3-(4-nitrophenyl)-N-methyl-N-phenylpropiolamide | 1158968-96-7

• 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: 3-(4-nitrophenyl)-N-methyl-N-phenylpropiolamide
• 英文别名: N-methyl-3-(4-nitrophenyl)-N-phenylprop-2-ynamide
• CAS: 1158968-96-7
• 化学式: C₁₆H₁₂N₂O₃
• 分子量: 280.283
• InChiKey: ZYEXFKTUKIQHNT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  66.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(4-nitrophenyl)-N-methyl-N-phenylpropiolamide 在 N-溴代丁二酰亚胺(NBS) 、 水 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以52%的产率得到3-bromo-1-methyl-4-(4-nitrophenyl)-1-azaspiro[4.5]deca-3,6,9-triene-2,8-dione
  参考文献：
  名称：

  Intramolecular ipso-Halocyclization of 4-(p-Unsubstituted-aryl)-1-alkynes Leading to Spiro[4,5]trienones: Scope, Application, and Mechanistic Investigations

  摘要：

  A new, general method for the synthesis of spiro[4,5]trienores is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the O-18-labeling experiments and DFT calculations.

  DOI：

  10.1021/jo300037n
• 作为产物：
  描述：

  N-甲基苯胺 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 3-(4-nitrophenyl)-N-methyl-N-phenylpropiolamide
  参考文献：
  名称：

  高价碘试剂介导的N-芳基丙炔酰胺的碘环化：碘化喹啉-2-酮和螺[4,5]三烯酮的不同合成

  摘要：

  PhI（OCOCF 3）2既充当非金属氧化剂，又充当碘化试剂，触发N-芳基丙炔酰胺的碘化，同时根据取代基的类型，选择性提供碘化的喹啉-2-酮或螺[4,5]三烯酮骨架。在N-芳基丙炔酰胺在苯胺环上带有对氟的情况下，螺环化合物是通过专有的脱氟过程形成的；否则，产物为喹啉-2-酮。

  DOI：

  10.1021/acs.orglett.6b03455

文献信息

• Electrophilic <i>ipso</i>-Halocyclization of <i>N</i>-Arylpropynamides with Polyfluoro­alkyl Alcohols: Selective Synthesis of 8-(Polyfluoroalkoxy)azaspiro[4.5]trienes
  作者：Zhi-Qiang Wang、Bo-Xiao Tang、Hong-Ping Zhang、Feng Wang、Jin-Heng Li

  DOI：10.1055/s-0028-1087972

  日期：——

  polyfluoroalkyl alcohols. In the presence of N-halosuccinimides (NXS), a variety of N-arylpropynamides underwent an electrophilic ipso-halocyclization reaction with poly­fluoroalkyl alcohols to afford the corresponding 8-(polyfluoroalkoxy)spiro[4.5]trienes in good yields. Note that molecular sieves can improve the yield of the reaction. electrophilic ipso-halocyclization - N-arylpropynamide - N-halosuccinimide

  为8-（多氟烷）合成了一种新的且有效的方法-1-氮杂螺[4.5]癸-3,6,9-三烯-2-酮已经经由展示了电本位的-halocyclization Ñ与多氟烷醇-arylpropynamides 。在存在Ñ -halosuccinimides（NXS），各种Ñ -arylpropynamides经历亲电本位-halocyclization与多氟烷醇的反应，得到相应的8-（多氟烷基）螺[4.5]以良好的收率三烯。注意分子筛可以提高反应的产率。 电本位-halocyclization - ñ -arylpropynamide - ñ -halosuccinimide -螺[4.5]癸烷-多氟烷取代
• Efficient Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Iodoethynes with Arylboronic Acids under Aerobic Conditions
  作者：Jian-Sheng Tang、Jin-Heng Li、Ye-Xiang Xie、Zhi-Qiang Wang

  DOI：10.1055/s-0030-1260126

  日期：2011.9

  iodoethynes with arylboronic acids under aerobic conditions has been developed. In the presence of palladium(II) acetate and cesium carbonate, a variety of iodoethynes underwent the Suzuki­-Miyaura cross-coupling reaction with arylboronic acids at room temperature to afford the corresponding internal alkynes in moderate to good yields. It is noteworthy that this protocol proceeds under mild and aerobic conditions

  在有氧条件下，开发了无配体钯催化的碘乙炔与芳基硼酸的铃木-宫浦交叉偶联。在乙酸钯（II）和碳酸铯的存在下，各种碘乙炔在室温下与芳基硼酸进行了Suzuki-Miyaura交叉偶联反应，以中等至良好的收率提供了相应的内部炔烃。值得注意的是，该方案在温和有氧条件下进行而无需配体的帮助。 钯-碘乙炔-芳基硼酸-铃木宫浦-交叉偶联-炔烃
• CsPbBr₃ Perovskite Photocatalyst in Chemodivergent Functionalization of <i>N</i>-Methylalkanamides Using CBr₄
  作者：Buddhadeb Pal、Ashis Mathuri、Anupam Manna、Prasenjit Mal

  DOI：10.1021/acs.orglett.3c01268

  日期：2023.6.9

  Herein we have developed a strategy for chemodivergent functionalization of N-methylalkanamides via C–Br bond activation of CBr4, using an orthorhombic CsPbBr3 perovskite photocatalyst under blue LEDs (450–470 nm). The selectivity of whether a 5-exo-trig spiro cyclization or a 6-endo-trig cyclization occurred depended on the stability of the radical intermediate that was formed after the addition of

  在此，我们开发了一种通过 CBr 4的 C-Br 键激活对N-甲基链烷酰胺进行化学发散功能化的策略，使用蓝色 LED（450-470 nm）下的斜方晶系 CsPbBr 3钙钛矿光催化剂。是否发生 5-exo-trig 螺环化或 6-endo-trig 环化的选择性取决于将溴化物自由基添加到起始化合物以获得 3,8-二溴后形成的自由基中间体的稳定性-1-methyl-4-phenyl-1-azaspiro[4.5]deca-3,6,9-trien-2-on 或 3-bromo-1-methyl-4-phenyl-1-azaspiro[4.5]deca-3 ,6,9-triene-2,8-dione 或 3-bromo-6-( tert -butyl)-1-methyl-4-phenylquinolin-2(1 H )-one。
• A General and Highly Versatile Heterogeneous Pd‐Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines
  作者：Juan Camilo Arango‐Daza、Jose R. Cabrero‐Antonino、Rosa Adam

  DOI：10.1002/cssc.202400331

  日期：2024.7.8

  A heterogeneously-catalysed oxidative aminocarbonylation of alkynes with aromatic and aliphatic amines has been developed for the first time. By using a [Pd/Mg3Al-LDH]-300(D) as a general and highly versatile nanocatalyst, composed by a partially dehydrated and dehydroxylated LDH basic matrix support together with homogeneously surface-distributed palladium metallic centers, more than 60 propiolamides

  首次开发了炔烃与芳香族和脂肪族胺的非均相催化氧化氨基羰基化反应。通过使用[Pd/Mg 3 Al-LDH]-300(D)作为通用且高度通用的纳米催化剂，由部分脱水和脱羟基的LDH基本基质载体以及均匀表面分布的钯金属中心组成，超过60种丙炔酰胺以可持续的方式获得了优异的产量。
• AgSCF₃-Mediated Oxidative Trifluoromethythiolation of Alkynes with Dearomatization to Synthesize SCF₃-Substituted Spiro[4,5]trienones
  作者：Dong-Po Jin、Pin Gao、Dao-Qian Chen、Si Chen、Jia Wang、Xue-Yuan Liu、Yong-Min Liang

  DOI：10.1021/acs.orglett.6b01702

  日期：2016.7.15

  A new method for the AgSCF3-mediated radical cascade difunctionalizing trifluoromethythiolation of alkynes with dearomatization is developed. This protocol provides a novel route to SCF3-substituted spirocyclic compounds via the formation of one C-SCF3 bond, one C-C bond, and one C-O double bond in a single step.