N-tert-butyl-N-(2-pyridyl)hydroxylamine | 942265-96-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-tert-butyl-N-(2-pyridyl)hydroxylamine
• 英文别名: N-t-butyl-N-2-pyridylhydroxylamine；N-tert-butyl-N-pyridin-2-ylhydroxylamine
• CAS: 942265-96-5
• 化学式: C₉H₁₄N₂O
• 分子量: 166.223
• InChiKey: RGEHAHINTINULH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  36.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-tert-butyl-N-(2-pyridyl)hydroxylamine 在 air 作用下， 生成 tert-butyl-2-pyridyl nitroxide
  参考文献：
  名称：

  Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines

  摘要：

  N-tert-Butyl-N-2-pyridylhydroxylamines were synthesized from 2-halopyridines and 2-methyl-2-nitrosopropane using magnesium halogen exchange. The use of Turbo Grignard generated the metallo-2-pyridyl intermediate more reliably than alkyllithium reagents. The hydroxylamines were characterized using NMR, electrochemistry, and density functional theory. Substitution of the pyridyl ring in the 3-, 4-, and 5-positions was used to vary the potential of the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations of the electrochemical properties agree with experiment and provide a toolset for the predictive design of pyridyl nitroxides.

  DOI：

  10.1021/jo400944r
• 作为产物：
  描述：

  2-溴吡啶 、 2-methyl-2-nitrosopropane dimer 在 isopropyl magnesium chloride - lithium chloride complex 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以80%的产率得到N-tert-butyl-N-(2-pyridyl)hydroxylamine
  参考文献：
  名称：

  Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines

  摘要：

  N-tert-Butyl-N-2-pyridylhydroxylamines were synthesized from 2-halopyridines and 2-methyl-2-nitrosopropane using magnesium halogen exchange. The use of Turbo Grignard generated the metallo-2-pyridyl intermediate more reliably than alkyllithium reagents. The hydroxylamines were characterized using NMR, electrochemistry, and density functional theory. Substitution of the pyridyl ring in the 3-, 4-, and 5-positions was used to vary the potential of the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations of the electrochemical properties agree with experiment and provide a toolset for the predictive design of pyridyl nitroxides.

  DOI：

  10.1021/jo400944r

文献信息

• Homoleptic Cerium(III) and Cerium(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State
  作者：Justin A. Bogart、Andrew J. Lewis、Scott A. Medling、Nicholas A. Piro、Patrick J. Carroll、Corwin H. Booth、Eric J. Schelter

  DOI：10.1021/ic401974t

  日期：2013.10.7

  [2-(tBuNO)py]− = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [nBu4N]2[Ce(NO3)6] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework

  电化学实验在复杂的Ce进行IV [2-（吨BUNO）吡啶] 4，其中[2-（吨BUNO）吡啶] - = ñ -叔丁基- ñ -2- pyridylnitroxide，表示的一个2.51 V稳定与[ n Bu 4 N] 2 [Ce（NO 3）6与乙腈在水溶液中的离子电势相比，具有2.95 V的稳定度（与离子的标准电势相比）。密度泛函理论计算表明，这种对较高氧化态的偏爱是由于Ce阳离子上的四（硝基氧）配体骨架的结果，该骨架允许将有效的电子捐赠给具有δ对称性的空的4f轨道，并与之部分共价重叠。结果证明了CeO 2和相关固溶体在氧气吸收和运输应用中的行为，特别是稳定4+氧化态的键的固有局部特征。结果表明，铈（IV）配合物已通过调整其配体场环境而被稳定到了前所未有的程度。
• Complexation and redox chemistry of neptunium, plutonium and americium with a hydroxylaminato ligand
  作者：Jing Su、Thibault Cheisson、Alex McSkimming、Conrad A. P. Goodwin、Ida M. DiMucci、Thomas Albrecht-Schönzart、Brian L. Scott、Enrique R. Batista、Andrew J. Gaunt、Stosh A. Kozimor、Ping Yang、Eric J. Schelter

  DOI：10.1039/d1sc03905a

  日期：——

  monitoring and remediation efforts. Here, we report syntheses and characterization of Np(IV), Pu(IV) and Am(III) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(tBuNO)py]−(interchangeable hereafter with [(tBuNO)py]−), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(tBuNO)py]4 (An = Pu, 1; Np, 2) have been synthesized, characterized

  人们对可以稳定氧化态的锕系元素离子的配体非常感兴趣，这些配体可用于化学区分 5f 和 4f 元素。应用范围从开发用于核工业加工的大规模锕系元素分离策略到进行支持环境监测和修复工作的分析研究。这里，我们报告合成和Np个表征（IV），普（IV）和AM（III）配合物的N-叔丁基- ñ - （吡啶-2-基）hydroxylAMinato，[2-（吨BUNO）吡啶] -（以后可与 [( t BuNO)py互换] -)，一种先前被发现赋予+4氧化态铈显着稳定性的配体。An[( t BuNO)py] 4 (An = Pu, 1 ; Np, 2 ) 已合成，通过 X 射线衍射、X 射线吸收、1 H NMR 和 UV-vis-NIR 光谱以及循环伏安法表征，以及计算建模和分析。在Pu的情况下，在与[( t BuNO)py] -配体络合后观察到Pu( III )氧化成Pu( IV ) 。Pu复合物1和Np复合物2也直接从Pu(
• Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure
  作者：Alex McSkimming、Jing Su、Thibault Cheisson、Michael R. Gau、Patrick J. Carroll、Enrique R. Batista、Ping Yang、Eric J. Schelter

  DOI：10.1021/acs.inorgchem.7b03238

  日期：2018.4.16

  remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine

  f块元素的分离是核废料处理的关键方面。基于氧化还原的分离提供了希望，但是在高氧化态下稳定和区分act系元素方面仍然存在挑战。对可为高价act系元素提供热力学稳定性的新型配体类型的研究，对于扩展其基本化学性质以及拟订新的分离技术和存储方法至关重要。我们在此报告吡啶基-羟胺配体的Th和U络合物的制备和表征，Ñ -叔丁基- ñ - （吡啶-2-基）羟胺（pyNO - ）。均化复合物[M（pyNO）4的电化学研究]（M ＝ Th，U）显示出在单电子氧化时U配合物的显着稳定。盐[U（pyNO）4 ] +用的化学氧化分离[U（pyNO）4 ]; 光谱和计算数据支持将其指定为U V阳离子。
• A Ligand Field Series for the 4f-Block from Experimental and DFT Computed Ce(IV/III) Electrochemical Potentials
  作者：Justin A. Bogart、Andrew J. Lewis、Michael A. Boreen、Heui Beom Lee、Scott A. Medling、Patrick J. Carroll、Corwin H. Booth、Eric J. Schelter

  DOI：10.1021/ic503000z

  日期：2015.3.16

  Understanding of the sensitivity of the reduction potential of cerium(IV) cations to ligand field strength has yet to benefit from systematic variation of the ligand environment. Detailed analyses for a series of seven cerium(IV) tetrakis(pyridyl-nitroxide) compounds and their cerium(III) analogues in varying ligand field strengths are presented. Electrochemical, spectroscopic, and computational results

  铈（IV）阳离子的还原电势对配体场强的敏感性的了解尚未受益于配体环境的系统变化。详细分析了一系列七种铈（IV）四（吡啶基-硝基氧）化合物及其铈（III）类似物在不同配体场强下的分布。电化学，光谱和计算结果表明，电子性质与配体取代基密切相关。结合已报道的八配位化合物的电化学数据，DFT计算揭示了与配体场强相关的大量铈（IV / III）氧化还原电势，建立了用于调节铈氧化还原热力学和配体场强的半经验预测模型。各种科学领域的应用都利用了铈的基本氧化还原热力学。这样的应用将从评估铈化合物的氧化还原循环的实验和理论相结合的方法中受益。
• Ferro- and Antiferromagnetic Coupling Switch Accompanied by Twist Deformation around the Copper(II) and Nitroxide Coordination Bond
  作者：Atsushi Okazawa、Daisuke Hashizume、Takayuki Ishida

  DOI：10.1021/ja102163d

  日期：2010.8.25

  Two novel copper(II) complexes with tert-butyl 2-pyridyl nitroxide (2pyNO(*)), [Cu(2+)(2pyNO(-))(2pyNO(*))](2)(BF(4)(-))(2) (1 x BF(4)) and [Cu(2+)(2pyNO(-))(2pyNO(*))](2)(ClO(4)(-))(2) (1 x ClO(4)), were prepared and structurally characterized. They contained mixed-valent ligands from 2pyNO, whose oxygen atoms were located at equatorial positions of the copper ion. The [Cu(2+)(2pyNO(-))(2pyNO(*))]

  两种新型铜 (II) 与叔丁基 2-吡啶基氮氧化物 (2pyNO(*))、[Cu(2+)(2pyNO(-))(2pyNO(*))](2)(BF(4)( -))(2) (1 x BF(4)) 和 [Cu(2+)(2pyNO(-))(2pyNO(*))](2)(ClO(4)(-))(2) ( 1 x ClO(4))，进行了制备和结构表征。它们包含来自 2pyNO 的混合价配体，其氧原子位于铜离子的赤道位置。[Cu(2+)(2pyNO(-))(2pyNO(*))] 单元通过阴离子配体的 mu-oxo 桥进行二聚化，给出了一个涉及四个顺磁性 S = 1/2 中心的锯齿形线性自旋系统。这两种化合物在正交 Pbca 空间群中是同晶的。磁性研究表明 1 x ClO(4) 显示在这里调查的所有温度范围内的铁磁铜自由基耦合。另一方面，1 x BF(4) 在 64 K 表现出结构相变，其中磁化率在冷却时急剧下