N-ethynyl-N-(2-methylallyl)-4-methyl-benzenesulfonamide | 312329-86-5

• 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-ethynyl-N-(2-methylallyl)-4-methyl-benzenesulfonamide
• 英文别名: N-ethynyl-4-methyl-N-(2-methylallyl)benzenesulfonamide；N-ethynyl-4-methyl-N-(2-methylprop-2-enyl)benzenesulfonamide
• CAS: 312329-86-5
• 化学式: C₁₃H₁₅NO₂S
• 分子量: 249.334
• InChiKey: RQEWQKXICRQBMG-UHFFFAOYSA-N

物化性质

• 熔点：
  69 °C
• 沸点：
  361.2±45.0 °C(predicted)
• 密度：
  1.154±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-ethynyl-N-(2-methylallyl)-4-methyl-benzenesulfonamide 在 di(rhodium)tetracarbonyl dichloride 、 3,5-二氯吡啶 N-氧化物 、 三(1,1,1,3,3,3-六氟-2-丙基)亚磷酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 以72%的产率得到
  参考文献：
  名称：

  Generation of Rhodium(I) Carbenes from Ynamides and Their Reactions with Alkynes and Alkenes

  摘要：

  Rh(I) carbenes were conveniently generated from readily available ynamides. These metal carbene intermediates could undergo metathesis with electron-rich or neutral alkynes to afford 2-oxopyrrolidines or be trapped by tethered alkenes to yield 3-azabicyclo[3.1.0]-hexanes, a common skeleton in numerous bioactive pharmaceuticals. Although the scope of the former is limited, the latter reaction tolerates various substituted alkenes.

  DOI：

  10.1021/ja4047069
• 作为产物：
  描述：

  N-Formyl-4-methyl-N-(2-methyl-allyl)benzenesulfonamide 在 正丁基锂 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 生成 N-ethynyl-N-(2-methylallyl)-4-methyl-benzenesulfonamide
  参考文献：
  名称：

  Stereoselective synthesis of alcohols. Part LV. Domino hydroformylation-allylboration-hydroformylation reactions to give trans-perhydropyrano[3,2-b]pyridine derivatives

  摘要：

  N-烯丙基-(E)-γ-氨基烯丙基硼酸盐8和18，在氢甲酰化条件下，进入多米诺氢甲酰化-烯丙基硼化-氢甲酰化反应级联，生成双环N,O-杂环12和20。在甲基烯丙基化合物8b反应时，初始氢甲酰化过程中生成一个手性中心，控制烯丙基硼化反应产生的两个新手性中心的相对构型。

  DOI：

  10.1039/b009259m

文献信息

• Coupling of Carboxylic Acids with Ynamides and Subsequent Rearrangement for the Synthesis of Imides/Amides
  作者：Yangyong Shen、Qi Li、Gang Xu、Sunliang Cui

  DOI：10.1021/acs.orglett.8b02134

  日期：2018.9.7

  A coupling of carboxylic acids with ynamides and subsequent rearrangement for the synthesis of imides and amides is reported. The carboxylic acids could couple with ynamides to form α-acyloxyenamide followed by sulfonyl group migration and Mumm rearrangement to furnish the amides. Additionally, the products could be subjected to further rearrangement to deliver β-keto amides. This metal-free process

  报道了羧酸与炔酰胺的偶联以及随后用于酰亚胺和酰胺的合成的重排。羧酸可以与酰胺结合形成α-酰氧基烯酰胺，然后进行磺酰基迁移和Mumm重排以提供酰胺。另外，可以对产物进行进一步的重排以递送β-酮酰胺。这种无金属的过程代表了一种有趣的化学键裂解和再生方法。此外，进行了产物的发散转化以递送一系列化合物。
• Metal-free C8–H functionalization of quinoline <i>N</i>-oxides with ynamides
  作者：Weican Hu、Feiyang Zhang、Chen Chen、Tianhang Qi、Yanlong Shen、Guoying Qian、Zhouting Rong

  DOI：10.1039/d1cc02138a

  日期：——

  The metal-free C8–H functionalization of quinoline N-oxides with ynamides is unveiled for the first time by the intramolecular Friedel–Crafts-type reaction of quinolyl enolonium intermediates generated from Brønsted acid-catalyzed addition of quinoline N-oxides to ynamides. Various quinoline N-oxides and terminal ynamides prove to be suitable substrates for this method. A one-pot protocol was then

  喹啉N-氧化物与ynamides的无金属C8-H官能化首次通过由Brønsted酸催化将喹啉N-氧化物加成到ynamides产生的喹啉基烯醇中间体的分子内Friedel-Crafts型反应首次公开。各种喹啉N-氧化物和末端 ynamides 被证明是该方法的合适底物。然后开发了一种用于喹啉的无金属直接 C8-H 功能化的一锅法。
• Nickel-catalyzed acetamidation and lactamization of arylboronic acids
  作者：Bo Huang、Linwei Zeng、Yangyong Shen、Sunliang Cui

  DOI：10.1039/c7cc07055a

  日期：——

  A nickel-catalyzed acetamidation and lactamization of arylboronic acids via a one-pot reaction with ynamides and N-hydroxyphthalimide is described. This protocol features with mild reaction conditions and a broad substrate scope, and has been successfully applied to late-stage functionalization of pharmaceuticals. Moreover, control reactions were conducted to elucidate a plausible mechanism.

  描述了通过与酰胺和N-羟基邻苯二甲酰亚胺的一锅反应，镍催化的芳基硼酸的乙酰胺化和内酰胺化。该方案具有温和的反应条件和广泛的底物范围，并已成功应用于药物的后期功能化。此外，进行了对照反应以阐明合理的机制。
• 1,4-Conjugate addition/esterification of <i>ortho</i>-quinone methides in a multicomponent reaction
  作者：Renjie Chen、Yu Liu、Sunliang Cui

  DOI：10.1039/c8cc07328g

  日期：——

  A novel 1,4-conjugate addition/esterification of ortho-quinone methides in a multicomponent reaction has been developed. In this protocol, numerous carboxylic acids, ynamides and in situ generated ortho-quinone methides could assemble rapidly to constitute this process for the synthesis of functionalized 3,3-diarylpropanamides with sufficient structural diversity. Furthermore, the products could be

  的新的1,4-共轭加成/酯化邻-quinone的甲基化物中的多组分反应已经研制成功。在该方案中，许多羧酸，乙酰胺和原位生成的邻醌甲基化物可以迅速组装，从而构成用于合成具有足够结构多样性的官能化3,3-二芳基丙酰胺的过程。此外，可以将产物转化为一系列化合物。
• Synthesis of ynamides from formamides
  作者：David Brückner

  DOI：10.1016/j.tet.2005.11.091

  日期：2006.4

  N-Formyl-tosylamides can be efficiently converted to N-ethynyl-tosylamides in two steps via the corresponding dichlorovinylamides. (c) 2006 Elsevier Ltd. All rights reserved.