benzonitrile-15N | 24949-34-6

• 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: benzonitrile-15N
• 英文别名: ¹⁵N-benzonitrile；<15N>benzonitrile；benzonitrile；Benzonitril-N¹⁵；(15N)benzonitrile
• CAS: 24949-34-6
• 化学式: C₇H₅N
• 分子量: 104.117
• InChiKey: JFDZBHWFFUWGJE-VJJZLTLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• 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：

  benzonitrile-15N 在 盐酸羟胺 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 1,4-二氧六环 、 乙醇 为溶剂， 反应 7.0h， 生成
  参考文献：
  名称：

  钴稳态催化烯胺酮和恶二唑酮与喹唑啉酮的偶联

  摘要：

  过渡金属催化以其多种配位反应模式彻底改变了现代合成化学。然而，这种反应性的多样性也是催化剂失活的主要原因，这是一个持续存在的问题，可能会显着损害其合成价值。稳态催化是一种即使在化学干扰时也能维持其生产催化循环的催化过程，本文提出将其作为应对挑战的有效策略。特别是，已经开发了一种钴稳态催化过程，用于烯胺酮和恶二唑酮与喹唑啉酮的耐水偶联。动态共价键作为机械手柄，优先将水缓冲到烯胺酮上，并通过释放的仲胺进行反向交换，从而确保可逆地进入钴的休眠和活性状态以进行生产催化。通过这种稳态催化模式，喹唑啉酮具有广泛的结构范围，可以进一步细化为不同的药物活性剂。

  DOI：

  10.1021/acs.joc.2c01934
• 作为产物：
  描述：

  3-phenyl-1,2,4-thiadiazole-(2-15N) 以 乙腈 为溶剂， 反应 2.5h， 以71%的产率得到benzonitrile-15N
  参考文献：
  名称：

  Photochemistry of Phenyl-Substituted 1,2,4-Thiadiazoles. ¹⁵N-Labeling Studies

  摘要：

  Irradiation of 5-phenyl-1,2,4-thiadiazole (6) resulted in the formation of benzonitrile (5), 3-phenyl-1,2,4-thiadiazole (4), phenyl- and diphenyl-1,3,5-triazines (7 and 8), and a trace quantity of diphenyl-1,2,4-thiadiazole (9). The formation of 4 5, 7, and 8 can be explained in terms of photoinduced electrocyclic ring closure resulting in the formation of an intermediate 4-phenyl-1,3-diaza-5thiabicyclo[2.1.0]pentene. N-15-labeling experiments revealed that sulfur can undergo sigmatropic shifts around all four sides of the diazetine ring. Thus, irradiation of 6-4-N-15 led to the formation of 6-2-N-15 and an equimolar mixture of 4-2-N-15 and 4-4-N-15. The thiabicyclo[2.1.0]pentene intermediate is also suggested to undergo sulfur elimination resulting in the formation of phenyldiazacyclobutadiene, which can undergo complete fragmentation to benzonitrile or [4+2] cycloaddition leading to unstable tricyclic adducts, the suggested precursors of the 1,3,5-triazine products 7 and 8. The observed N-15 distribution in 7 and 8 is consistent with this mechanism. Irradiation of 4 led only to the formation of 5. N-15-labeling experiments show that 4 does not undergo electrocyclic ring closure but reacts exclusively by photofragmentation of the thiadiazole ring.

  DOI：

  10.1021/jo0340915

文献信息

• An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine
  作者：Attila Vörös、Zoltán Mucsi、Zoltán Baán、Géza Timári、István Hermecz、Péter Mizsey、Zoltán Finta

  DOI：10.1039/c4ob00854e

  日期：——

  The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

  在不同分子溶剂和离子液体中，对腈与羟胺生成脒基肟的工业相关反应进行了研究。在工业上，这一过程在吨级的醇溶液中进行，而上述转化过程会产生大量意外的酰胺副产物，这取决于腈的性质，可能导致进一步的分析和纯化问题。尽管之前有人尝试提出这一转化的机理，但真正的反应途径仍在讨论之中。基于理论和实验证据，给出了一个新的详细反应机理解释，以增强先前的机理，这使我们能够找到一种更高效、无副产物的方法。通过对所获得理论结果的解释，结果显示，使用特定的咪唑鎓、磷鎓和季铵盐基离子液体，不仅可以同时缩短反应时间，还能消除酰胺副产物，从而选择性地得到目标产物。这一稳健且经济的程序现在提供了一种快速、选择性的无酰胺脒基肟合成方法。
• Oxadiazolone-Enabled Synthesis of Primary Azaaromatic Amines
  作者：Xiaolong Yu、Kehao Chen、Fan Yang、Shanke Zha、Jin Zhu

  DOI：10.1021/acs.orglett.6b02814

  日期：2016.10.21

  Despite their tremendous synthetic and pharmaceutical utility, primary azaaromatic amines remain elusive for access based on a generally applicable C–H functionalization strategy. An oxadiazolone-enabled approach is reported for convenient entry into N-unsubstituted 1-aminoisoquinolines through Co(III)-catalyzed redox-neutral, step-, atom-, and purification-economic C–H functionalization with alkynes

  尽管它们具有巨大的合成和制药用途，但基于普遍适用的C–H官能化策略，氮杂芳族伯胺仍然难以获得。恶二唑酮使能的方法据报道可方便地通过炔烃通过Co（III）催化的氧化还原中性，阶跃，原子和纯化经济的CHH功能化进入N-未取代的1-氨基异喹啉。甲15 Ñ标记实验揭示了两个恶二唑酮N原子作为引导位点的有效性。可以将已安装的伯胺用作合成有用的手柄，用于附接发散的附件。
• A practical base mediated synthesis of 1,2,4-triazoles enabled by a deamination annulation strategy
  作者：Chunyan Zhang、Zuyu Liang、Xiaofei Jia、Maorong Wang、Guoying Zhang、Mao-Lin Hu

  DOI：10.1039/d0cc05828a

  日期：——

  A rapid and efficient base mediated synthesis of 1,3,5-trisubstituted 1,2,4-triazoles has been developed from annulation of nitriles with hydrazines, which can be scaled up to a wide range of triazoles in good to excellent yields. Ammonia gas is liberated during the reaction, and halo, hetero functional groups as well as free hydroxyl, amino are tolerated in this transformation. A variety of alkyl

  通过腈与肼的环合反应，已经开发出一种快速，有效的碱介导的1,3,5-三取代的1,2,4-三唑合成方法，该方法可按比例放大至各种三唑，且收率良好至优异。在反应过程中释放出氨气，并且在这种转化过程中，卤素，杂官能团以及游离羟基，氨基都可以被吸收。可以使用此程序将各种烷基，芳基取代的腈用芳香族和脂肪族肼官能化。这一发现为合成各种15N标记的1,2,4-三唑衍生物提供了一种实用且有用的策略，两种类型的mGlu5受体药物可以很容易地以一锅方式组装。
• Synthesis of Densely Substituted Pyridine Derivatives from 1-Methyl-1,3-(ar)enynes and Nitriles by a Formal [4+2] Cycloaddition Reaction
  作者：Dandan He、Bowen Wang、Kanghui Duan、Yang Zhou、Meng Li、Huanfeng Jiang、Wanqing Wu

  DOI：10.1021/acs.orglett.1c04192

  日期：2022.2.18

  densely substituted pyridine derivatives from 1-methyl-1,3-(ar)enynes and nitriles via a formal [4+2] cycloaddition has been established. The well-balanced affinities of two alkali metal salts enable C(sp3)–H bond activation and excellent chemo- and regioselectivities. Experimental studies revealed that nitrile functions only as a partial nitrogen source for pyridine synthesis, and the addition of a metalated

  已经建立了一种通过形式 [4+2] 环加成从 1-甲基-1,3-(ar)enynes 和腈类组装密集取代的吡啶衍生物的有吸引力的方法。两种碱金属盐的平衡亲和力使 C(sp 3 )-H 键活化和优异的化学和区域选择性成为可能。实验研究表明，腈仅作为吡啶合成的部分氮源，将金属化亚胺中间体添加到分子内炔烃是限速步骤。
• Nickel-Catalyzed Synthesis of an Aryl Nitrile via Aryl Exchange between an Aromatic Amide and a Simple Nitrile
  作者：Yang Long、Yanling Zheng、Ying Xia、Lang Qu、Yuhe Yang、Haifeng Xiang、Xiangge Zhou

  DOI：10.1021/acscatal.2c01029

  日期：2022.4.15

  Herein, a nickel-catalyzed synthesis of an aryl nitrile via aryl exchange between an aromatic amide and a simple nitrile was developed. By using cheap, easy-to-handle, and low-toxic 4-cyanopyridine as the cyanating source, cyanation of various aromatic amides afforded an assortment of aryl nitriles including bioactive drugs and organic luminescent molecules in good yields. The reaction exhibited wide

  在此，开发了一种通过芳族酰胺和简单腈之间的芳基交换，在镍催化下合成芳基腈的方法。通过使用廉价、易于处理和低毒的 4-氰基吡啶作为氰化源，各种芳香酰胺的氰化反应以良好的收率提供了包括生物活性药物和有机发光分子在内的各种芳基腈。该反应具有广泛的底物范围、良好的官能团耐受性和独特的选择性，与传统方法互补。此外，通过X射线晶体学获得并确定了通过氧化添加到每个基材中形成的两个关键镍配合物，这为机理阐明提供了有力支持。