[13C]氰化氢 | 20722-83-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: [13C]氰化氢
• 英文名称: [¹³C]hydrogen cyanide
• 英文别名: <¹³C>-Cyanwasserstoff；azanylidyne(113C)methane
• CAS: 20722-83-2
• 化学式: CHN
• 分子量: 28.0146
• InChiKey: LELOWRISYMNNSU-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [13C]氰化氢 生成 丙烷-1-13C
  参考文献：
  名称：

  The Isomerization of Propane with C¹³in One End Position

  摘要：

  DOI：

  10.1063/1.1746860
• 作为产物：
  描述：

  POTASSIUM CYANIDE-13C 在 磷酸 作用下， 反应 3.0h， 生成 [13C]氰化氢
  参考文献：
  名称：

  Mechanisms of Catalyst Poisoning in Palladium-Catalyzed Cyanation of Haloarenes. Remarkably Facile C−N Bond Activation in the [(Ph₃P)₄Pd]/[Bu₄N]⁺ CN^- System

  摘要：

  Reaction paths leading to palladium catalyst deactivation during cyanation of haloarenes (eq 1) have been identified and studied. Each key step of the catalytic loop (Scheme 1) can be disrupted by excess cyanide, including ArX oxidative addition, X/CN exchange, and ArCN reductive elimination. The catalytic reaction is terminated via the facile formation of inactive [(CN)(4)Pd](2-), [(CN)(3)PdH](2-), and [(CN)(3)PdAr](2-). Moisture is particularly harmful to the catalysis because of facile CN- hydrolysis to HCN that is highly reactive toward Pd(0). Depending on conditions, the reaction of [(Ph3P)(4)Pd] with HCN in the presence of extra CN- can give rise to [(CN)(4)Pd](2-) and/or the remarkably stable new hydride [(CN)(3)PdH](2-) (NMR, X-ray). The X/CN exchange and reductive elimination steps are vulnerable to excess CN- because of facile phosphine displacement leading to stable [(CN)(3)PdAr](2-) that can undergo ArCN reductive elimination only in the absence of extra CN-. When a quaternary ammonium cation such as [Bu4N](+) is used as a phase-transfer agent for the cyanation reaction, C-N bond cleavage in the cation can occur via two different processes. In the presence of trace water, CN- hydrolysis yields HCN that reacts with Pd(0) to give [(CN)(3)PdH)(2-). This also releases highly active OH- that causes Hofmann elimination of [Bu4N](+) to give Bu3N, 1-butene, and water. This decomposition mode is therefore catalytic in H2O. Under anhydrous conditions, the formation of a new species, [(CN)(3)PdBu](2-), is observed, and experimental studies suggest that electron-rich mixed cyano phosphine Pd(0) species are responsible for this unusual reaction. A combination of experimental (kinetics, labeling) and computational studies demonstrate that in this case C-N activation occurs via an S(N)2-type displacement of amine and rule out alternative 3-center C-N oxidative addition or Hofmann elimination processes.

  DOI：

  10.1021/ja078298h

文献信息

• <i>Ex situ</i> generation of stoichiometric HCN and its application in the Pd-catalysed cyanation of aryl bromides: evidence for a transmetallation step between two oxidative addition Pd-complexes
  作者：Steffan K. Kristensen、Espen Z. Eikeland、Esben Taarning、Anders T. Lindhardt、Troels Skrydstrup

  DOI：10.1039/c7sc03912c

  日期：——

  methodology was also suitable for the synthesis of 13C-labelled benzonitriles with ex situ generated 13C-hydrogen cyanide. Stoichiometric studies with the metal complexes were undertaken to delineate the mechanism for this catalytic transformation. Treatment of Pd(P(tBu)3)2 with H13CN in THF provided two Pd-hydride complexes, (P(tBu)3)2Pd(H)(13CN), and [(P(tBu)3)Pd(H)]2Pd(13CN)4, both of which were isolated

  首次报道了使用接近化学计量和气态氰化氢的钯催化芳基溴化物氰化的方案。采用两室反应器在密闭环境中安全释放异位生成的HCN，事实证明该方法在Ni催化的氢氰化反应中非常有效。随后，利用该装置将一定范围的芳基和杂芳基溴化物（28个实例）直接高产率地转化为相应的苄腈，而无需使用氰化物盐。在二恶烷-水溶剂混合物中，使用Pd（0）预催化剂P（t Bu）3 -Pd-G3和弱碱乙酸钾实现氰化。该方法也适用于13的合成C-标记的苄腈与异位生成13 C-氰化氢。进行了金属配合物的化学计量研究，以描述这种催化转化的机理。在THF中用H 13 CN处理Pd（P（t Bu）3）2提供了两种Pd-氢化物配合物（P（t Bu）3）2 Pd（H）（13 CN）和[（P（t Bu） ）3）Pd（H）] 2 Pd（13 CN）4，两者均已分离，并通过NMR光谱和X射线晶体结构分析进行了表征。当在KOAc存在下在THF∶水混合物中进行相同的反应时，仅形成（P（t
• Thiophosphate – A Versatile Prebiotic Reagent?
  作者：Dougal Ritson、John Sutherland、Jiangfeng Xu

  DOI：10.1055/s-0036-1589414

  日期：——

  Described are our preliminary studies on the reactivity of thiophosphate in a setting which correlates with the cyanosulfidic systems chemistry we have previously reported. Thiophosphate adds to various nitrile groups giving the corresponding thioamides in a highly efficient manner and the mechanistic implications are briefly discussed. Thiophosphate can also act as a phosphorylating agent, which was

  描述的是我们对硫代磷酸盐在与我们之前报道的氰硫系统化学相关的环境中的反应性的初步研究。硫代磷酸盐以高效的方式添加到各种腈基中，产生相应的硫代酰胺，并简要讨论了其机理含义。硫代磷酸盐也可以作为磷酸化剂，腺苷证明了这一点。硫代磷酸盐的益生元可用性必须受到质疑，但如果能够找到合理的合成方法，那么它为益生元化学领域带来的优势似乎是非常有益的。
• Selective Formation of Triplet Alkyl Nitrenes from Photolysis of β-Azido-Propiophenone and Their Reactivity
  作者：Pradeep N. D. Singh、Sarah M. Mandel、Jagadis Sankaranarayanan、Sivaramakrishnan Muthukrishnan、Mingxin Chang、Rachel M. Robinson、Paul M. Lahti、Bruce S. Ault、Anna D. Gudmundsdóttir

  DOI：10.1021/ja077523s

  日期：2007.12.1

  formation of triplet alkyl nitrenes 2 that were detected directly with laser flash photolysis (lambdamax = 325 nm, tau = 27 ms) and ESR spectroscopy (|D/hc| = 1.64 cm-1, |E/hc| = 0.004 cm-1). Nitrenes 2 were further characterized with argon matrix isolation, isotope labeling, and molecular modeling. The triplet alkyl nitrenes are persistent intermediates that do not abstract H-atoms from the solvent but

  具有内置敏化剂单元的 β-叠氮基苯丙酮衍生物 1 的光解导致选择性形成三线态烷基氮烯 2，可通过激光闪光光解（λmax = 325 nm，tau = 27 ms）和 ESR 光谱法 (| D/hc| = 1.64 cm-1，|E/hc| = 0.004 cm-1)。氮烯 2 进一步表征为氩气基质分离、同位素标记和分子建模。三线态烷基氮烯是持久性中间体，不会从溶剂中提取 H 原子，而是通过与另一个三线态氮烯二聚形成偶氮产物而不是与叠氮化物前体反应而发生衰变。偶氮二聚体互变异构并重排形成杂环化合物 3。 具有 n,pi* 构型的氮烯 2a 作为其酮敏化剂部分的最低三重激发态，经历分子内 1，4-H 原子抽象形成双基 6，通过氩气基质分离、同位素标记和分子建模鉴定。β-叠氮基-对甲氧基苯丙酮，其三线态敏化剂部分的 pi,pi* 最低激发态不经历任何二次光反应，但选择性地仅产生三线态烷基氮烯中间体，二聚形成
• Cyanide and chloride exchange on homoleptic gold(III) square-planar complexes: variable pressure kinetic investigation by heteronuclear NMR
  作者：Florence J. Monlien、Lothar Helm、Amira Abou-Hamdan、André E. Merbach

  DOI：10.1016/s0020-1693(01)00818-0

  日期：2002.3

  operation of an Ia or A mechanism for this exchange pathway. The proton exchange on HCN was determined by 13C NMR as a function of pH and the rate constant of the three reaction pathways involving H2O, OH− and CN− were determined: k0HCN,H=113±17 s−1, k1HCN,H=(2.9±0.7)×109 s−1 mol−1 kg and k2HCN,H=(0.6±0.2)×106 s−1 mol−1 kg at 298.1 K. The rate law of the cyanide exchange on [Au(CN)4]− was found to be second

  X的动力学研究-交换上[AUX 4 ] -正方形平面复合物（其中X = Cl -和CN -在酸性pH下在氯系的情况下和作为pH为氰化物一个的函数被执行）。氯化物NMR研究（330–365 K）给出了[AuCl 4 ] -的二级速率定律，其动力学参数为：（k 2 Au，Cl）298 = 0.56±0.03 s -1  mol -1  kg; Δ ħ 2 ‡金，氯= 65.1±1千焦耳摩尔-1 ; Δ小号2 ‡金，氯= -31.3±3Ĵ摩尔-1 K -1和ΔV 2 ‡  Au，Cl = -14±2 cm 3  mol -1。可变压力数据清楚地表明了该交换路径的I a或A机制的操作。对HCN质子交换通过测定13 C NMR作为pH的函数和包含h三个反应途径的速率常数2 O，OH -和CN -测定：ķ 0 HCN，H = 113±17号-1，k 1 HCN，H =（2.9±0.7）×10 9 s -1
• Rotational spectroscopy of 3d transition-metal cyanides: Millimeter-wave studies of ZnCN (X 2Σ+)
  作者：M. A. Brewster、L. M. Ziurys

  DOI：10.1063/1.1498466

  日期：2002.9.8

  The pure rotational spectrum of the ZnCN radical in its X 2Σ+ ground electronic state has been recorded using millimeter/sub-mm direct absorption techniques in the range 339–543 GHz. This work is the first spectroscopic observation of this molecule, which was created by the reaction of zinc vapor and cyanogen gas in a dc discharge. Twenty-one rotational transitions were recorded for the main zinc isotopomer

  使用毫米/亚毫米直接吸收技术在 339-543 GHz 范围内记录了处于 X 2Σ+ 基态电子态的 ZnCN 自由基的纯旋转光谱。这项工作是对这种分子的首次光谱观察，它是由锌蒸气和氰气在直流放电中的反应产生的。记录了主要锌同位素 64ZnCN 在其基态振动状态下的 21 次旋转跃迁，以及 66Zn、68Zn 和 13C 同位素体的 8-16 次跃迁。还获得了 ZnCN 在其弯曲模式的几个量子和 (100) 伸缩振动中的数据。这些测量表明锌和氰化物部分的最稳定形式是线性氰化物结构，铜和镍也发现了这种结构。相比之下，对于镓和铝，线性异氰化物几何结构的能量最低。已经对 (000) 和激发的振动数据进行了光谱分析，确定了旋转、自旋和 l-...