1-[2-Dichloromethyl-5,5-dimethyl-3-(toluene-4-sulfonyl)-4,5-dihydro-3H-imidazol-4-yl]-ethanone | 405518-83-4

• 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: 1-[2-Dichloromethyl-5,5-dimethyl-3-(toluene-4-sulfonyl)-4,5-dihydro-3H-imidazol-4-yl]-ethanone
• 英文别名: 1-[2-(dichloromethyl)-5,5-dimethyl-3-(4-methylphenyl)sulfonyl-4H-imidazol-4-yl]ethanone
• CAS: 405518-83-4
• 化学式: C₁₅H₁₈Cl₂N₂O₃S
• 分子量: 377.292
• InChiKey: YYICFUHYMJRRTA-UHFFFAOYSA-N

物化性质

• 熔点：
  95-97 °C(Solv: acetonitrile (75-05-8))
• 沸点：
  470.6±55.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  75.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-[2-Dichloromethyl-5,5-dimethyl-3-(toluene-4-sulfonyl)-4,5-dihydro-3H-imidazol-4-yl]-ethanone 在 盐酸 作用下， 以 氯仿 为溶剂， 反应 0.5h， 以94%的产率得到2,2-Dichloro-N-[1,1-dimethyl-3-oxo-2-(toluene-4-sulfonylamino)-butyl]-acetamide
  参考文献：
  名称：

  Novel imidazolination reaction of alkenes provides an easy access to new α,β-differentiated 1,2-vicinal diamines

  摘要：

  α,β-分化的1,2-邻二胺已通过新型电亲核咪唑化反应高效合成。咪唑啉的水解是在70°C下使用6 M HCl在THF中处理完成的，且没有发生表异构化。研究中考察了八个例子，产率良好至优异（87-96%）。

  DOI：

  10.1039/b305149h
• 作为产物：
  描述：

  二氯胺T 、 4-甲基-3戊烯-2-酮 、 乙腈 在 dirhodium(II) tetrakis(perfluorobutyrate) 作用下， 反应 44.0h， 以82%的产率得到1-[2-Dichloromethyl-5,5-dimethyl-3-(toluene-4-sulfonyl)-4,5-dihydro-3H-imidazol-4-yl]-ethanone
  参考文献：
  名称：

  烯烃的新型亲电子化反应。

  摘要：

  三组分亲电反应将烯烃转化为咪唑啉和二胺衍生物。七氟丁酸铑（II）二聚物（2mol％）用作催化剂，N，N-二氯对甲苯磺酰胺（TsNCl 2）和乙腈作为氮源。获得了中等至良好的产率（45-82％）以及高的区域选择性和立体选择性。

  DOI：

  10.1002/1521-3773(20011119)40:22<4277::aid-anie4277>3.0.co;2-i

文献信息

• Electrophilic Diamination of Alkenes by Using FeCl₃−PPh₃ Complex as the Catalyst
  作者：Han-Xun Wei、Sun Hee Kim、Guigen Li

  DOI：10.1021/jo0200769

  日期：2002.7.1

  electrophilic diamination reaction of electron-deficient alkenes. Improvements on yields and stereoselectivity have been achieved for both alpha,beta-unsaturated carboxylic esters and ketones. Under the new catalytic system, alpha,beta-unsaturated carboxylic esters were found to be superior to their ketone counterparts, which is opposite to the previous (C(3)F(7)CO(2))(2)Rh](2)-catalyzed diamination. The reaction

  FeCl（3）-PPh（3）络合物被发现可以有效地催化缺电子烯烃的亲电子重整反应。对于α，β-不饱和羧酸酯和酮，已经实现了产率和立体选择性的提高。在新的催化体系下，发现α，β-不饱和羧酸酯优于它们的酮对应物，这与以前的（C（3）F（7）CO（2））（2）Rh]（2 ）催化的金属化。该反应采用现成的N，N-二氯对甲苯磺酰胺（TsNCl（2））和乙腈作为氮源，并且在室温下非常容易进行，而无需特殊保护惰性气体。所得的二氨基产物属于咪唑烷类似物，并且可以进一步增强新反应的重要性。
• The Combination of TsNH2 and NCS as Nitrogen and Chlorine Sources for Direct Diamination of Enones
  作者：Cody Timmons、Dianjun Chen、Xin Xu、Guigen Li

  DOI：10.1002/ejoc.200300326

  日期：2003.10

  observation of any haloamines. The reaction employs the readily available inexpensive combination of NCS and TsNH2 as an electrophilic nitrogen source, and three nitriles as nucleophilic nitrogen sources. A novel mechanism involving the formation of aziridinium intermediates from the reaction of TsNHCl with olefins and a new [2+3] cyclic addition for aziridinim ring opening has been proposed for the

  在没有观察到任何卤胺的情况下，已经实现了烯酮的区域选择性、立体选择性和化学选择性二胺化。该反应使用易于获得的 NCS 和 TsNH2 的廉价组合作为亲电子氮源，以及三个腈作为亲核氮源。已经提出了一种新的机制，涉及从 TsNH4Cl 与烯烃的反应形成氮丙啶中间体，并提出了一种新的 [2+3] 环加成来进行氮丙啶开环，用于烯烃的亲电二胺化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Direct Electrophilic Diamination of Functionalized Alkenes without the Use of Any Metal Catalysts
  作者：Dianjun Chen、Cody Timmons、Han-Xun Wei、Guigen Li

  DOI：10.1021/jo030098a

  日期：2003.7.1

  A new direct electrophilic diamination reaction of alpha,beta-unsaturated ketones and esters has been established without the use of any metal catalysts. Three types of nitriles (CH3CN, CH3CH2CN, and CH3CH2CH2CN) were employed as nucleophilic nitrogen sources. A new mechanism has also been proposed to explain the resulting regio- and stereoselectivity.
• Organocatalyzed regio- and stereoselective diamination of functionalized alkenes
  作者：Hui Wu、Xiaoyun Ji、Hao Sun、Guanghui An、Jianlin Han、Guigen Li、Yi Pan

  DOI：10.1016/j.tet.2010.04.054

  日期：2010.6

  The first organocatalyzed diamination reaction of alkenes with N,N-dichlorotoluenesulfonamide (TsNCl2) and acetonitrile as nitrogen sources was reported. The catalytic diamination reaction was convenient to carry out, resulting in imidazoline products with good yields and excellent regio- and stereoselectivities. Several other organic molecules were also tried as catalyst for this reaction and good results were achieved. A new one-pot synthesis of vicinal diamines via the current PPh3-catalyzed diamination and the hydrolysis of resulting imidazoline products with SnCl4 as promoter was also established. (C) 2010 Elsevier Ltd. All rights reserved.
• A Novel Electrophilic Diamination Reaction of Alkenes
  作者：Guigen Li、Han-Xun Wei、Sun Hee Kim、Michael D. Carducci

  DOI：10.1002/1521-3773(20011119)40:22<4277::aid-anie4277>3.0.co;2-i

  日期：2001.11.19

  A three-component electrophilic reaction transforms olefins into imidazoline and diamine derivatives. Rhodium(II) heptafluorobutyrate dimer (2 mol %) was utilized as the catalyst and N,N-dichloro-p-toluenesulfonamide (TsNCl2 ) and acetonitrile as the nitrogen sources. Modest to good yields (45-82 %) and high regio- and stereoselectivity were achieved.

  三组分亲电反应将烯烃转化为咪唑啉和二胺衍生物。七氟丁酸铑（II）二聚物（2mol％）用作催化剂，N，N-二氯对甲苯磺酰胺（TsNCl 2）和乙腈作为氮源。获得了中等至良好的产率（45-82％）以及高的区域选择性和立体选择性。