N-3-bromophenyl-N-tert-butyl-N-tert-butyldimethylsiloxyamine | 233584-39-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-3-bromophenyl-N-tert-butyl-N-tert-butyldimethylsiloxyamine
• 英文别名: 3-bromo-N-tert-butylamino-N-tert-butyldimethylsiloxybenzene；3-bromo-N-tert-butyldimethylsiloxy-N-tert-butylaminobenzene；tert-butyl(3-bromophenyl)(tert-butyldimethylsiloxy)amine；3-bromo-N-tert-butyl-N-[tert-butyl(dimethyl)silyl]oxyaniline
• CAS: 233584-39-9
• 化学式: C₁₆H₂₈BrNOSi
• 分子量: 358.394
• InChiKey: PVCKAHLKHZBMTQ-UHFFFAOYSA-N

物化性质

• 沸点：
  336.4±34.0 °C(Predicted)
• 密度：
  1.127±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.99
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  12.47
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N-3-bromophenyl-N-tert-butyl-N-tert-butyldimethylsiloxyamine 在 palladium diacetate 、 三丁基膦 、 四丁基氟化铵 、 sodium ethanolate 、 lead dioxide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 48.5h， 生成 3,5-di-tert-butyl-3'--4-methoxybiphenyl
  参考文献：
  名称：

  3,5-Di-tert-butyl-3‘-(N-tert-butyl-N-aminoxy)-4-oxybiphenyl:  A Heterospin Diradical with Temperature Dependent Behavior

  摘要：

  The title diradical was synthesized and investigated by ESR and UV-vis spectroscopy. It was found to have a lifetime of weeks even in the presence of oxygen, and even survives brief heating in toluene up to about 60 degrees C. In the W-vis spectrum, the diradical showed reversible thermochromic behavior in the -10 to 50 OC range. In the ESR spectrum, hyperfine analysis showed nearly isolated behavior by the phenoxyl and nitroxide spin carrying units. Upon warming,additional, broad lines appeared at the expense of the lower temperature lines. This temperature behavior was reversible over the 0 to 50 degrees C range, so long as the raised temperatures were not maintained for long time periods. The spectral behavior is interpreted as being due to temperature-dependent conformational effects on the exchange coupling between the spin carrying units, i.e., J-modulated exchange behavior.

  DOI：

  10.1021/jo990317l
• 作为产物：
  描述：

  1,3-二溴苯 在 咪唑 、 正丁基锂 作用下， 以 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.5h， 生成 N-3-bromophenyl-N-tert-butyl-N-tert-butyldimethylsiloxyamine
  参考文献：
  名称：

  3,5-Di-tert-butyl-3‘-(N-tert-butyl-N-aminoxy)-4-oxybiphenyl:  A Heterospin Diradical with Temperature Dependent Behavior

  摘要：

  The title diradical was synthesized and investigated by ESR and UV-vis spectroscopy. It was found to have a lifetime of weeks even in the presence of oxygen, and even survives brief heating in toluene up to about 60 degrees C. In the W-vis spectrum, the diradical showed reversible thermochromic behavior in the -10 to 50 OC range. In the ESR spectrum, hyperfine analysis showed nearly isolated behavior by the phenoxyl and nitroxide spin carrying units. Upon warming,additional, broad lines appeared at the expense of the lower temperature lines. This temperature behavior was reversible over the 0 to 50 degrees C range, so long as the raised temperatures were not maintained for long time periods. The spectral behavior is interpreted as being due to temperature-dependent conformational effects on the exchange coupling between the spin carrying units, i.e., J-modulated exchange behavior.

  DOI：

  10.1021/jo990317l

文献信息

• Photolysis and Oxidation of Azidophenyl-Substituted Radicals:  Delocalization in Heteroatom-Based Radicals
  作者：Paul R. Serwinski、Burak Esat、Paul M. Lahti、Yi Liao、Richard Walton、Jiang Lan

  DOI：10.1021/jo049500r

  日期：2004.8.1

  |D/hc| = 0.336 cm-1, |E/hc| = 0.004 cm-1 (11 from 25). UB3LYP/6-31G* computations and ESR spectroscopic analyses suggest that these are nitreno radicals, even para-linked systems with possible quinonoidal resonance forms. Neat samples of azidophenyl radicals 14 and 21 showed bulk paramagnetic behavior, consistent with the lack of close contacts in their crystal structures. Efforts to make photolabile

  2-（4-叠氮苯基）-4,4,5,5-四甲基-4,5-二氢-1 H-咪唑-3-氧化物-1-氧基（14），2-（4-叠氮苯基）苯并咪唑-1 -氧化物-3-氧基（16），2-（4-叠氮基苯基）-1,2,6-三苯基枯基（19），2-（3-叠氮基苯基）-4,4,5,5-四甲基-4,5二氢1H -咪唑-3-氧化物-1-氧基（21），和（3-叠氮基苯基） - ñ -叔丁基- ñ -aminoxyl（25）中的冷冻溶液中光解，得到小号= 3/2状态具有以下零场分裂参数的相应亚硝基苯基自由基的ESR谱：| D / hc | =0.277厘米- 1，| E / hc | ≤0.002厘米- 1（7从14）; | D / hc | = 0.256 cm - 1，| E / hc | | ≤0.002厘米- 1（8从16）; | D / hc | = 0.288 cm - 1，| E / hc | | ≤0.002厘米-
• Redox-switching of intramolecular magnetic interaction through π-conjugation mode change of 1,2-bis(4-dianisylamino)-1,2-bis(3-N-oxylamino)-substituted tetraarylethylene
  作者：Yoshiaki Nakano、Akihiro Ito、Kazuyoshi Tanaka

  DOI：10.1016/j.poly.2011.02.046

  日期：2011.11

  To develop the redox-switching system of intramolecular magnetic interaction, 1,2-bis[3-(N-tert-butyl-N-oxylamino)phenyl]-1,2-bis[4-N,N-bis(4-methoxyphenyl)amino)phenyl]ethylene, tetraarylethylene with two nitroxide radical groups at the meta-position, was synthesized, and characterized by the electrochemical method and ESR spectroscopy. Cyclic voltammetry showed the tetraarylethylene core has the lower oxidation potential than the substituted nitroxide radical moiety. ESR spectroscopy in frozen solution revealed that the neutral form shows the fine-structured spectrum characteristic of the spin triplet species, while the dicationic form shows the anisotropic hyperfine-structured spectrum characteristic of the randomly-oriented nitroxide radical, indicating the drastic change of intramolecular magnetic interaction. (C) 2011 Elsevier Ltd. All rights reserved.
• Cyclic M₂(RL)₂ Coordination Complexes of 5-(3-[<i>N</i>-<i>tert</i>-Butyl-<i>N</i>-aminoxyl]phenyl)pyrimidine with Paramagnetic Transition Metal Dications
  作者：Martha Baskett、Paul M. Lahti、Armando Paduan-Filho、Nei F. Oliveira

  DOI：10.1021/ic050435t

  日期：2005.9.1

  5-(3-(N-tert-Butyl-N-aminoxyl)phenyl)pyrimidine (RL = 3NITPhPyrim) forms isostructural Cyclic M-2(RL)(2) cyclic dimers with M-2(hfac)(2) (M = Mn, Co, Cu; hfac = hexafluoroacetylaceton ate). Mn-2(hfaC)(4)(RL)(2) exhibits strong antiferromagnetic Mn-RL exchange, with weak ferromagnetic exchange (0.7 cm(-1)) between Mn-RL units that is consistent with a spin polarization exchange mechanism. The magnetic moment Of Co-2(hfac)(4)(RL)(2) at higher temperatures is consistent with strongly antiferromagnetic exchange within the Co-NIT units and tends toward zero below 50 K at lower magnetic fields, Cu-2(hfac)(4)(RL)(2) shows more complex behavior, with no high-temperature plateau in XT(T) up to 300 K but a monotonic decrease down to about 100 K. The Cu(II)-nitroxide bonds decrease by 0.2-0.3 angstrom over the same temperature range, corresponding to a change of nitroxide coordination from axial to equatorial. This thermally reversible Jahn-Teller distortion leads to a thermally induced spin state conversion from a high-spin, paramagnetic state at higher temperature to a low-spin state at lower temperature, This spin state conversion is accompanied by a reversible solid-state thermochromic change between dull yellow-brown at room temperature and green at 77 K.