氰化铜(I)-13C | 93596-81-7

• 中文名称: 氰化铜(I)-13C
• 英文名称: copper(I) cyanide
• 英文别名: cuprous [(13)C]cyanide；(13)C-copper(I) cyanide；Azanylidyne(113C)methane;copper(1+)
• CAS: 93596-81-7
• 化学式: CN*Cu
• 分子量: 90.5527
• InChiKey: DOBRDRYODQBAMW-YTBWXGASSA-N

物化性质

• 熔点：
  454 °C (lit.)
• 密度：
  2.920 g/mL at 25 °C

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  3
• 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：
  2

安全信息

• 危险品标志：
  T+
• 安全说明：
  S22,S26,S36/37/39,S45
• 危险类别码：
  R26/27/28
• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  氰化铜(I)-13C 、 Fmoc-L-4-碘苯丙氨酸 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以11.6 mg的产率得到N-Fmoc-L-p-(13)C-cyanophenylalanine
  参考文献：
  名称：

  A Solvatochromic Model Calibrates Nitriles’ Vibrational Frequencies to Electrostatic Fields

  摘要：

  Electrostatic interactions provide a primary connection between a protein's three-dimensional structure and its function. Infrared probes are useful because vibrational frequencies of certain chemical groups, such as nitriles, are linearly sensitive to local electrostatic field and can serve as a molecular electric field meter. IR spectroscopy has been used to study electrostatic changes or fluctuations in proteins, but measured peak frequencies have not been previously mapped to total electric fields, because of the absence of a field-frequency calibration and the complication of local chemical effects such as H-bonds. We report a solvatochromic model that provides a means to assess the H-bonding status of aromatic nitrile vibrational probes and calibrates their vibrational frequencies to electrostatic field. The analysis involves correlations between the nitrile's IR frequency and its C-13 chemical shift, whose observation is facilitated by a robust method for introducing isotopes into aromatic nitriles. The method is tested on the model protein ribonuclease S (RNase 5) containing a labeled p-CN-Phe near the active site. Comparison of the measurements in RNase S against solvatochromic data gives an estimate of the average total electrostatic field at this location. The value determined agrees quantitatively with molecular dynamics simulations, suggesting broader potential for the use of lit probes in the study of protein electrostatics.

  DOI：

  10.1021/ja303895k
• 作为产物：
  描述：

  potassium [13C]cyanide 、 copper(ll) sulfate pentahydrate 在 硫酸 、 sodium hydrogensulfite 作用下， 以 水 为溶剂， 生成 氰化铜(I)-13C
  参考文献：
  名称：

  导电金属大环组件。高分辨率固态NMR光谱作为酞菁分子和大分子“金属”中局部结构和电子结构的探针。

  摘要：

  DOI：

  10.1021/ja00263a013

文献信息

• Cyclic Alkenenitriles: Copper-Catalyzed Deconjugative α-Alkylation
  作者：Xun Yang、Dinesh Nath、Jared Morse、Craig Ogle、Emine Yurtoglu、Ramazan Altundas、Fraser Fleming

  DOI：10.1021/acs.joc.6b00367

  日期：2016.5.20

  An amido cuprate formed from CuCN and LDA allows a general deconjugative α-alkylation of cyclic alkenenitriles. Deprotonating cyclic alkenenitriles with LDA-CuCN avoids polymerization that otherwise plagues these alkylations and generates a reactive metalated nitrile for alkylations with a range of carbon and heteroatom electrophiles. The strategy provides an effective synthesis of quaternary 5-, 6-

  由CuCN和LDA形成的酰胺基铜酸盐允许环状烯基腈的一般去共轭α-烷基化。用LDA-CuCN使质子化的环状烯腈避免聚合反应，否则该聚合反应会困扰这些烷基化反应，并生成反应性金属腈，用于与一系列碳原子和杂原子亲电试剂进行烷基化反应。该策略提供了在含腈碳原子上取代的5元，6元和7元环烷基-1-烯腈的有效合成方法。
• Elongated Gilman Cuprates: The Key to Different Reactivities of Cyano- and Iodocuprates
  作者：Maria Neumeier、Ruth M. Gschwind

  DOI：10.1021/ja501055c

  日期：2014.4.16

  cuprates. In addition, the effect of these copper-rich complexes on the yields of cross-coupling reactions with an alkyl halide was tested, resulting in reduced yields for iodocuprates. Thus, this study gives an explanation for the thus far confusing results of both similar and different reactivities of cyano- and iodocuprates. In the case of small substituents the produced alkyl copper precipitates and

  过去，关于氰基与碘铜酸盐的特殊反应性的长期且非常有争议的讨论集中在高阶铜酸盐结构的存在上。后来的大量结构研究证明了碘和氰基吉尔曼铜酸盐及其后续中间体的结构等效性。对于二甲基铜酸盐，也显示出类似的反应性。然而，关于氰铜酸盐具有更高反应性的报道在许多合成工作组中顽固地存在。在这项研究中，我们提出了氰基和碘铜酸盐之间的另一种结构差异，这与双方的结果一致。关键是在反应过程中烷基铜可能掺入碘中，但不会掺入氰基吉尔曼铜酸盐中。在具有高溶解性取代基（R = Me3SiCH2）的铜酸盐的例子中，我们表明在反应过程中碘铜酸盐的情况下形成了几种富含铜的配合物，它们消耗额外的碘铜酸盐并提供较低的反应性。为了证实这一点，合成了各种高溶解性的富铜配合物，并通过核磁共振光谱方法研究了它们的分子式、平衡位置、单体及其聚集趋势，揭示了扩展的碘吉尔曼铜酸盐。此外，还测试了这些富含铜的配合物对与卤代烷交叉偶联反应产率的影响，
• Effect of HMPA on the Composition of Organocyanocuprates. First Observation of a <i>²</i><i>J</i>^₁₃_C_-^₁₃_CN Coupling Constant in a Vinylcyanocuprate
  作者：Jorge A. Cabezas、Allan C. Oehlschlager

  DOI：10.1021/ja962697n

  日期：1997.4.1

  1-alkynyl ethers have been conducted. When prepared in the presence of HMPA, the reagents and addition products formed exist as mixtures in which some free lithium cyanide is present and the remaining cyanide is otherwise complexed. When stannylcyanocuprates were prepared in THF solutions no LiCN was detected. Heteronuclear NMR of the intermediates formed in the low-temperature reaction of a 13C-labeled

  已经对氰基铜酸甲锡酯的 THF 和 THF-HMPA 溶液及其与 1-炔基醚的加成产物进行了变温 1H-和 13C-NMR 光谱分析。当在 HMPA 存在下制备时，形成的试剂和加成产物以混合物形式存在，其中存在一些游离的氰化锂，而剩余的氰化物则以其他方式络合。当在 THF 溶液中制备氰基铜酸甲锡盐时，未检测到 LiCN。在 13C 标记的乙炔醚与氰基铜酸锡 (Bu3Sn)2Cu(13CN)Li2 的 THF-HMPA 溶液低温反应中形成的中间体的异核 NMR 显示 13CN-13C-乙烯基碳偶联与含有氰化物和乙烯基键合到一个公共中心。在中间体中观察到金属结合的 119Sn 和 13C-乙烯基碳之间的偶联，表明这两个原子结合到一个共同的中心。中间体中缺乏 119Sn-13CN 耦合表明 119Sn 和 13CN 我们...
• Synthesis of labeled ambroxol and its major metabolites
  作者：Bachir Latli、Matt Hrapchak、Heinz-Karl Switek、Daniel M. Retz、Dhileepkumar Krishnamurthy、Chris H. Senanayake

  DOI：10.1002/jlcr.1694

  日期：——

  Ambroxol is a mucolytic agent used in the treatment of respiratory diseases. Herein, we report the synthesis of carbon-14-labeled ambroxol with the radioactive atom(s) either on the benzylic carbon or uniformly in the cyclohexyl ring with specific activities of 59 and 81 mCi/mmol, respectively. We also describe the preparation of deuterium-labeled ambroxol, its deuterium-labeled tetrahydroquinazoline metabolite (DHTQ), carbon-13-labeled 3,5-dibromoanthranilic acid metabolite, as well as an unlabeled O-glucuronide conjugate. Copyright © 2009 John Wiley & Sons, Ltd.

  氨溴索是一种用于呼吸系统疾病治疗的溶解粘液剂。在此，我们报告了碳-14标记的氨溴索的合成，其中放射性原子位于苄基碳上或均匀分布在环己烷环中，特定活度分别为59和81 mCi/mmol。我们还描述了氘标记氨溴索的制备、其氘标记的四氢喹啉代谢物（DHTQ）、碳-13标记的3,5-二溴氨基苯甲酸代谢物，以及一种未标记的O-葡萄糖苷酸结合物。版权所有 © 2009 John Wiley & Sons, Ltd.
• Initiator Control of Conjugated Polymer Topology in Ring-Opening Alkyne Metathesis Polymerization
  作者：Stephen von Kugelgen、Donatela E. Bellone、Ryan R. Cloke、Wade S. Perkins、Felix R. Fischer

  DOI：10.1021/jacs.6b02422

  日期：2016.5.18

  Molybdenum carbyne complexes [RC≡Mo(OC(CH3)(CF3)2)3] featuring a mesityl (R = Mes) or an ethyl (R = Et) substituent initiate the living ring-opening alkyne metathesis polymerization of the strained cyclic alkyne, 5,6,11,12-tetradehydrobenzo[a,e][8]annulene, to yield fully conjugated poly(o-phenylene ethynylene). The difference in the steric demand of the polymer end-group (Mes vs Et) transferred during

  钼碳炔配合物 [RC≡Mo(OC(CH3)(CF3)2)3] 以甲基 (R = Mes) 或乙基 (R = Et) 取代基为特征，引发了应变环炔烃的活性开环炔烃复分解聚合, 5,6,11,12-四脱氢苯并[a,e][8]环烯，得到完全共轭的聚（邻亚苯基乙炔）。在引发步骤中转移的聚合物端基（Mes 与 Et）的空间需求差异决定了所得聚合物链的拓扑结构。虽然 [MesC≡Mo(OC( )( )2)3] 仅产生线性聚（邻亚苯基乙炔），但由 [EtC≡Mo(OC( )( )2)3] 引发的聚合导致环状大小从 n = 5 到 20 个单体单元的聚合物。