N,N-dideuterio-benzylamine | 45579-94-0

• 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: N,N-dideuterio-benzylamine
• 英文别名: benzylamine-d₂；N,N-dideuterobenzylamine；benzylamine-d2；benzylamine；PhCH2ND2；BnND2；alpha-Amino-d2-toluene；N,N-dideuterio-1-phenylmethanamine
• CAS: 45579-94-0
• 化学式: C₇H₉N
• 分子量: 109.139
• InChiKey: WGQKYBSKWIADBV-ZSJDYOACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-dideuterio-benzylamine 在 Ru2Cl4(4'-azulenyl-2,2':6',2''-terpyridine)2 、 氧气 作用下， 以 甲醇 为溶剂， 60.0 ℃ 、2.53 MPa 条件下， 反应 5.0h， 生成 苯甲腈
  参考文献：
  名称：

  新型钌-叔吡啶基络合物，可将胺直接氧化为腈†

  摘要：

  使用Ru 2 Cl 4（az-tpy）2络合物，在良性条件下用双氧或空气将脂肪族和芳香族胺氧化为腈，已证明具有高催化活性和选择性。发现转化率受到反应物的烷基链长度的强烈影响，与具有较长链的胺相比，具有较短链胺的反应物具有较低的转化率。重要的是，通过使用在中央吡啶核的4位上的氮杂烯基部分官能化的钌三联吡啶配合物，与报道的一系列基于钌三联吡啶的配体配合物相比，提供了更高的反应活性催化剂。使用氘代苄胺的机理研究证明了RuOH在该反应中的重要性。

  DOI：

  10.1039/c3cy00209h
• 作为产物：
  描述：

  苯甲腈 在 lithium aluminium deuteride 作用下， 生成 N,N-dideuterio-benzylamine
  参考文献：
  名称：

  Model Studies of Topaquinone-Dependent Amine Oxidases. 2. Characterization of Reaction Intermediates and Mechanism

  摘要：

  The reaction of 2-hydroxy-5-tert-butyl-1,4-benzoquinone (1a) and benzylamine in acetonitrile was studied under anaerobic conditions. Addition of benzylamine to the quinone 1a solution generates the anionic form of the quinone (lambda(max) at 492 nm), followed by the formation of the product Schiff base 11 with lambda(max) at 368 nm and the aminoresorcinol 13 with lambda(max) at 304 nm. The rapid dissociation of the 2-hydroxyl proton was confirmed by the isolation of the amine salt 5a in the reaction of tert-butylamine and 1a. The substrate Schiff base 6a was not spectrally detected due to its lower extinction coefficient and rapid conversion to the product Schiff base 11. However, when alpha-methylbenzylamine was employed as a substrate, the formation of the substrate Schiff base 7 was detected by H-1 NMR and W-vis spectroscopy, Cyclohexylamine, n-propylamine, and ammonia also gave the substrate Schiff bases 8, 9, and 10, respectively, Both the steric bulk and the acidity of the C-1 proton of the substrate are found to be factors controlling the further reaction (C-1 proton abstraction). Detailed structural analysis of the substrate Schiff base was performed on 8 by 2D NMR spectroscopy, showing that 8 is in its amine salt form and has undergone nucleophilic addition at C-1, the carbonyl carbon next to the 2-hydroxyl group. W-vis spectroscopy supports the view that 8 is not a solvent-separated ion pair (lambda(max) at 454 nm) but an intimate ion pair (lambda(max) at 352 nm) in CH3CN. The latter lambda(max) value is very similar to lambda(max) observed for the Schiff base complex seen in bovine serum amine oxidase and different from a Schiff base complex with 4-methoxy-5-tert-butyl-1,2-benzoquinone 14. The product Schiff base 11 was prepared by the reaction of the hydrochloride salt of the aminoresorcinol 13 and benzaldehyde. It has an epsilon value 10 times larger than that of the substrate Schiff base (7, 8, or 9) at 368 nm. Treatment of 11 with benzylamine yielded the aminoresorcinol 13 and the product, N-benzylidenebenzylamine (PhCH=NCH(2)Ph). Comparison of these results to catalytic properties of the copper amine oxidases provides support for an aminotransferase mechanism from a Schiff base of topa in a localized p-quinone form (B in Scheme 1).

  DOI：

  10.1021/ja00139a003

文献信息

• Intermolecular N–H Oxidative Addition of Ammonia, Alkylamines, and Arylamines to a Planar σ³-Phosphorus Compound via an Entropy-Controlled Electrophilic Mechanism
  作者：Sean M. McCarthy、Yi-Chun Lin、Deepa Devarajan、Ji Woong Chang、Hemant P. Yennawar、Robert M. Rioux、Daniel H. Ess、Alexander T. Radosevich

  DOI：10.1021/ja412469e

  日期：2014.3.26

  Ammonia, alkyl amines, and aryl amines are found to undergo rapid intermolecular N-H oxidative addition to a planar mononuclear σ(3)-phosphorus compound (1). The pentacoordinate phosphorane products (1·[H][NHR]) are structurally robust, permitting full characterization by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. Isothermal titration calorimetry was employed to quantify the

  发现氨、烷基胺和芳胺会发生快速的分子间 NH 氧化加成到平面单核 σ(3)-磷化合物 (1)。五配位正膦产物 (1·[H][NHR]) 结构坚固，可以通过多核 NMR 光谱和单晶 X 射线衍射进行全面表征。采用等温滴定量热法来量化正丙胺与 1 ((n)PrNH2 + 1 → 1·[H][NH(n)Pr] 的 NH 氧化加成的焓，ΔHrxn(298) = -10.6 kcal/摩尔）。正丙胺 NH 氧化加成的动力学由原位紫外吸收光谱和速率法测定显示出异常大的分子度 (ν = k[1][(n)PrNH2](3))。在 10-70 °C 的温度范围内进行的动力学实验表明，反应速率随着温度的升高而降低。从 Eyring 分析中提取的活化参数 (ΔH(⧧) = -0.8 ± 0.4 kcal/mol, ΔS(⧧) = -72 ± 2 cal/(mol·K)) 表明强 NH 键被 1 裂解为熵由于高度
• Mechanistic Investigation of the Ruthenium-N-Heterocyclic-Carbene-Catalyzed Amidation of Amines with Alcohols
  作者：Ilya S. Makarov、Peter Fristrup、Robert Madsen

  DOI：10.1002/chem.201202400

  日期：2012.12.3

  The mechanism of the ruthenium–N‐heterocyclic‐carbene‐catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study with dispersion‐corrected density functional theory (DFT/M06). The Hammett study indicated that a small positive charge builds‐up at the benzylic position in the transition state

  通过实验技术（Hammett研究，动力学同位素效应）和利用色散校正的密度泛函理论（DFT / M06）进行的计算研究，研究了钌-N-杂环卡宾催化由醇和胺形成酰胺的机理。 。Hammett研究表明，在周转限制步骤的过渡态中，苄基位置会积累少量正电荷。动力学同位素效应确定为2.29（±0.15），表明C断裂H键不是限速步骤，但它是催化循环中几个缓慢的步骤之一。用氘标记的底物观察到氢和氘在醇的α位上的快速争夺，这表明催化活性物质是二氢化钌。通过使用DFT / M06表征可能的催化循环，为实验结果提供了支持。既顺-dihydride和反式-dihydride中间体被认为是，但是，当（的Tofs）直接从所计算的DFT / M06能量导出的理论周转频率，我们发现，只有反-dihydride途径是在与实验确定的Tofs协议。
• Synthesis and Reactivity of Polydisulfonimides
  作者：Benjamin T. Burlingham、Theodore S. Widlanski

  DOI：10.1021/ja002465v

  日期：2001.4.1

  oligomers, previously unreported reactivity of the N-substituted disulfonimide functional group was discovered. Under basic conditions, unexpected lengthening of the oligomers occurs through a "transdisulfonimidation" reaction, whereby new disulfonimides are synthesized from existing ones by reaction with sulfonamide anion. This process appears to proceed via formation of a sulfene intermediate. Support for

  首次合成烷基二磺酰亚胺低聚物。在合成这些低聚物的过程中，发现了以前未报道的 N-取代二磺酰亚胺官能团的反应性。在碱性条件下，低聚物通过“转二磺酰亚胺化”反应发生意外延长，由此通过与磺酰胺阴离子反应从现有二磺酰亚胺合成新的二磺酰亚胺。该过程似乎是通过形成亚砜中间体来进行的。对 E1cB(Rev) 机制的支持包括同位素加扰、取代基效应和亚砜捕获。
• Straightforward carbamoylation of nucleophilic compounds employing organic azides, phosphines, and aqueous trialkylammonium hydrogen carbonate
  作者：Andrey Yagodkin、Kerstin Löschcke、Janne Weisell、Alex Azhayev

  DOI：10.1016/j.tet.2010.01.017

  日期：2010.3

  the intermediate formation of the corresponding isocyanate, which, in turn, reacts further with a nucleophilic reagent also present in the mixture and results in carbamoylation with good yield. On the basis of this reaction a practical carbamoylation procedure was devised and a comparative study on suitability of different solvents and phosphorus (III) derivatives for carbamoylation reaction was conducted

  在碳酸氢三烷基铵水溶液的存在下，施陶丁格反应导致相应异氰酸酯的中间形成，该异氰酸酯又与混合物中也存在的亲核试剂进一步反应，并以高收率进行氨基甲酰化反应。在此反应的基础上，设计了一种实用的氨基甲酰化方法，并进行了对比研究，研究了不同溶剂和磷（III）衍生物对氨基甲酸酯化反应的适用性。该方法的多功能性通过不同类别的亲核化合物（包括氨基甲基树脂和在有机溶剂中显示不良溶解性的天然化合物）的实例得到证明。
• Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide
  作者：Keshab Kumar Adhikary、Hai-Whang Lee

  DOI：10.5012/bkcs.2011.32.3.857

  日期：2011.3.20

  :Benzylaminolysis, N-Methyl-α-bromoacetanilides, Cross-interaction constant, Deuterium kineticisotope effect, Biphasic nonlinear free energy correlationIntroductionIn a series of the nucleophilic substitution reactions ofα-halocarbonyl compounds,

  < 1) 对于 Y = 吸电子取代基。N-甲基-Y-α-溴乙酰苯胺的苄基氨基分解的机制是一种协同机制，具有五元环 TS，涉及 NH(D) 中的氢（氘）原子和 C = O 中的氧原子之间的氢键Y = 给电子，而与烯醇状 TS 的协同机制，其中亲核试剂攻击 α-碳以获得 Y = 吸电子取代基。关键词：苄氨解，N-甲基-α-溴乙酰苯胺，交叉相互作用常数，氘动力学同位素效应，双相非线性自由能相关介绍在α-卤代羰基化合物的一系列亲核取代反应中，