N-(2-bromophenyl)-N-methyl-3-phenylpropiolamide | 1013905-86-6

• 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: N-(2-bromophenyl)-N-methyl-3-phenylpropiolamide
• 英文别名: N-(2-bromophenyl)-N-methyl-3-phenylprop-2-ynamide
• CAS: 1013905-86-6
• 化学式: C₁₆H₁₂BrNO
• 分子量: 314.181
• InChiKey: VEHQVMFZFRMKJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 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：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(2-bromophenyl)-N-methyl-3-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80%的产率得到3,6-dibromo-1-methyl-4-phenyl-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：

  2-溴苯胺 在 4-二甲氨基吡啶 、 sodium hydride 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 N-(2-bromophenyl)-N-methyl-3-phenylpropiolamide
  参考文献：
  名称：

  通过烯基过氧化物自由基中间体通过酸引发的氧化级联反应获得3-（2-氧代烷基）-氮杂螺[4.5]三烯酮

  摘要：

  由N-烷基-芳基丙丙酰胺和酮经炔烃的1,2-二官能团氧化制得在3位带有酮侧链的Azaspiro [4.5]三烯酮。级联序列始于过氧化烯基中间体的产生，这是通过在催化量的强酸存在下将叔丁基氢过氧化物加到酮中而获得的。然后，酮自由基加成炔烃，随后进行螺环化和脱芳香化过程。该方法代表了炔烃双官能化的一个新实例，该一步同时形成了两个碳-碳单键和一个碳-氧双键。

  DOI：

  10.1002/adsc.201801203

文献信息

• Silver-catalyzed direct spirocyclization of alkynes with thiophenols: a simple and facile approach to 3-thioazaspiro[4,5]trienones
  作者：Huanhuan Cui、Wei Wei、Daoshan Yang、Jimei Zhang、Zhihong Xu、Jiangwei Wen、Hua Wang

  DOI：10.1039/c5ra16548b

  日期：——

  A new and convenient silver-catalyzed direct oxidative spirocyclization of alkynes with thiophenols is described. This methodology provides a simple and practical approach to various 3-thioazaspiro[4,5]trienones in moderate to good yields with high atom efficiency and excellent functional group tolerance.

  描述了一种新的且方便的用硫酚对炔烃进行银催化的银催化直接氧化螺环化反应。该方法为中度到良好的产率，高原子效率和出色的官能团耐受性提供了各种3-thioazaspiro [4,5] trienones的简单实用方法。
• Palladium‐Catalyzed 5‐ <i>exo‐dig</i> Cyclization Cascade, Sequential Amination/Etherification for Stereoselective Construction of 3‐Methyleneindolinones
  作者：Youpeng Zuo、Xinwei He、Qiang Tang、Wangcheng Hu、Tongtong Zhou、Wenbo Hu、Yongjia Shang

  DOI：10.1002/adsc.202001369

  日期：2021.4.13

  An cascade intramolecular 5‐exo‐dig cyclization of N‐(2‐iodophenyl)propiolamides and sequential amination/etherification (with N‐hydroxybenzamides, phenyl hydroxycarbamate) protocol for the synthesis of amino‐ and phenoxy‐substituted 3‐methyleneindolinones using unexpensive Pd(PPh3)4 as catalyst has been developed. The protocol enables the assembly of structurally important oxindole cores featuring

  N-（2-碘代苯基）丙酰胺的级联分子内5 -exo-dig环化反应和顺序胺化/醚化（与N-羟基苯甲酰胺，苯基羟基氨基甲酸酯）方案，使用廉价的Pd（已经开发了作为催化剂的PPh 3）4。该协议使具有重要官能团耐受性（特别是卤素基团）的结构重要的羟吲哚核的组装成为可能，从而提供了具有各种取代基的多种产品，收率良好至极佳。
• Synthesis of [1,2,3]Triazolo[1,5-<i>a</i>]quinoxalin-4(5<i>H</i>)-ones through Copper-Catalyzed Tandem Reactions of <i>N</i>-(2-Haloaryl)propiolamides with Sodium Azide
  作者：Jiajie Yan、Fengtao Zhou、Dongguang Qin、Tong Cai、Ke Ding、Qian Cai

  DOI：10.1021/ol300114w

  日期：2012.3.2

  A simple and efficient approach for the synthesis of [1,2,3]triazolo[1,5-a]quinoxalin-4(5H)-ones is described. The methodology is based on a tandem reaction of 1-(2-haloaryl)propiolamides with sodium azide through a [3 + 2] azide–alkyne cycloaddition and intramolecular Ullmann-type C–N coupling process.

  描述了一种简单有效的合成[1,2,3]三唑并[1,5 - a ]喹喔啉-4（5 H）-的方法。该方法基于1-（2-卤代芳基）丙酰胺与叠氮化钠通过[3 + 2]叠氮化物-炔烃环加成反应以及分子内Ullmann型C-N偶联过程的串联反应。
• 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
• One-pot synthesis of a white-light emissive bichromophore operated by aggregation-induced dual emission (AIDE) and partial energy transfer
  作者：Melanie Denißen、Ricarda Hannen、Dana Itskalov、Lukas Biesen、Nithiya Nirmalananthan-Budau、Katrin Hoffmann、Guido J. Reiss、Ute Resch-Genger、Thomas J. J. Müller

  DOI：10.1039/d0cc03451g

  日期：——

  are readily synthesized by sequentially Pd-catalyzed insertion–alkynylation–Michael–Suzuki four-component reactions. White-light emissive systems form upon aggregation in 1 : 99 and 0.1 : 99.9 vol% CH2Cl2–cyclohexane mixtures, ascribed to aggregation-induced dual emission (AIDE) in combination with partial energy transfer between both chromophore units as supported by spectroscopic studies.

  通过连续的Pd催化的插入-炔基化-Michael-Suzuki四组分反应可以轻松合成花青-三芳基胺双发色团。聚集在1:99和0.1：99.9 vol％的CH 2 Cl 2-环己烷混合物中形成白光发射系统，这归因于聚集诱导的双发射（AIDE），并结合了两个发色团之间的部分能量转移（如光谱法所支持）学习。