tert-butyl(3-bromophenyl)hydroxylamine | 40686-36-0

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: tert-butyl(3-bromophenyl)hydroxylamine
• 英文别名: 1-[N-tert-butyl-N-(hydroxylamino)]-3-bromobenzene；N-(m-bromophenyl)-N-(tert-butyl)hydroxylamine；N-3-bromophenyl-N-tert-butylhydroxyamine；N-(3-bromophenyl)-N-tert-butylhydroxylamine
• CAS: 40686-36-0
• 化学式: C₁₀H₁₄BrNO
• 分子量: 244.131
• InChiKey: DJRQYSBFDFBING-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl(3-bromophenyl)hydroxylamine 在 咪唑 、 palladium diacetate 、 三丁基膦 、 四丁基氟化铵 、 sodium methylate 、 lead dioxide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 96.67h， 生成 3,5-di-tert-butyl-3'-(N-tert-butyl-N-aminoxy)-4-oxybiphenyl
  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：

  亚硝基叔丁烷 、 1,3-二溴苯 在 正丁基锂 作用下， 生成 tert-butyl(3-bromophenyl)hydroxylamine
  参考文献：
  名称：

  硅烷桥联双基分子中磁性交换的实验和理论研究。

  摘要：

  研究了通过甲硅烷（7 ad）或噻吩（12）环作为成色剂连接的五个双（叔丁基硝基氧）双自由基。化合物12在正交晶体空间群Pna2（1）中结晶，其a = 20.752（5），b = 5.826（5）和c = 34.309（5）A。X射线晶体结构测定，电子光谱，可变温度EPR光谱学，SQUID测量和DFT计算（UB3LYP / 6-31 + G *）用于研究该系列分子的分子构象和电子自旋耦合。化合物7b，7c和7d在溶液和固态下都非常稳定，而化合物7b和7d则部分地电子重排为反磁性喹诺酮形式和单自由基物质，这是因为它们对应于π共轭Kekule结构的开放形式。在固态下 磁测量表明，双基自由基都是反铁磁耦合的，正如其拓扑结构所预期的那样。这些交互作用最好通过“ Bleaney-Bowers”模型重现，该模型给出7 a的J = -142.0 cm（-1），7 b的-1.8 cm（-1），-1.3 cm（-1）的值7

  DOI：

  10.1002/chem.200501280

文献信息

• Biradical pincers involving two phenylene, biphenylene or terphenylene arms: Evidence for approach of two terminal nitroxides
  作者：Rika Uesugi、Rina Takano、Takayuki Ishida

  DOI：10.1016/j.tet.2024.133929

  日期：2024.4

  -CHCHO-(-CH)-(-CH)–N(O•)-Bu} ( and for = 2 and 3, respectively) were prepared, where -xylylenedioxy was chosen as a hinge and phenylene, biphenylene, and terphenylene were selected as an arm. The crystallographic analysis clarified the intramolecular proximity of the two radical groups was observed for , whereas and possess an open V-shape. In toluene solution ESR, five hyperfine splitting lines were

  四种新的钳型双硝基氧，-CHCHO-(-CH)-N(O•)-Bu}（分别缩写为 和 for = 2 和 3；for = 1（已知））和 -CHCHO制备了-(-CH)-(-CH)–N(O·)-Bu}（和分别为= 2和3），其中选择-苯二甲氧基作为铰链，选择亚苯基、联亚苯基和三联苯作为一只手臂。晶体学分析阐明了观察到的两个自由基基团的分子内接近性，而 和 具有开放的 V 形。在甲苯溶液 ESR 中，在室温或更高温度下为每种化合物记录了 5 条超细分裂线。根据 ESR 模拟，反铁磁交换相互作用估计为 2/ = -0.05 至 -0.0002 K。交换相互作用的顺序如下：>>关于臂长和>关于位置异构体。在本研究中发现出现交替线宽的温度是一个方便的温标。
• 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.
• Forced proximity of nitroxide groups in pincer compounds with a xanthene spacer
  作者：Naoki Koizumi、Takayuki Ishida

  DOI：10.1016/j.tetlet.2017.06.004

  日期：2017.7

  We designed bisnitroxide compounds where the radical sites are located close to each other in a molecule. Two new pincer-type bisnitroxide compounds have been synthesized, involving xanthene-4,5-diyl as a spacer and tert-butyl phenyl nitroxides as arms. From the X-ray crystal structure analysis, the shortest intramolecular interatomic N center dot center dot center dot N and O center dot center dot center dot O distances respectively are 5.074(6) and 5.258(6) (A) over circle for the m,m'-derivative and 3.624(3) and 3.771(3) (A) over circle for the p,p'-derivative. The N center dot center dot center dot O distance in the latter satisfies the empirical criterion for possible dimerizationidegradation reaction accompanied by dia-/paramagnetic transition. However, the magnetic study clarified paramagnetic behavior in all the temperature range. According to a singlet-triplet model, antiferromagnetic couplings were characterized with 2j/k(B) = 7.71(2) and -8.83(4) K for the m,m' and p,p'-derivatives, respectively. The present result suggests that a more flexible spacer is required for realization of possible dia-/paramagnetic transition. (C) 2017 Elsevier Ltd. All rights reserved.