bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl]diselenide | 205828-75-7

• 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: bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl]diselenide
• 英文别名: 2-[2-[[2-(4,4-dimethyl-5H-1,3-oxazol-2-yl)phenyl]diselanyl]phenyl]-4,4-dimethyl-5H-1,3-oxazole
• CAS: 205828-75-7
• 化学式: C₂₂H₂₄N₂O₂Se₂
• 分子量: 506.365
• InChiKey: HPHVWGDTODVJRK-UHFFFAOYSA-N

物化性质

• 沸点：
  591.2±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.07
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl]diselenide 在 碘 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 以90%的产率得到<2-(4,4-Dimethyl-2-oxazolinyl)phenyl>selenyl iodide
  参考文献：
  名称：

  Selenenyl iodide: a new substrate for mammalian thioredoxin reductaseElectronic supplementary information (ESI) available: additional data. See http://www.rsc.org/suppdata/ob/b3/b302220j/

  摘要：

  我们合成了通过内部螯合稳定的烯硒碘化物，并将其作为硫代还原酶（TrxR）的底物进行了评估。研究发现，从人类胎盘中提取的 TrxR 对硒碘化物的反应活性远高于大肠杆菌酶，这表明人类酶活性位点中的硒半胱氨酸残基是必不可少的。加入硫代氧化酶（Trx）后，TrxR 催化的碘化硒还原作用明显增强 1。这些关于硫氧还蛋白系统还原硒碘化物的研究表明，稳定的硒碘化物可能是人类 TrxR 的新底物。Trx 系统可以作为碘甲腺氨酸脱碘酶的辅助因子，在脱碘酶催化周期的后半段还原硒基碘化物中间体，以再生活性位点。抗甲状腺药物 PTU 不抑制 TrxR 催化的 1 的还原，这表明 Trx 系统参与脱碘酶循环可能是某些脱碘酶对临床有用的硫脲类药物不敏感的原因。

  DOI：

  10.1039/b302220j
• 作为产物：
  描述：

  4,4-二甲基-2-苯基-2-噁唑啉 在 正丁基锂 、 selenium 、 氧气 、 碳酸氢钠 作用下， 以 正己烷 为溶剂， 反应 3.25h， 以60%的产率得到bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl]diselenide
  参考文献：
  名称：

  二芳基二硒化物的谷胱甘肽过氧化物酶样抗氧化活性：机理研究

  摘要：

  描述了几种具有分子内配位氨基的二芳基二硒化物的合成、结构和硫醇过氧化物酶样抗氧化活性。源自对映体纯 R-(+)- 和 S-(-)-N,N-二甲基（1-二茂铁基乙基）胺的二硒化物显示出优异的过氧化物酶活性。为了研究各种有机硒中间体的机械作用，通过 (77)Se NMR 光谱对中间体进行了详细的原位表征。虽然大多数二硒化物通过硒醇、硒酸和硒基硫化物中间体发挥其过氧化物酶活性，但二硒化物相对活性的差异是由于分子内硒相互作用的程度不同。二硒化物具有强硒。由于其硒基硫化物衍生物能够增强反向 GPx 循环（RSeSR + H(2)O(2) = RSeOH），N 相互作用被发现处于非活动状态。在这些情况下，硫醇的亲核攻击优先发生在硒而不是硫上，这通过终止正向反应来减少硒醇的形成。另一方面，由于硒基硫化物衍生物与硫醇快速反应生成二苯基二硫化物和预期的硒醇（RSeSR + PhSH = PhSSPh + RSeH），因此发现具有弱

  DOI：

  10.1021/ja994467p

文献信息

• Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation
  作者：Tapash Chakraborty、Kriti Srivastava、Harkesh B. Singh、Ray J. Butcher

  DOI：10.1016/j.jorganchem.2011.04.018

  日期：2011.8

  respectively. The complexes were characterized by elemental analysis and NMR (1H and 77Se) spectroscopy. Complexes 4 and 5 were also characterized by mass spectrometry. Molecular structures of 4, 5, 9, 14 and 15 have been established by single crystal X-ray diffraction analysis. Complexes 4 and 9 are isomorphous and crystallize in the space group P21/c of the monoclinic system where the selenolato and halo ligands

  将双[2-（4,4-二甲基-2-恶唑啉基）苯基]二硒化物氧化添加到Pd（PPh 3）4中，得到两种不同的单核硒硒化钯络合物Pd（Se∩N）（PPh 3）Cl（4） [Se∩N=螯合2-（4,4-二甲基-2-恶唑啉基）苯基硒酸酯]和Pd（Se∩N）（Se∩N*）（PPh 3）（5）[Se∩N=螯合，Se∩ N * ＝分别在二氯甲烷和甲苯中的非螯合的2-（4，4-二甲基-2-恶唑啉基）苯基硒烯基配体]。复杂4也被氧化加成的2-（4,4-二甲基-2-恶唑啉基）苯硒酰氯的Pd（PPh合成3）4。4（的溴和碘类似物通过将2-（4,4-二甲基-2-恶唑啉基）苯基硒烯基溴和碘分别氧化添加到Pd（PPh 3）4中，类似地合成了图9和图10）。将2-（N，N-二甲基氨基甲基）苯基硒烯溴化物和碘化物氧化添加到Pd（PPh 3）4中，得到单核硒化钯钯络合物Pd（Se∩N）（PPh 3）X（13和14）[Se∩N
• Synthesis and Structural Characterization of Monomeric Selenolato Complexes of Zinc, Cadmium, and Mercury
  作者：G. Mugesh、Harkesh B. Singh、Rajan P. Patel、Ray J. Butcher

  DOI：10.1021/ic970714j

  日期：1998.6.1

  enantiomers. (1)H, (13)C, and (77)Se NMR measurements indicate that complex 1 retains its "helical" structure in solution. Crystal data (Mo Kalpha; 293(2) K) are as follows: 1, monoclinic space group P2(1), a = 9.3900(12) Å, b = 11.618(2) Å, c = 10.8822(14) Å, beta = 98.245(8) degrees, Z = 2; 2, orthorhombic space group Pbca, a = 12.777(6) Å, b = 17.841(10) Å, c = 21.010(8) Å, Z = 8; 3, monoclinic space

  描述了结合分子内螯合恶唑啉配体的硒化锌（II），镉（II）和汞（II）的合成和表征。衍生物M [Se（Ox）]（2）[M = Zn（1），Cd（2），Hg（3）; Ox = 2-（4,4-二甲基-2-恶唑啉基）苯]是通过MCl（2）与异戊烯酸锂OxSe（-）Li（+）的复分解反应以高收率制备的。还通过用元素汞处理相应的二硒化物来合成汞配合物3。该配合物非常稳定，并高度溶于常见的非极性有机溶剂。X射线衍射结果表明，该配合物是固态的单体。发现所有络合物中金属离子周围的几何形状都是扭曲的四面体。Zn [Se（Ox）]（2）（1）的晶体结构表明该络合物为“螺旋形” 手性和对映体纯。外消旋体的自发分裂表明外消旋体和纯对映体之间的溶解度差异。（1）H，（13）C和（77）Se NMR测量表明，络合物1在溶液中保留了其“螺旋”结构。晶体数据（Mo Kalpha; 293（2）K）如下：1，单斜空间群P2（1），a
• Synthesis, Structure and Antioxidant Activity of Cyclohexene-Fused Selenuranes and Related Derivatives
  作者：Poonam Prasad、Harkesh Singh、Ray Butcher

  DOI：10.3390/molecules200712670

  日期：——

  Synthesis, structure and antioxidant activity of new cyclohexene-fused spiroselenuranes and a spirotellurane is reported. Oxidation reactions of bis(o-formylcyclohex- 1-ene)selenide/bis(2-hydroxymethylcyclohex-1-ene)selenide provide the corresponding spiroselenuranes. The glutathione peroxidase-like activity of the newly synthesized compounds has been evaluated.

  报告了新型环己烯融合螺硒脲和一种螺硒脲的合成、结构和抗氧化活性。双（邻甲酰基环己-1-烯）硒化物/双（2-羟甲基环己-1-烯）硒化物的氧化反应提供了相应的螺硒脲类化合物。对新合成化合物的谷胱甘肽过氧化物酶样活性进行了评估。
• Intramolecular Se⋅⋅⋅N Nonbonding Interactions in Low-Valent Organoselenium Derivatives: A Detailed Study by1H and77Se NMR Spectroscopy and X-Ray Crystallography
  作者：G. Mugesh、Arunashree Panda、Harkesh B. Singh、Ray J. Butcher

  DOI：10.1002/(sici)1521-3765(19990503)5:5<1411::aid-chem1411>3.0.co;2-m

  日期：1999.5.3

  A series of novel low-valent organoselenium compounds stabilized by Se...N intramolecular interactions has been synthesized. The existence of Se...N nonbonding interactions was determined by H-1 and Se-77 NMR spectroscopy and X-ray crystallography. These interactions result in an apparent downfield shift of the Se-77 NMR signals; the shift values roughly correspond with the strength of the Se...N interaction. Single-crystal X-ray studies show that the strength of the Se...N interactions depends on the relative electronegativity of the group attached to the selenium and the nature of the heteroatom. These interactions lengthen the Se-X (X = Se, Cl, Br, I, CH2-) bond trans to the N...Se bond and increase the possibility of nucleophilic attack on the selenium. In addition to the Se...N intramolecular interaction, Se...X (X = Cl, Br, I) intermolecular interactions were observed in [2-(4,4-dimethyl-2-oxazolinyl)phenyl]-selenenyl chloride (4), bromide (5), and iodide (6), indicative of the hypervalent (pseudo-high-valent) nature of the selenium. The strength of the Se...N intramolecular interaction decreases in the order RSeCl, RSeBr, RSeI, whereas the Se...X intermolecular interaction increases in the same order. The aryl benzylic compounds [2-(4,4-dimethyl-2-oxazolinyl)phenyl]benzyl selenide (7), alpha,alpha'-di[2-(4,4-dimethyl-2-oxazoliny1)-phenylselenenyl]-m-xylene (8), alpha,alpha'-di[2-(4,4-dimethyl-2-oxazolinyl)phenyl-selenenyl]-o-xylene (9), and 1,3,5-tri[2-(4,3-dimethyl-2-oxazolinyl)phenylselenenyl]-2,4,6-trimethylbenzene (10) are unusually stable and also show weak Se...N interactions in the solid state. The strong Se...N interactions in all the compounds suggest that the sp(2) nitrogen may coordinate with the selenium more strongly than the sp(3) nitrogen and the resonance contributions from the five-membered heterocyclic rings further increase the extent of Se...N interactions between selenium and tertiary nitrogen. A correlation between the Se...N intramolecular distance and the Se-77 chemical shift was attempted.
• Selenoether ligand assisted Heck catalysis
  作者：Tapash Chakraborty、Kriti Srivastava、Harkesh B. Singh、Ray J. Butcher

  DOI：10.1016/j.jorganchem.2011.03.047

  日期：2011.7

  Selenoether ligands, 2,2'-methylenebis(selanediyl)bis(2,1-phenylene)dimethanol (5), (2,2'-(ethane-1,2-diylbis(selanediyl))bis(2,1-phenylene))dimethanol (6) and (2-(benzylselanyl)phenyl)methanol (7) have been synthesized by reducing di-o-formylphenyl diselenide and reacting the in situ generated selenolate with dibromomethane, 1,2-dibromoethane and benzyl chloride, respectively. The ligands, bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenylselanyl)methane (8) and 1,2-bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenylselanyl)ethane (9) have been synthesized similarly from bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide using electrophiles dibromomethane and 1,2-dibromoethane, respectively. Activity of ligands 5-9 along with 2-(2-(benzylselanyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (10) and 1-(2-(benzylselanyl)phenyl)-N,N-dimethylmethanamine (11) were examined for the Heck reaction of aryl halides with olefins. Bidentate Se,N ligand 11 was found to be the best one in the series and constitutes an efficient phosphine-free catalytic system with PdCl2. The catalytic system showed moderate activity for the coupling of activated aryl chlorides in the presence of tetra-n-butyl ammonium bromide (TBAB). Complexes [10-PdCl2] (12) and [11-PdCl2] (13) have shown marginally better activity in comparison to the in situ generated catalysts from PdCl2 and 10 and 11, respectively in the coupling of 4-bromoacetophenone with n-butylacrylate. Ligand 9 and complex 13 have been characterized by single crystal X-ray diffraction analysis. (C) 2011 Elsevier B.V. All rights reserved.