[2-¹³C]-cyanoacetic acid | 119770-97-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: [2-¹³C]-cyanoacetic acid
• 英文别名: 2-cyanoacetic acid
• CAS: 119770-97-7
• 化学式: C₃H₃NO₂
• 分子量: 86.0513
• InChiKey: MLIREBYILWEBDM-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [2-¹³C]-cyanoacetic acid 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Regiochemistry of the Condensation of 2-Aroyl-cyclohexanones and 2-Cyanoacetamide: ¹³C-Labeling Studies and Semiempirical MO Calculations

  摘要：

  Hydroxy-aryl-5,6,7,8-tetrahydroisoquinoline-4-carbonitriles represent interesting chemical scaffolds, but synthetic access to these compounds is limited. The reaction of 2-aroyl-cyclohexanones with 2-cyanoacetamide and base in ethanol has been reported to lead to the formation of the tetrahydroisoquinoline isomer. We show that depending on the electronic nature of the para-substituent on the aryl ring, formation of the regioisomeric tetrahydroquinoline isomer can significantly compete. The electron-donating or -withdrawing properties of the para-substituent of the aryl ring determines the ratio of product isomers. A series of 2-aroyl-cyclohexanones, with para-substituents ranging from electron-donating to electron-withdrawing, were reacted with [2-C-13]-cyanoacetamide. The product ratio and absolute regiochemistry were directly determined by quantitative C-13, HMBC, and NOESY NMR spectroscopy on the reaction mixtures. A clear relationship between the regioisomeric product ratio and the Hammett sigma values of the substituents is demonstrated. This is explained by the separate in situ yields, which reveal that the pathway leading to the tetrahydroquinoline regioisomer is significantly more sensitive toward the electronic nature of the para-substituent than the pathway leading to the tetrahydroisoquinoline. Semiempirical AM1 molecular orbital calculations on the starting electrophile 2-aroyl-cyclohexanone support a correlation between the energy of the LUMOs and the regioisomeric product ratio. Our results facilitate synthetic access to a range of these interesting synthetic intermediates.

  DOI：

  10.1021/jo301138w
• 作为产物：
  描述：

  溴乙酸-2-13C 、 alkaline earth salt of/the/ methylsulfuric acid 以80%的产率得到[2-¹³C]-cyanoacetic acid
  参考文献：
  名称：

  Biosynthesis of boromycin

  摘要：

  DOI：

  10.1021/jo00326a010

文献信息

• Biosynthesis of porphyrins and related macrocycles. Part 16. Proof that the single intramolecular rearrangement leading to natural porphyrins (type-III) occurs at the tetrapyrrole level
  作者：Alan R. Battersby、Christopher J. R. Fookes、Mary J. Meegan、Edward McDonald、Hanns K. W. Wurziger

  DOI：10.1039/p19810002786

  日期：——

  established earlier is thus proved to take place at the tetrapyrole level. Synthesis of singly 13C-labelled bilane (2) followed by its enzymic conversion into uro'gen-III serves to register each of the pyrrole rings of the product relative to the initial bilane. Finally, methods for synthesis of the bilane are developed in two different doubly 13C-labelled forms to allow the following key points to be established

  未重排的氨基甲基胆烷（2）是通过合理的途径合成的，并被脱氨酶和辅酶合成，并协同作用转化为uro'gen-III（3）。因此证明了较早建立的单个重排步骤发生在四吡咯水平。单独合成13 C标记的胆烷（2），然后将其酶促转化为uro'gen-III，相对于初始胆烷来说，该产物的每个吡咯环均具有配准作用。最后，以两种不同的双13 C标记形式开发了合成胆烷的方法，从而可以通过13 C nmr光谱学在很大程度上确定以下关键点：（a）随着胆烷体系被转化为尿根-III，发生了末端环D的分子内重排，并且（b）线性四吡咯被完整地转化为尿根-III。
• Deuterium and carbon-13 kinetic isotope effects for the isomerization of 5,5-dimethylbicyclo[2.1.0]pent-2-ene to 5,5-dimethylcyclopentadiene
  作者：John E. Baldwin、Naresh D. Ghatlia

  DOI：10.1021/ja00191a032

  日期：1989.4

  and the 2-sup 2}H, 1,2,4-sup 2}Hsub 3}, 1,2,3,4-sup 2}Hsub 4}, and 1,4-sup 13}Csub 2} isotopic variants of this system have been determined at 43.6-44.0degree}C. There is no detectable carbon-13 effect; deuterium substitution at C(2) is associated with a small ksub H}/ksub D} effect, 1.02, and a deuterium at C(1) results in a very large effect, 1.26. The ksub H}/ksub D}(dsub 3}) effect

  5,5-二甲基双环(2.1.0)戊-2-烯和2-sup 2}H, 1,2,4-sup 2}Hsub 3}, 1,该系统的 2,3,4-sup 2}Hsub 4} 和 1,4-sup 13}Csub 2} 同位素变体已在 43.6-44.0degree}C 下确定。没有可检测到的碳 13 效应；C(2) 处的氘取代与小的 ksub H}/ksub D} 效应 1.02 相关，而 C(1) 处的氘导致非常大的效应 1.26。ksub H}/ksub D}(dsub 3}) 效应在 24.6 到 54.7°C}C 之间显示出对温度的一些敏感性，范围从 1.83 到 1.64。该数据排除了对异构化的重要磁同位素效应，并且不支持沿反应坐标交叉的单线态产率}三线态系统间交叉。
• Efficient Preparation of [2-13C]- and [3-13C]-3-Cyano-4-methyl-3-pyrrolin-2-one
  作者：Prativa Bade Shrestha-Dawadi、Johan Lugtenburg

  DOI：10.1002/ejoc.200600830

  日期：2007.3

  [2-13C]- and [3-13C]-3-cyano-4-methyl-3-pyrrolin-2-one have been prepared by a new synthetic route. α,α-Dimethoxy ketones react with bifunctional molecules in an extended Knoevenagel reaction. The products of this reaction are converted in a few steps and in high yields into the biologically important 3-pyrrolin-2-ones. This new approach also allows simple stable isotope incorporation at many sites

  [2-13C]-和[3-13C]-3-cyano-4-methyl-3-pyrrolin-2-one是通过新的合成路线制备的。α,α-二甲氧基酮在扩展的 Knoevenagel 反应中与双功能分子反应。该反应的产物通过几个步骤以高产率转化为具有生物学意义的 3-pyrrolin-2-ones。这种新方法还允许在环系统的许多位点进行简单的稳定同位素掺入。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Chemo-enzymatic synthesis of 13C- and 19F-labeled uridine-5′-triphosphate for RNA NMR probing
  作者：Kehinde M. Taiwo、Owen B. Becette、Guanghui Zong、Bin Chen、Peter Y. Zavalij、Theodore Kwaku Dayie

  DOI：10.1007/s00706-021-02757-z

  日期：2021.4

  Solution NMR of the magnetically active fluorine-19 (19F) isotope offers tremendous advantages in the study of RNA structure and conformational changes. However, exploiting these advantages requires the synthesis of fluorinated RNA-building blocks, and this comes with certain challenges in overall yield of nucleotides, purity, and cost. Here, we detail a scalable and reliable method to produce [1′

  具有磁性的氟19（19 F）同位素的溶液NMR在研究RNA结构和构象变化方面具有巨大优势。但是，要利用这些优势，就需要合成氟化的RNA构件，这给核苷酸的总产量，纯度和成本带来了一定的挑战。在这里，我们详细地可扩展和可靠的方法来产生[1'，5- 13 Ç 2，5- 19女，6- 2 H] -和[1'，5- 13 Ç 2，5- 19女，6- 2 H，1,3- 15 N 2] -5-氟尿嘧啶-5'-三磷酸酯。我们进一步介绍了将标记的核苷酸掺入具有相关生物学活性的RNA之前表征其特征的步骤。 图形摘要
• Regiochemistry of the Condensation of 2-Aroyl-cyclohexanones and 2-Cyanoacetamide: ¹³C-Labeling Studies and Semiempirical MO Calculations
  作者：Oscar P. J. van Linden、Maikel Wijtmans、Luc Roumen、Lonneke Rotteveel、Rob Leurs、Iwan. J. P. de Esch

  DOI：10.1021/jo301138w

  日期：2012.9.7

  Hydroxy-aryl-5,6,7,8-tetrahydroisoquinoline-4-carbonitriles represent interesting chemical scaffolds, but synthetic access to these compounds is limited. The reaction of 2-aroyl-cyclohexanones with 2-cyanoacetamide and base in ethanol has been reported to lead to the formation of the tetrahydroisoquinoline isomer. We show that depending on the electronic nature of the para-substituent on the aryl ring, formation of the regioisomeric tetrahydroquinoline isomer can significantly compete. The electron-donating or -withdrawing properties of the para-substituent of the aryl ring determines the ratio of product isomers. A series of 2-aroyl-cyclohexanones, with para-substituents ranging from electron-donating to electron-withdrawing, were reacted with [2-C-13]-cyanoacetamide. The product ratio and absolute regiochemistry were directly determined by quantitative C-13, HMBC, and NOESY NMR spectroscopy on the reaction mixtures. A clear relationship between the regioisomeric product ratio and the Hammett sigma values of the substituents is demonstrated. This is explained by the separate in situ yields, which reveal that the pathway leading to the tetrahydroquinoline regioisomer is significantly more sensitive toward the electronic nature of the para-substituent than the pathway leading to the tetrahydroisoquinoline. Semiempirical AM1 molecular orbital calculations on the starting electrophile 2-aroyl-cyclohexanone support a correlation between the energy of the LUMOs and the regioisomeric product ratio. Our results facilitate synthetic access to a range of these interesting synthetic intermediates.