(E)-N-4-methylbenzylidene-4-toluenesulfonamide | 75159-10-3

• 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: (E)-N-4-methylbenzylidene-4-toluenesulfonamide
• 英文别名: (E)-4-methyl-N-(4-methylbenzylidene)benzenesulfonamide；4-Methyl-N-(4-methyl-benzylidene)benzenesulfonamide；(NE)-4-methyl-N-[(4-methylphenyl)methylidene]benzenesulfonamide
• CAS: 75159-10-3
• 化学式: C₁₅H₁₅NO₂S
• 分子量: 273.356
• InChiKey: CEZQVKAFKQRFDG-LFIBNONCSA-N

物化性质

• 熔点：
  114-115 °C
• 沸点：
  425.1±48.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  54.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-N-4-methylbenzylidene-4-toluenesulfonamide 在 正丁基锂 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 乙醚 为溶剂， -78.0~35.0 ℃ 、199.98 Pa 条件下， 反应 6.66h， 生成 N-[(1E)-2-iodo-2-(4-methylphenyl)ethylidene]-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Synthesis of cis-C-Iodo-N-Tosyl-Aziridines using Diiodomethyllithium: Reaction Optimization, Product Scope and Stability, and a Protocol for Selection of Stationary Phase for Chromatography

  摘要：

  The preparation of C-iodo-N-Ts-aziridines with excellent cis-diastereoselectivity has been achieved in high yields by the addition of diiodomethyllithium to N-tosylimines and N-tosylimine-HSO(2)Tol adducts. This addition-cyclization protocol successfully provided a wide range of cis-iodoaziridines, including the first examples of alkyl-substituted iodoaziridines, with the reaction tolerating both aryl imines and alkyl imines. An ortho-chlorophenyl imine afforded a beta-amino gem-diiodide under the optimized reaction conditions due to a postulated coordinated intermediate preventing cyclization. An effective protocol to assess the stability of the sensitive iodoaziridine functional group to chromatography was also developed. As a result of the judicious choice of stationary phase, the iodoaziridines could be purified by column chromatography; the use of deactivated basic alumina (activity IV) afforded high yield and purity. Rearrangements of electron rich aryl-iodoaziridines have been promoted, selectively affording either novel alpha-iodo-N-Ts-imines or alpha-iodo-aldehydes in high yield.

  DOI：

  10.1021/jo400956x
• 作为产物：
  描述：

  4-methyl-N-(p-tolyl(tosyl)methyl)benzenesulfonamide 在 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到(E)-N-4-methylbenzylidene-4-toluenesulfonamide
  参考文献：
  名称：

  Practical and General Entry toN‐Tosyl Aryl Aldimines Promoted by Sulfamic Acid in Water and Alcohol

  摘要：

  A practical, indirect procedure composed of a three-component condensation using aromatic aldehydes, p-tosylamide, and sodium p-toluenesulfinate in the presence of sulfamic acid in tap water-alcohol solvents to afford amidosulfones, and the subsequent water two-phase basic elimination of the amidosulfones to N-tosyl arylimines, was developed. The process has little environmental impact, easy workup, mild reaction conditions, and good yields and is amenable to large-scale preparations.

  DOI：

  10.1080/00397910601131387

文献信息

• The azomethine ylide strategy for β-lactam synthesis. Azapenams and 1-azacephams
  作者：David Brown、Giles A. Brown、Mark Andrews、Jonathan M. Large、Dominique Urban、Craig P. Butts、Neil J. Hales、Timothy Gallagher

  DOI：10.1039/b203890k

  日期：——

  Reaction of the β-lactam-based oxazolidinone 5 with N-sulfonylimines provides the exo and endo azapenams 8 in 22–54% yield. The reactivity of 2H-azirines as 1,3-dipolarophiles towards β-lactam-based azomethine ylides derived from oxazolidinones 5 and 15 has also been evaluated. Azirines 11 and 12a provide cycloadducts 13a,b and 16 respectively, which incorporate the novel 2,6-diazatricyclo[4.2.0.02,4]octan-7-one ring system. These adducts were resistant towards C–N cleavage as the basis of an entry to 1-azacephams (1,5-diazabicyclo[4.2.0]octan-8-ones) 4. The use of the 3-(4-methoxyphenyl)-2H-azirine 19 provides a labile initial cycloadduct, which undergoes in situ ring-cleavage and further reaction to give the 2 ∶ 1 adduct 1-azacepham 22. The initial product is stable when 3-(4-nitrophenyl)-2H-azirine 23 is employed, and cycloadducts 24a and 24b are converted under mild reducing conditions to the 1-azacepham derivatives 25 and 26.

  β-内酰胺基恶唑啉酮5与N-磺酰亚胺反应生成外环和内环氮杂佩兰8，产率为22-54%。还评估了2H-氮杂环丙烷作为1,3-偶极亲偶极体与源自恶唑啉酮5和15的β-内酰胺基亚胺叶立德的反应活性。氮杂环丙烷11和12a分别生成含新型2,6-二氮杂三环[4.2.0.02,4]辛烷-7-酮环系的环加成物13a,b和16。这些加成物对C-N键断裂具有抗性，从而为获得1-氮杂头孢烷（1,5-二氮杂双环[4.2.0]辛烷-8-酮）4提供了途径。使用3-(4-甲氧苯基)-2H-氮杂环丙烷19得到了一个不稳定的初始环加成物，它通过原位环断裂和进一步反应生成2∶1加成物1-氮杂头孢烷22。当使用3-(4-硝基苯基)-2H-氮杂环丙烷23时，初始产物是稳定的，并且环加成物24a和24b在温和还原条件下转化为1-氮杂头孢烷衍生物25和26。
• Aza-heterocycles via copper-catalyzed, remote C–H desaturation of amines
  作者：Leah M. Stateman、Ross M. Dare、Alyson N. Paneque、David A. Nagib

  DOI：10.1016/j.chempr.2021.10.022

  日期：2022.1

  desaturation of amines. Inspired by the Hofmann-Löffler-Freytag (HLF) synthesis of five-membered pyrrolidines, we tackled the century-old challenge of synthesizing six-membered piperidines by H-atom transfer. Herein, we present a double, vicinal C–H oxidation by dual catalysis, entailing Ir photocatalytic initiation of 1,5-HAT by an N-centered radical and Cu-catalyzed interception of the C-centered radical

  大多数药物在五元或六元环中含有一个氮原子。为了快速获得这两种氮杂杂环化合物，我们试图开发一种远程 C-H 胺去饱和方法。受五元吡咯烷的 Hofmann-Löffler-Freytag (HLF) 合成的启发，我们解决了通过氢原子转移合成六元哌啶的百年挑战。在这里，我们提出了一个 双，通过双催化进行邻位 C-H 氧化，需要 Ir 光催化引发 1,5-HAT 由 N 中心自由基和 Cu 催化拦截 C 中心自由基以促进去饱和。通过这种机制，两个 C-H 键（δ 和 ε 到 N）被区域选择性地从烷基链的无偏、远程位置移除。超过 50 个实例说明了合成内部和末端 δ 乙烯基胺和氮杂杂环的效率、选择性、官能团耐受性和药用价值。机理实验探索了烷基铜中间体，以及 HAT 和消除步骤的动力学和区域选择性。
• Palladium-Catalyzed Addition of Arylboronic Acids to <i>N</i>-Tosylarylimines
  作者：Huayue Wu、Jiang Cheng、Qiang Zhang、Jiuxi Chen、Miaochang Liu、Changming Qin、Weike Su、Jinchang Ding

  DOI：10.1055/s-2008-1042932

  日期：2008.4

  Pd-catalyzed addition of arylboronic acids to N-tosyl­arylimines was described by employing easily prepared, air-stable aminophosphine ligands, cheap inorganic base, and common organic solvents, providing diarylmethylamine derivatives through one-pot synthesis in moderate to good yields. The efficiency of this reaction was demonstrated by the compatibility with nitro, trifluoro­methyl, fluoro, chloro, and methoxy groups. Moreover, rigorous exclusion of air/moisture is not required in these transformations.

  通过使用易于制备、空气稳定且价格低廉的氨基膦配体、廉价的碱和常见的溶剂，钯催化的芳基硼酸与N-甲磺酰芳基亚胺的加成反应，可在温和至良好产率下通过一锅法合成二芳基甲基胺衍生物。该反应的高效性体现在其对硝基、三氟甲基、氟、氯和甲氧基等官能团的兼容性。此外，这些转化过程并不严格要求无空气/水分的环境。
• Lewis Acid-Catalyzed CH Functionalization for Synthesis of Isoindolinones and Isoindolines
  作者：Bo Qian、Shengmei Guo、Chungu Xia、Hanmin Huang

  DOI：10.1002/adsc.201000556

  日期：2010.12.17

  The Lewis acid-catalyzed CH functionalization of 2-substituted azaarenes with N-sulfonylaldimines has been developed, which provides a rapid and efficient approach for synthesis of heterocycle-containing isoindolinones and isoindolines.

  已经开发了用N-磺酰基醛二胺的路易斯酸催化的2-取代的氮杂芳烃的CH官能化，其为合成含杂环的异吲哚啉酮和异吲哚啉提供了一种快速有效的方法。
• Lewis Base-Catalyzed Perfluoroalkylation of Carbonyl Compounds and Imines with (Perfluoroalkyl)trimethylsilane
  作者：Yoshikazu Kawano、Nobuya Kaneko、Teruaki Mukaiyama

  DOI：10.1246/bcsj.79.1133

  日期：2006.7

  Lewis base-catalyzed perfluoroalkylation of carbonyl compounds and aldimines with (perfluoroalkyl)trimethylsilanes (TMSCF3, TMSC2F5, and TMSC3F7) is described. The nitrogen- or oxygen-containing an...

  描述了路易斯碱催化羰基化合物和醛亚胺与（全氟烷基）三甲基硅烷（TMSCF3、TMSC2F5 和 TMSC3F7）的全氟烷基化。含氮或含氧...