N-(1-methyl-1-ethyl-2-propinyl)-p-toluensulphonamide | 16079-23-5

• 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-(1-methyl-1-ethyl-2-propinyl)-p-toluensulphonamide
• 英文别名: (R)(S)-N-(1-methyl-1-ethyl-2-propinyl)-p-toluenesulfonamide；N-(1-methyl-1-ethyl-2-propynyl)-p-toluenesulfonamide；N-(1-methyl-1-ethyl-2-propynyl)-p-toluensulphonamide；4-methyl-N-(3-methylpent-1-yn-3-yl)benzenesulfonamide
• CAS: 16079-23-5
• 化学式: C₁₃H₁₇NO₂S
• 分子量: 251.349
• InChiKey: KZMVTGRGVPHYPE-UHFFFAOYSA-N

物化性质

• 熔点：
  92 °C(Solv: toluene (108-88-3))
• 沸点：
  362.4±52.0 °C(Predicted)
• 密度：
  1.128±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  54.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(1-methyl-1-ethyl-2-propinyl)-p-toluensulphonamide 在 dodecacarbonyltetrarhodium(0) 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 20.0~100.0 ℃ 、3.04 MPa 条件下， 反应 24.0h， 生成 (E/Z)-2-benzyl-3-methyl-2-pentenal
  参考文献：
  名称：

  甲硅烷基化 - 氟化物辅助炔属衍生物的芳基迁移以多功能方法合成多官能化合物

  摘要：

  多官能化醛和二氢吡喃是从容易获得的官能化 1-炔烃通过两步甲硅烷基甲酰化/芳基迁移序列制备的。甲硅烷基化过程在温和的实验条件下进行，并以高产率提供相应的 β-甲硅烷基链烯醛。氟化物促进的迁移步骤与定量转化同时发生。化学选择性、区域选择性和立体选择性可以根据乙炔前体上官能团的性质和位置进行调节。当炔烃的脂肪链的ω位置存在良好的离去基团时，获得环化产物，而α，p-不饱和醛则由炔丙基甲苯磺酰胺产生。((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)。

  DOI：

  10.1002/ejoc.200500883
• 作为产物：
  描述：

  3-甲基-3-氨基-1-戊炔 、 对甲苯磺酰氯 在 sodium hydroxide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以77%的产率得到N-(1-methyl-1-ethyl-2-propinyl)-p-toluensulphonamide
  参考文献：
  名称：

  Silylation–desilylation of propargyl amides: rapid synthesis of functionalised aldehydes and β-lactams

  摘要：

  Propargyl functionalised beta-silylalkenals were easily prepared starting from suitable propargyl compounds by a silylformylation process. In particular the use of propargyl tosyl amides allowed the synthesis of alpha, beta-unsaturated aldehydes through a two-step sequence of silylformylation -desilylation reactions. TBAF was employed to induce the desilylation process that was performed under very mild experimental conditions and occurred along with an elimination step of the tosylamido moiety affording 2-methylaryl-2-alkenals with good yields and stereoselectivity. When the tosyl amides were reacted with a hydrosilane in the presence of catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) alpha-silylmethylene-beta-lactams were synthesised through a silylcarbocyclisation process. A high chemoselectivity towards the b-lactam was observed when dialkyl propargyl amides were employed. The obtained b-lactams were easily transformed into the corresponding methylaryl-b-lactams by fluoride induced aryl migration -desilylation with total retention of configuration of the migrating group and complete stereoselectivity towards the more stable b-lactam (E)-isomer. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.04.064

文献信息

• Silylformylation–desilylation of propargyl amides: synthesis of α,β-unsaturated aldehydes
  作者：Laura Antonella Aronica、Patrizio Raffa、Giulia Valentini、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1016/j.tetlet.2005.11.054

  日期：2006.1

  α,β-Unsaturated aldehydes are prepared from easily available propargyl amides through a two-step sequence of silylformylation–desilylation reactions. The substituent on the nitrogen atom markedly influences both reactions, β-silylalkenals being formed in the presence of tosyl or tert-butoxycarbonyl protected amines. TBAF is employed to induce the desilylation process that is performed under very mild

  α，β-不饱和醛是由容易获得的炔丙基酰胺通过两步的甲硅烷基甲酰化-去甲硅烷基化反应制得的。氮原子上的取代基显着影响两个反应，在甲苯磺酰基或叔丁氧羰基保护的胺存在下会形成β-甲硅烷基烯醛。TBAF用于诱导在非常温和的实验条件下进行的脱甲硅烷基化过程。当甲苯磺酰胺醛反应生成2-甲基芳基-2-烯醛时，发生了当代的消除步骤，同时可以抑制该过程，将官能团改变为NBOC，从而形成β-氨基羰基化合物。
• Isobaev, M. D.; Venger, E. F.; Grigina, I. N., Journal of Organic Chemistry USSR (English Translation), 1989, vol. 25, # 11.2, p. 2125 - 2129
  作者：Isobaev, M. D.、Venger, E. F.、Grigina, I. N.、Glazunova, E. M.

  DOI：——

  日期：——
• Metal vapour derived supported rhodium nanoparticles in the synthesis of β-lactams and β-lactones derivatives
  作者：Laura Antonella Aronica、Anna Maria Caporusso、Claudio Evangelisti、Maria Botavina、Gabriele Alberto、Gianmario Martra

  DOI：10.1016/j.jorganchem.2011.11.008

  日期：2012.3

  Functionalised beta-lactones and beta-lactams were prepared starting from propargyl alcohols and propargyl tosyl amides by means of efficient silylcarbocyclisation reactions catalysed by rhodium nanoparticles derived from mesitylene-solvated Rh atoms (Metal Vapour Synthesis technique, MVS) and deposited on inorganic (C, gamma-Al2O3 Fe2O3) and organic matrices (PBI). All the MVS supported nanoclusters resulted more active than the analogous commercial Rh/C and Rh/gamma-Al2O3, as well as homogeneous Rh-4(CO)(12) used as reference catalyst. In particular, metal vapour derived Rh/C afforded the beta-lactones and beta-lactams in high yields and chemoselectivity. Preliminary investigations on the nature of the real active metal species involved in the catalytic process showed that rhodium(0) naked nanoparticles are leached by the support. The high catalytic activity encountered with Rh/C could be ascribed to the easy leaching of metal nanoparticles from carbon into solution. Indeed, the presence of a more polar matrix determined a minor catalytic efficiency probably due to a stronger interaction between the metal and the support. Therefore MVS Rh/C species represents a source, stable with ageing at room temperature, of highly active metal nanoparticles. (C) 2011 Elsevier B. V. All rights reserved.
• Silylation–desilylation of propargyl amides: rapid synthesis of functionalised aldehydes and β-lactams
  作者：Laura Antonella Aronica、Giulia Valentini、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1016/j.tet.2007.04.064

  日期：2007.7

  Propargyl functionalised beta-silylalkenals were easily prepared starting from suitable propargyl compounds by a silylformylation process. In particular the use of propargyl tosyl amides allowed the synthesis of alpha, beta-unsaturated aldehydes through a two-step sequence of silylformylation -desilylation reactions. TBAF was employed to induce the desilylation process that was performed under very mild experimental conditions and occurred along with an elimination step of the tosylamido moiety affording 2-methylaryl-2-alkenals with good yields and stereoselectivity. When the tosyl amides were reacted with a hydrosilane in the presence of catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) alpha-silylmethylene-beta-lactams were synthesised through a silylcarbocyclisation process. A high chemoselectivity towards the b-lactam was observed when dialkyl propargyl amides were employed. The obtained b-lactams were easily transformed into the corresponding methylaryl-b-lactams by fluoride induced aryl migration -desilylation with total retention of configuration of the migrating group and complete stereoselectivity towards the more stable b-lactam (E)-isomer. (c) 2007 Published by Elsevier Ltd.
• Silylformylation – Fluoride-Assisted Aryl Migration of Acetylenic Derivatives in a Versatile Approach to the Synthesis of Polyfunctionalised Compounds
  作者：Laura Antonella Aronica、Patrizio Raffa、Giulia Valentini、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1002/ejoc.200500883

  日期：2006.4

  Polyfunctionalised aldehydes and dihydropyrans are prepared from easily available functionalised 1-alkynes through a two-step silylformylation/aryl migration sequence. The silylformylation process is performed under mild experimental conditions and affords the corresponding beta-silylalkenals in high yields. The fluoride-promoted migration step occurs instantaneously with quantitative conversion. The

  多官能化醛和二氢吡喃是从容易获得的官能化 1-炔烃通过两步甲硅烷基甲酰化/芳基迁移序列制备的。甲硅烷基化过程在温和的实验条件下进行，并以高产率提供相应的 β-甲硅烷基链烯醛。氟化物促进的迁移步骤与定量转化同时发生。化学选择性、区域选择性和立体选择性可以根据乙炔前体上官能团的性质和位置进行调节。当炔烃的脂肪链的ω位置存在良好的离去基团时，获得环化产物，而α，p-不饱和醛则由炔丙基甲苯磺酰胺产生。((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)。