N-(2,2-dichloropropylidene)propan-2-amine | 950850-88-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-(2,2-dichloropropylidene)propan-2-amine
• 英文别名: 2,2-dichloro-N-propan-2-ylpropan-1-imine
• CAS: 950850-88-1
• 化学式: C₆H₁₁Cl₂N
• 分子量: 168.066
• InChiKey: UUMWYRLXXKPSPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(2,2-dichloropropylidene)propan-2-amine 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 以89%的产率得到Isopropyl-2,2-dichlor-propylamin
  参考文献：
  名称：

  Synthesis and reactivity of alkenyl- and alkynyl-substituted β,β-dihalo-and β,β,β-trichloroamines

  摘要：

  beta,beta-Dihalo and beta,beta,beta-trichloroamines, obtained by Lewis acid-promoted Petasis-type reaction of alpha,alpha-dichlorinated and alpha,alpha,alpha-trichlorinated imines or reduction of alpha,alpha-dihaloaldimines, were subjected to a reactivity study and turned out to be remarkably stable compounds. In general, only the bases KO'Bu and NaOMe cause a 1,2-dehydrochlorination with formation of unsaturated alpha-chloroimines Or Unsaturated alpha,alpha-dichloroimines. Hydrolysis of the alpha-chloroimines with aqueous oxalic acid resulted in the formation of the corresponding unsaturated alpha-chloroketones. The reaction of simple beta,beta-dihaloamines with NaOMe and KO'Bu generated 2-haloprop-2-enylmines and 2,2-dimethoxypropylamines. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.01.034

文献信息

• An Indium(III)-Catalyzed Synthesis of 4,4-Dichloro-1-aryl-<i>N</i>-alkyl-1-yn-3-amines<i>via</i>an Intermolecular C(<i>sp</i>²)C(<i>sp</i>) Bond Formation
  作者：Chandi C. Malakar、Bert U. W. Maes、Kourosch Abbaspour Tehrani

  DOI：10.1002/adsc.201200680

  日期：2012.12.14

  This paper demonstrates an indium(III) triflate-catalyzed reaction of electron-deficient α,α-dichloroaldimines with terminal alkynes leading to a rapid and selective access to highly functionalized propargylic amines in good to excellent yields. The dichloromethylene moiety of the aldimine acts as an activating group to accomplish this transformation under very mild conditions.

  本文证明了缺电子的α，α-二氯醛亚胺与末端炔烃的三氟甲磺酸铟（III）催化反应可快速且选择性地获得高官能度的炔丙基胺，并具有良好的收率。该醛亚胺的二氯亚甲基部分充当活化基团，以在非常温和的条件下完成该转化。
• Metal-Free Synthesis of Chlorinated β-Amino Ketones<i>via</i>an Unexpected Reaction of Imines with Arylacetylenes in 1,1,1,3,3,3-Hexafluoro-2-propanol
  作者：Khushbu Kushwaha、Balazs Pinter、Syeda A. Shehzadi、Chandi C. Malakar、Christophe M. L. Vande Velde、Frank de Proft、Kourosch Abbaspour Tehrani

  DOI：10.1002/adsc.201500519

  日期：2016.1.7

  The metal‐free reaction of terminal arylacetylenes with α,α‐dichloroaldimines in 1,1,1,3,3,3‐hexafluoro‐2‐propanol as the sole solvent results in the rapid and selective formation of γ,γ‐dichloro‐β‐amino ketones. In this solvent the expected dichlorinated propargylamines and/or allylic amines are not formed. The dichloromethylene moiety of the aldimine acts as an activating group and is essential to

  末端芳基乙炔与α，α-二氯醛亚胺在1,1,1,3,3,3-六氟-2-丙醇中作为唯一溶剂的无金属反应导致γ，γ-二氯β-氨基酮。在该溶剂中，未形成预期的二氯化炔丙基胺和/或烯丙基胺。醛亚胺的二氯亚甲基部分用作活化基团，并且对于完成该转化是必不可少的。富电子乙炔导致最佳结果和工作以及与所有亚胺（具有或不α'-H在氮取代基），而缺电子乙炔仅与反应ñ -叔-丁基醛亚胺（无α'-H）。机理途径表明1,1,1,3,3,3-六氟-2-丙醇使醛亚胺质子化，该醛在速率确定步骤中将与芳基乙炔反应形成共振稳定的丙二烯阳离子，并被捕获通过HFIP分子产生烯醇醚，该烯醇醚迅速水解，仅提供β-氨基酮。使用DFT技术，我们发现第一个CC键形成步骤是速率确定步骤，并与约21 kcal mol -1的势垒相关。
• Lewis Acid Mediated Vinyl-Transfer Reaction of Alkynes to<i>N</i>-Alkylimines by Using the<i>N</i>-Alkyl Residue as a Sacrificial Hydrogen Donor
  作者：Chandi C. Malakar、Sara Stas、Wouter Herrebout、Kourosch Abbaspour Tehrani

  DOI：10.1002/chem.201300469

  日期：2013.10.11

  A variety of N‐alkyl‐α,α‐dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)3 or BF3⋅OEt2 and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β‐dichloroamines. This approach is complementary to previously reported transition‐metal‐catalyzed vinyl‐transfer methods, which

  各种ñ -烷基- α，α-dichloroaldimines通过终端炔乙烯基化在Lewis的存在酸如在（OTF）3或BF 3 ⋅ OET 2和六氟异丙醇（HFIP）作为添加剂。反应在环境温度下进行，并生成几何上纯净的烯丙基β，β-二氯胺。这种方法是对先前报道的过渡金属催化的乙烯基转移方法的补充，后者不适用于脂族亚胺，仅限于含有吸电子氮取代基的亚胺。在本方法中，末端炔烃用作乙烯基残基的来源，而N亚胺的烷基部分起着牺牲氢供体的作用。该方法的另一个优点是不需要使用外部有毒或有害的还原剂或分子氢的事实。这种新方法很好地结合了C（sp 2）C（sp）键的形成，氢化物转移以及未活化的CN键的异常裂解，从而产生了功能化的伯烯丙基胺。进行了详细的实验研究，并通过DFT对该机制进行了计算。
• Synthesis and reactivity of alkenyl- and alkynyl-substituted β,β-dihalo-and β,β,β-trichloroamines
  作者：Kourosch Abbaspour Tehrani、Sara Stas、Bart Lucas、Norbert De Kimpe

  DOI：10.1016/j.tet.2009.01.034

  日期：2009.3

  beta,beta-Dihalo and beta,beta,beta-trichloroamines, obtained by Lewis acid-promoted Petasis-type reaction of alpha,alpha-dichlorinated and alpha,alpha,alpha-trichlorinated imines or reduction of alpha,alpha-dihaloaldimines, were subjected to a reactivity study and turned out to be remarkably stable compounds. In general, only the bases KO'Bu and NaOMe cause a 1,2-dehydrochlorination with formation of unsaturated alpha-chloroimines Or Unsaturated alpha,alpha-dichloroimines. Hydrolysis of the alpha-chloroimines with aqueous oxalic acid resulted in the formation of the corresponding unsaturated alpha-chloroketones. The reaction of simple beta,beta-dihaloamines with NaOMe and KO'Bu generated 2-haloprop-2-enylmines and 2,2-dimethoxypropylamines. (C) 2009 Elsevier Ltd. All rights reserved.