<2-(4,4-Dimethyl-2-oxazolinyl)phenyl>benzyl selenide | 228411-94-7

• 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: <2-(4,4-Dimethyl-2-oxazolinyl)phenyl>benzyl selenide
• 英文别名: 2-(2-(benzylselanyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole；2-(4,4-dimethyl-2-oxazolinyl)phenyl benzylselenide；Oxazole, 4,5-dihydro-4,4-dimethyl-2-[2-[(phenylmethyl)seleno]phenyl]-；2-(2-benzylselanylphenyl)-4,4-dimethyl-5H-1,3-oxazole
• CAS: 228411-94-7
• 化学式: C₁₈H₁₉NOSe
• 分子量: 344.315
• InChiKey: XSRWDEUSVFTRBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  双(乙腈)氯化钯(II) 、 <2-(4,4-Dimethyl-2-oxazolinyl)phenyl>benzyl selenide 以 二氯甲烷 为溶剂， 以96%的产率得到(2-(4,4-dimethyl-2-oxazolinyl)phenyl benzylselenide)dichloridopalladium(II)
  参考文献：
  名称：

  Selenoether ligand assisted Heck catalysis

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2011.03.047
• 作为产物：
  描述：

  4,4-二甲基-2-苯基-2-噁唑啉 、 氯化苄 在 selenium 、 正丁基锂 作用下， 生成 <2-(4,4-Dimethyl-2-oxazolinyl)phenyl>benzyl selenide
  参考文献：
  名称：

  Intramolecular Se⋅⋅⋅N Nonbonding Interactions in Low-Valent Organoselenium Derivatives: A Detailed Study by1H and77Se NMR Spectroscopy and X-Ray Crystallography

  摘要：

  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.

  DOI：

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

文献信息

• 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.