N,N-di(prop-2-yn-1-yl)benzenesulfonamide | 13630-88-1

• 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,N-di(prop-2-yn-1-yl)benzenesulfonamide
• 英文别名: N,N-bis(2-propynyl)benzenesulfonamide；N,N-Di-(2-propinyl)benzolsulfonamid；N,N-Dipropargyl-benzolsulfonamid；N.N-Dipropargylbenzolsulfonamid；N,N-bis(prop-2-ynyl)benzenesulfonamide
• CAS: 13630-88-1
• 化学式: C₁₂H₁₁NO₂S
• 分子量: 233.291
• InChiKey: RKLZJNFXQKVJPO-UHFFFAOYSA-N

物化性质

• 熔点：
  87-89 °C
• 沸点：
  356.7±52.0 °C(Predicted)
• 密度：
  1.237±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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,N-di(prop-2-yn-1-yl)benzenesulfonamide 在 正丁基锂 作用下， 以 甲苯 为溶剂， 反应 3.0h， 生成 2-Benzenesulfonyl-4-[2-hydroxy-2-methyl-prop-(Z)-ylidene]-6,7-dimethoxy-1,2,3,4-tetrahydro-isoquinoline-5,8-dione
  参考文献：
  名称：

  Ring Expansion of 4-Alkynylcyclobutenones. Synthesis of Piperidinoquinones, Highly Substituted Dihydrophenanthridines, Benzophenanthridines, and the Naturally Occurring Pyrrolophenanthridine, Assoanine

  摘要：

  New synthetic routes to a variety of N-heterocyclic quinones and hydroquinones are described. These include thermolyses of 4-hydroxy-4-[4-N-(benzenesulfonyl)-4-aza-1,6-dialkynyl]cyclobutenones to piperidinoquinones and 4-hydroxy-4-[3-(N-phenylamino)-1-propynyl] cyclobutenones to dihydrophenanthridinediols. Included in the array of products available by this method are benzophenanthridines, indolophenanthridines, isoindoloindoles, and pyrrolophenanthridines. The methodology was employed in a five-step synthesis of the alkaloid assoanine starting with dimethyl squarate and indoline. The key step in all of these transformations is the ring expansion of appropriately substituted 4-hydroxy-4-alkynylcyclobutenones. These are envisaged to undergo electrocyclic ring opening to the corresponding enynylketenes which ring close to diradical intermediates that then lead to products via either radical additions to proximal alkyne moieties or undergo homolytic aromatic substitution to appropriately placed aryl groups. The synthetic scope and mechanism of the ring expansion reactions are discussed.

  DOI：

  10.1021/jo9613803
• 作为产物：
  描述：

  苯磺酰胺 、 3-溴丙炔 在 potassium carbonate 作用下， 以 甲苯 、 乙腈 为溶剂， 以46 %的产率得到N,N-di(prop-2-yn-1-yl)benzenesulfonamide
  参考文献：
  名称：

  铑催化[2+2+2]环加成中未活化内炔的相容性评估

  摘要：

  官能化的1,2,4,5-四取代苯在合成上很难或很难获得。 Rh 催化的二炔和内炔的 [2+2+2] 环加成为这些支架提供了一条看似简单的途径；然而，这在很大程度上仅限于带有活化（配位）官能团的炔烃，很少有未活化的炔烃。在这项工作中，我们公开了对使用未活化的内部炔烃的 Rh 催化的 [2+2+2] 环加成的评估，重点关注炔烃和二炔组分的结构多样性和相容性。该方法的局限性被揭示，特别大的炔烃和特定的官能团会发生副反应。此外，还证明了克级反应和催化剂回收/再利用的实用性。

  DOI：

  10.1055/a-2285-0007

文献信息

• N-Prop-2-ynylmaleimide. Application to Sequential One-pot Rh(I) Catalysed [2+2+2]-Alkyne Cyclotrimerisation–Imine Cycloaddition
  作者：Ronald Grigg、Visuvanathar Sridharan、Jun Wang、Juan Xu

  DOI：10.1016/s0040-4020(00)00849-8

  日期：2000.11

  Rh(I) catalysed [2+2+2]-cyclotrimerisation of 1,6-diynes with monoynes in combination with stereospecific thermal or Ag(I) catalysed aldimine→(metallo) azomethine ylide→cycloaddition cascades affords rapid access to complex heterocyclic benzene derivatives in one-pot processes with the generation 5 new bonds, 4 stereocentres and 3 rings.

  Rh（I）催化1,6-二炔与单炔的[2 + 2 + 2]-环三聚，与立体有择的热或Ag（I）催化的亚胺[→金属]甲亚胺叶立德→环加成级联反应提供了对复杂杂环苯的快速访问一锅法衍生的衍生物，带有5个新键，4个立体中心和3个环。
• Radical Cyclization in Heterocycle Synthesis. 12. Sulfanyl Radical Addition-Addition-Cyclization (SRAAC) of Unbranched Diynes and Its Application to the Synthesis of A-Ring Fragment of 1.ALPHA.,25-Dihydroxyvitamin D3.
  作者：Okiko MIYATA、Emi NAKAJIMA、Takeaki NAITO

  DOI：10.1248/cpb.49.213

  日期：——

  Sulfanyl radical addition-addition-cyclization (SRAAC) of unbranched diynes proceeded smoothly to give cyclized exo-olefins, while the sulfanyl radical addition-cyclization-addition (SRACA) of diynes having a quaternary carbon gave cyclized endo-olefins. This method was successfully applied to the synthesis of A-ring fragment of 1α, 25-dihydroxyvitamin D3.

  无支链二炔的硫基自由基加成-加成-环化 (SRAAC) 反应顺利进行，生成环状外烯烃，而具有季碳的二炔的硫基自由基加成-环化-加成 (SRACA) 反应则生成环状内烯烃。这一方法成功应用于1α, 25-二羟基维生素D3的A环片段的合成。
• A novel utilization of trifluoromethanide as a base: a convenient synthesis of trimethylsilylacetylene
  作者：Mitsuhiro Yoshimatsu、Masako Kuribayashi

  DOI：10.1039/b101537k

  日期：——

  Trifluoromethanide generated from CF3SiMe3–Bu4NF reacted with terminal acetylenes and acetylenic selenides as a base or a nucleophile to give trimethylsilylacetylenes in high yields.

  由 CF3SiMe3-Bu4NF 生成的三氟甲烷作为碱或亲核体与末端乙炔和乙炔硒化物反应，以高产率得到三甲基硅基乙炔。
• Iron-Catalyzed [2 + 2 + 2] Cycloaddition Reactions of Diynes with Oxyphosphaethynes To Construct 2-Phosphaphenol Derivatives
  作者：Kazunari Nakajima、Wenbin Liang、Yoshiaki Nishibayashi

  DOI：10.1021/acs.orglett.6b02462

  日期：2016.10.7

  Iron-catalyzed [2 + 2 + 2] cycloaddition reactions of diynes with siloxyphosphaethynes have been developed to give 2-phosphaphenol derivatives. The use of electronically neutral siloxyphosphaethynes generated in situ by the reaction of anionic phosphaethynolate with silyl triflates is key to achieving the reactions.

  已开发出铁催化的二炔与甲硅烷氧基磷杂环丁烷的[2 + 2 + 2]环加成反应，得到2-磷酚衍生物。使用通过阴离子磷酸胸苷酸与甲硅烷基三氟甲磺酸酯反应原位产生的电子中性的硅烷氧基磷酸胸苷是实现该反应的关键。
• Rhodium(III)-Catalyzed Cascade [5 + 1] Annulation/5-exo-Cyclization Initiated by C–H Activation: 1,6-Diynes as One-Carbon Reaction Partners
  作者：Fen Xu、Wei-Fen Kang、Yang Wang、Chun-Sen Liu、Jia-Yue Tian、Rui-Rui Zhao、Miao Du

  DOI：10.1021/acs.orglett.8b01105

  日期：2018.6.1

  n reaction of amidines with diynes is reported herein. This protocol provides highly atom-economical access to fabricate two nitrogen-containing heterocycles in one step with high efficiency and selectivity. Significantly, this reaction represents the first example of using diyne as a one-carbon reaction partner in C–H functionalization. Kinetic isotope effects suggested that the catalytic cycle of

  本文报道了with与二炔的催化[5 +1]环化/ 5-外环化反应。该方案提供了一种经济高效的原子制备方法，可一步一步高效地制备两个含氮杂环。重要的是，该反应代表了在C–H功能化中使用二炔作为单碳反应伙伴的第一个例子。动力学同位素效应表明该反应的催化循环是由N中邻位C–H键的裂解引发的idine的苯基环，可能参与限速步骤。基于密度泛函理论（DFT）的计算表明，C–H活化和通过5-exo环化形成Rh（V）物种可能是此级联转化的重要过程。