辛用Diels-Alder或分子内羟醛反应分别制备[1,4]-二硫氨酸或噻吩环。

  DOI：

  10.1016/s0040-4039(99)01851-1
• 作为产物：
  描述：

  4,7-Dibromo-2-oxo-4,5,6,7-tetrahydro-benzo[1,3]dithiole-5-carbaldehyde 以 乙腈 为溶剂， 生成 2-oxobenzo[d][1,3]dithiole-5-carbaldehyde
  参考文献：
  名称：

  新合成2- [1,3-二硫醇-2-亚烷基] -5,6-二氢-1,3-二硫代[4,5- b ] [1,4]二硫联苯胺上具有甲酰基的化合物，[1 ，4]二硫氨酸或噻吩环

  摘要：

  作为新型的基于TTF的退火供体，带有甲酰基的2- [1,3-二硫醇-2-亚烷基] -5,6-二氢-1,3-二硫代[4,5- b ] [1,4]二硫辛用Diels-Alder或分子内羟醛反应分别制备[1,4]-二硫氨酸或噻吩环。

  DOI：

  10.1016/s0040-4039(99)01851-1

文献信息

• Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes
  作者：Bo Zheng、Randy P. Sabatini、Wen-Fu Fu、Min-Sik Eum、William W. Brennessel、Lidong Wang、David W. McCamant、Richard Eisenberg

  DOI：10.1073/pnas.1509310112

  日期：2015.7.28

  The light-driven generation of H ₂ , the reductive side of water splitting, requires a light absorber or photosensitizer (PS) for electron-hole creation and photoinduced electron transfer. To increase the effectiveness of charge transfer chromophores as PSs, this report describes the attachment of a strongly absorbing organic dye (dipyrromethene-BF ₂ , commonly known as Bodipy) to Pt diimine dithiolate charge transfer chromophores and examination of systems containing these dyads for the light-driven generation of H ₂ . The use of these dyads increases system activity under green light irradiation (530 nm) relative to systems with either chromophore alone, validating such an approach in designing artificial photosynthetic systems. One dyad system exhibits both high activity and substantial durability (40,000 turnovers relative to PSs over 12 d).

  标题: 重要性 光驱动的H2生成，即水分裂的还原端，需要光吸收剂或光敏剂（PS）来产生电子-空穴并进行光诱导电子转移。为了增加电荷转移色素作为光敏剂的有效性，本报告描述了将强吸收的有机染料（二吡咯甲烷-BF2，通常称为Bodipy）附着到Pt二亚甲基二硫酸盐电荷转移色素上，并检查包含这些二聚体的系统对光驱动的H2生成的影响。使用这些二聚体在绿光照射（530 nm）下增加了系统活性，相对于仅有色素的系统，验证了这种设计人工光合系统的方法。其中一种二聚体系统表现出高活性和相当的耐久性（相对于PS在12天内的40,000次循环）。
• Rhodamine-Platinum Diimine Dithiolate Complex Dyads as Efficient and Robust Photosensitizers for Light-Driven Aqueous Proton Reduction to Hydrogen
  作者：Guocan Li、Michael F. Mark、Hongjin Lv、David W. McCamant、Richard Eisenberg

  DOI：10.1021/jacs.7b11581

  日期：2018.2.21

  rhodamine 1π-π* state to a charge separated (CS) RDM(0•)-Pt(+•) state is also observed. Differences in the relative activity of systems using the RDM-PtN2S2 dyads for H2 generation correlate well with the relative energies of the CS state and the PtN2S23CT state used for H2 production. These findings show how one can finely tune the excited state energy levels to direct excited state population to the

  合成了三个由罗丹明 (RDM) 染料共价连接到 Pt 二亚胺二硫醇 (PtN2S2) 电荷转移复合物的新二元组，并将其用作光敏剂，用于从水性质子中产生 H2。这三个二元组仅在罗丹明氨基上的取代基不同，分别表示为 Pt-RDM1、Pt-RDM2 和 Pt-RDM3。在乙腈中，三个二元组在可见光区显示出强吸收，对应于罗丹明 π-π* 吸收以及 PtN2S2 配合物的混合金属-二硫醇-二亚胺电荷转移带特征。罗丹明 π-π* 吸收最大值从 Pt-RDM1 到 Pt-RDM3 的偏移与电化学实验中测量的 HOMO-LUMO 能隙密切相关。在白光照射下，当连接到镀铂的 TiO2 纳米粒子 (Pt-TiO2) 时，二元组显示出高且稳定的 H2 生成活性。照射 40 小时后，含有 Pt-RDM1、Pt-RDM2 和 Pt-RDM3 的系统的周转数 (TON) 分别为 33600、42800 和 70700
• Mono- and di-substituted [FeFe]-hydrogenase H-cluster mimics bearing the 3,4-dimercaptobenzaldehyde bridge moiety: Insight into synthesis, characterization and electrochemical investigations
  作者：Hassan Abul-Futouh、Daniel Costabel、Konrad Hotzel、Phil Liebing、Helmar Görls、Wolfgang Weigand、Kalina Peneva

  DOI：10.1016/j.ica.2023.121469

  日期：2023.6

  describes the synthesis and characterization of [FeFe]-hydrogenase mimic, namely [Fe2(CO)6μ-bdtf}] (2, bdtf = 3,4-dimercaptobenzaldehyde) obtained from the reaction of 3,4-dimercaptobenzaldehyde with Fe3(CO)12. Moreover, treatment of complex 2 with PPh3 ligand yielded both mono- and disubstituted complexes [Fe2(CO)5PPh3μ-bdtf}] (3), [Fe2(CO)4(PPh3)2μ-bdtf}] (4), while in the case of P(OMe)3 ligand afforded

  本报告描述了 [FeFe]-氢化酶模拟物的合成和表征，即从 3,4-二巯基苯甲醛的反应中获得的[Fe 2 (CO) 6 μ -bdtf}] ( 2 , bdtf = 3,4-二巯基苯甲醛)与 Fe 3 (CO) 12。此外，用 PPh 3配体处理络合物2产生单取代和双取代络合物 [Fe 2 (CO) 5 PPh 3 μ -bdtf}] ( 3 ), [Fe 2 (CO) 4 (PPh 3 ) 2 μ -bdtf}] (4 ), 而在 P(OMe) 3配体的情况下，仅提供二取代络合物 [Fe 2 (CO) 4 (P(OMe) 3 ) 2 μ -bdtf}] ( 5 )。通过X 射线衍射分析证实了配合物2-5的分子结构。此外，已经通过循环伏安法评估了苯环和铁中心取代基对电化学和这些模拟物对质子还原的催化作用的影响。所有配合物都显示出它们在弱酸（例如乙酸 (AcOH)）存在下形成氢气的潜力。
• Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy−Pt(II)(diimine)(dithiolate) Conjugates
  作者：Theodore Lazarides、Theresa M. McCormick、Kristina C. Wilson、Soohyun Lee、David W. McCamant、Richard Eisenberg

  DOI：10.1021/ja1070366

  日期：2011.1.19

  The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)pi pi* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (MML)-M-1'CT (mixed metal-ligand to ligand charge transfer) excited state (tau(3)(SEnT) = 0.6 ps, tau(4)(SEnT) = 0.5 ps, and tau(6)(SEnT) = 1.6 ps), which undergoes rapid intersystem crossing to the (MMLL)-M-3'CT state due to the heavy Pt(II) ion. The (MMLL)-M-3'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3 pi pi* excited state (tau(3)(TEnT) = 8.2 ps, tau(4)(TEnT) = 5 ps, and tau(6)(TEnT) = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.
• New synthesis of 2-[1,3-dithiol-2-ylidene]-5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiins with formyl group on fused benzene, [1,4]dithiin, or thiophene ring
  作者：Yoshihiro Ishikawa、Tomoko Miyamoto、Asami Yoshida、Yuzo Kawada、Jotaro Nakazaki、Akira Izuoka、Tadashi Sugawara

  DOI：10.1016/s0040-4039(99)01851-1

  日期：1999.12

  As novel TTF-based annelated donors, 2-[1,3-dithiol-2-ylidene]-5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiins with a formyl group on fused benzene, [1,4]-dithiin, or thiophene ring, respectively, were prepared using Diels-Alder or an intramolecular aldol reaction.

  作为新型的基于TTF的退火供体，带有甲酰基的2- [1,3-二硫醇-2-亚烷基] -5,6-二氢-1,3-二硫代[4,5- b ] [1,4]二硫辛用Diels-Alder或分子内羟醛反应分别制备[1,4]-二硫氨酸或噻吩环。