benzyl 2-((dimethylamino)methyl)phenyl selenide | 228411-98-1

• 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: benzyl 2-((dimethylamino)methyl)phenyl selenide
• 英文别名: <2-(N,N-Dimethylaminomethyl)phenyl>benzylselenide；1-(2-(benzylselanyl)phenyl)-N,N-dimethylmethanamine；N,N dimethylaminobenzylselenide；1-(2-benzylselanylphenyl)-N,N-dimethylmethanamine
• CAS: 228411-98-1
• 化学式: C₁₆H₁₉NSe
• 分子量: 304.294
• InChiKey: HLVRADGUSYBGFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  benzyl 2-((dimethylamino)methyl)phenyl selenide 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以81%的产率得到rac-benzyl 2-((dimethylamino)methyl)phenyl selenoxide
  参考文献：
  名称：

  通过分子内配位稳定的硒氧化物的光学分辨率和构型稳定性。

  摘要：

  通过氨基与硒原子分子内配位而构型稳定的2-（（二甲基氨基）甲基）苯基烷基（或芳基）亚硒酸酯通过使用旋光色谱柱的高效液相色谱法光学拆分为对映异构体装满氨基甲酸直链淀粉的衍生物/硅胶。这是分离没有大取代基的光学纯亚硒酸盐的第一个实例，也是光学纯烷基芳基亚硒酸盐的首次分离。（-）-异构体的绝对构型可通过比较它们的比旋光度，圆二色性光谱和在光学活性柱上的行为与由安德森方法制备的硫类似物的行为进行比较，以S形表示。光学活性亚硒酸盐的外消旋不仅在酸性溶液中而且在碱性介质中都被加速。该结果表明它们在酸性和碱性介质中外消旋化有两种不同的机理。通过氨基与硒原子的分子内配位，亚硒酸盐的稳定能估计为约1。3 kcal mol（-）（1），基于可变温度（1）H NMR测量。

  DOI：

  10.1021/jo990993n
• 作为产物：
  描述：

  2-溴溴苄 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 19.17h， 生成 benzyl 2-((dimethylamino)methyl)phenyl selenide
  参考文献：
  名称：

  通过分子内配位稳定的硒氧化物的光学分辨率和构型稳定性。

  摘要：

  通过氨基与硒原子分子内配位而构型稳定的2-（（二甲基氨基）甲基）苯基烷基（或芳基）亚硒酸酯通过使用旋光色谱柱的高效液相色谱法光学拆分为对映异构体装满氨基甲酸直链淀粉的衍生物/硅胶。这是分离没有大取代基的光学纯亚硒酸盐的第一个实例，也是光学纯烷基芳基亚硒酸盐的首次分离。（-）-异构体的绝对构型可通过比较它们的比旋光度，圆二色性光谱和在光学活性柱上的行为与由安德森方法制备的硫类似物的行为进行比较，以S形表示。光学活性亚硒酸盐的外消旋不仅在酸性溶液中而且在碱性介质中都被加速。该结果表明它们在酸性和碱性介质中外消旋化有两种不同的机理。通过氨基与硒原子的分子内配位，亚硒酸盐的稳定能估计为约1。3 kcal mol（-）（1），基于可变温度（1）H NMR测量。

  DOI：

  10.1021/jo990993n
• 作为试剂：
  描述：

  丙烯酸丁酯 、 对氯苯乙酮 在 四丁基溴化铵 、 sodium acetate 、 palladium dichloride 、 benzyl 2-((dimethylamino)methyl)phenyl selenide 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 12.0h， 以45%的产率得到butyl 3-(4-acetylphenyl)acrylate
  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

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.