3-(2-硝基乙烯基)苯甲腈 | 62248-92-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3-(2-硝基乙烯基)苯甲腈
• 英文名称: 3-cyano-β-nitrostyrene
• 英文别名: m-Cyano-β-nitrostyrol；3-(2-Nitroethenyl)benzonitrile
• CAS: 62248-92-4
• 化学式: C₉H₆N₂O₂
• 分子量: 174.159
• InChiKey: CDJHTQWXSZMZNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  69.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(2-硝基乙烯基)苯甲腈 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以88%的产率得到3-(1H-(1,2,3)三氮唑-4-基)-苯腈
  参考文献：
  名称：

  Direct Synthesis of N-Unsubstituted 4-Aryl-1,2,3-triazoles Mediated by Amberlyst-15

  摘要：

  A highly efficient and effective method for the synthesis of N-unsubstituted 4-aryl-1,2,3-triazoles promoted by Amberlyst-15 is described. The promoter can be recycled and reused up to eight times without any reduction in its catalytic activity.

  DOI：

  10.1055/s-0035-1560488
• 作为产物：
  描述：

  硝基甲烷 、 3-氰基苯甲醛 生成 3-(2-硝基乙烯基)苯甲腈
  参考文献：
  名称：

  Kinetics of reversible thiolate ion addition to substituted .beta.-nitrostyrenes in water. Radicaloid transition state or principle of nonperfect synchronization?

  摘要：

  The kinetics of reversible nucleophilic thiolate ion (RS- with R = n-Bu, HOCH2CH2, MeO2CCH2CH2 and MeO2CCH2) addition to Z-substituted beta-nitrostyrenes (Z = 4-Me2N, 4-MeO, 4-MeS, 4-Me, H, 3-Cl, 4-Cl, 3-CN, 4-CN, and 3-NO2), to form ArCH(RS)CH = NO2-, have been measured in water at 20-degrees-C. Rate constants in the forward (k1) and reverse direction (k-1) and equilibrium constants (K1) correlate reasonably well with Hammett sigma-constants for the non-pi-donor substituents but show deviations for the pi-donors 4-Me2N, 4-MeO, and 4-MeS. These deviations are negative for K1 but positive for k1 and k-1; the positive deviations for the pi-donor substituents are also observed when plotting log k1 vs log K1 (Bronsted plots). The negative deviations of K1 are a consequence of resonance stabilization of the olefin. The positive deviations are attributed to a transition-state stabilization stemming from a preorganization created by the pi-donor which leads to a better delocalization of the negative charge into the nitro group. An alternative interpretation of the rate acceleration in terms of a radicaloid transition state (Gross, Z.; Hoz, S.J. Am. Chem. Soc. 1988, 110, 7489) cannot be ruled out but is shown to be less attractive and unnecessary. Bronsted parameters such as beta(nuc), beta(eq), beta(nuc)n, and beta(lg)n, and intrinsic rate constants (k(o) = k1 k-1 when K1 = 1) were determined from the dependence on RS- basicity for beta-nitrostyrene and 3-cyano-beta-nitrostyrene. Beta(eq) is low (0.5), indicating that the carbon basicity of RS- is less sensitive to electronic effects in R than its proton basicity. Beta(nuc) (beta(nuc)n) is very low, suggesting a transition state with very little C-S bond formation. The low beta(nuc)n (0.22) contrasts with a large alpha(nuc)n = d log k1/d log K1 = 0.74 (variation of Z), indicating a large transition-state imbalance (alpha(nuc)n - beta(nuc)n), as previously observed in the reaction of RS- with alpha-nitrostilbenes. The intrinsic rate constant (log k(o) = 3.5) is also similar to that for the reaction of RS- with alpha-nitrostilbenes and significantly higher than for the reaction of amines with beta-nitrostyrenes. Most of these features can, at least in part, be attributed to the soft acid-soft base interactions of RS- with the nitroolefins. Rate constants for carbon protonation of several of the ArCH(RS)CH = NO2- adducts by acetic acid (k(p)HA) were also determined. They display the unusual, but for nitronate ions typical, acceleration when Ar and/or R is made more electron withdrawing.

  DOI：

  10.1021/jo00034a032

文献信息

• Cooperative Multifunctional Catalysts for Nitrone Synthesis: Platinum Nanoclusters in Amine‐Functionalized Metal–Organic Frameworks
  作者：Xinle Li、Biying Zhang、Linlin Tang、Tian Wei Goh、Shuyan Qi、Alexander Volkov、Yuchen Pei、Zhiyuan Qi、Chia‐Kuang Tsung、Levi Stanley、Wenyu Huang

  DOI：10.1002/anie.201710164

  日期：2017.12.18

  in organic synthesis and the pharmaceutical industry. The heterogeneous synthesis of nitrones with multifunctional catalysts is extremely attractive but rarely explored. Herein, we report ultrasmall platinum nanoclusters (PtNCs) encapsulated in amine‐functionalized Zr metal–organic framework (MOF), UiO‐66‐NH2 (Pt@UiO‐66‐NH2) as a multifunctional catalyst in the one‐pot tandem synthesis of nitrones

  硝基是有机合成和制药行业的关键中间体。用多功能催化剂进行硝酮的非均相合成极具吸引力，但很少探索。在本文中，我们报告了一锅纵列中封装在胺官能化Zr金属有机框架（MOF），UiO-66-NH 2（Pt @ UiO-66-NH 2）中的超小型铂纳米簇（PtNC）。硝酮的合成。由于超小PtNC提供的选择性加氢活性与UiO-66-NH 2赋予的Lewis酸度/碱度/纳米约束作用之间的协同作用，与Pt相比，Pt @ UiO-66-NH 2表现出显着的活性和选择性。 / carbon，Pt @ UiO‐66和Pd @ UiO‐66‐NH 2。Pt @ UiO-66-NH 2的性能也优于同一MOF（Pt / UiO-66-NH 2）外表面负载的Pt纳米颗粒。据我们所知，这项工作展示了使用可回收的多功能非均相催化剂单锅合成硝酮的第一个实例。
• Highly diastereoselective and enantioselective direct Michael addition of phthalide derivatives to nitroolefins
  作者：Jie Luo、Haifei Wang、Fangrui Zhong、Jacek Kwiatkowski、Li-Wen Xu、Yixin Lu

  DOI：10.1039/c3cc42187b

  日期：——

  The first asymmetric Michael addition of 3-substituted phthalides to nitroolefins promoted by amino acid-incorporating multifunctional catalysts has been developed. The reported method led to the synthesis of 3,3-disubstituted phthalide derivatives in high yields, and in a highly diastereoselective and enantioselective manner. Facile synthesis of a chiral bicyclic lactam has also been demonstrated

  已经开发了通过结合氨基酸的多功能催化剂促进的3-取代的邻苯二甲酸酯到硝基烯烃的第一次不对称迈克尔加成反应。报道的方法导致高产率，高非对映选择性和对映选择性的方式合成3，3-二取代的邻苯二甲酰胺衍生物。还已经证明容易合成手性双环内酰胺。
• Nitroalkenes as Latent 1,2-Biselectrophiles – A Multicatalytic Approach for the Synthesis of 1,4-Diketones and Their Application in a Four-Step One-Pot Reaction to Polysubstituted Pyrroles
  作者：Patrick J. W. Fuchs、Kirsten Zeitler

  DOI：10.1021/acs.joc.7b00830

  日期：2017.8.4

  An NHC-catalyzed nitro-Stetter/elimination/Stetter reaction sequence employs nitroalkenes as latent 1,2-dication synthons providing a novel access to highly useful symmetrical and unsymmetrical 2-aryl substituted 1,4-diketone building blocks from commercially available aldehyde precursors. For less activated (aliphatic) aldehydes, a cooperative catalytic strategy has been developed via the merger of

  NHC催化的硝基-Stetter /消除/ Stetter反应序列使用硝基烯烃作为潜在的1,2-阳离子合成子，提供了从商业上可得的醛类前体获得高度有用的对称和不对称2-芳基取代的1,4-二酮结构单元的新途径。对于较少活化的（脂肪族）醛，已经通过NHC和H键催化的合并开发了一种协同催化策略。为了进一步展示我们方法的多功能性，使用了这些前所未有的1,4-二酮中的多种，可以有效地合成多取代的吡咯（包括带有杂芳基取代基的吡咯），并通过多步无金属四步法以良好的产率获得良​​好的收率。在温和但稳定的条件下进行罐级联反应。
• Pd‐Catalyzed Tandem Pathway for Stereoselective Synthesis of (<i>E</i>)‐1,3‐Enyne from <i>β</i>‐Nitroalkenes by Using a Sacrificial Directing Group
  作者：Subal Mondal、Siba P. Midya、Suman Das、Soumya Mondal、Abu S. M. Islam、Pradyut Ghosh

  DOI：10.1002/chem.202301637

  日期：2023.11.2

  Dancing hybridization: The first example of efficient and stereoselective (E)-1,3-enyne synthesis exclusively from alkene substrates is described. Inauguration of nitro group as a sacrificial directing group, formation of magical triple bond by promoting zero-order to third-order upgradation make this methodology atom and step efficient with sustainability.

  跳舞杂交：描述了仅从烯烃底物有效且立体选择性 ( E )-1,3-烯炔合成的第一个例子。硝基作为牺牲导向基团的诞生，通过促进零级到三级升级形成神奇的三键，使该方法原子和步骤高效且可持续。
• Organocatalytic Asymmetric Michael Addition of 5<i>H</i>-Oxazol-4-ones to Nitroolefins
  作者：Baokun Qiao、Yongqiang An、Qian Liu、Wenguo Yang、Hongjun Liu、Juan Shen、Lin Yan、Zhiyong Jiang

  DOI：10.1021/ol401062z

  日期：2013.5.17

  The first organocatalytic asymmetric Michael addition of 5H-oxazol-4-ones to nitroolefins has been developed. In the presence of easily prepared L-tert-leucine-derived tertiary amine/thiourea catalyst, the Michael addition of 5H-oxazol-4-ones to nitroolefins proceeded in an excellent diastereo- and enantioselective manner (up to 99% ee and >19:1 dr). The Michael adducts obtained are valuable precursors for the synthesis of chiral alpha-alkyl-alpha-hydroxy carboxylic acid derivatives, which represent a series of versatile building blocks in many biologically active compounds.