N-(2,2,2-trifluoro-1-ethoxyethyl)tosylamide | 235418-62-9

• 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-(2,2,2-trifluoro-1-ethoxyethyl)tosylamide
• 英文别名: N-(1-ethoxy-2,2,2-trifluoroethyl)-4-methylbenzenesulfonamide
• CAS: 235418-62-9
• 化学式: C₁₁H₁₄F₃NO₃S
• 分子量: 297.298
• InChiKey: DIRYILMZNIZBOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  63.8
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  正癸烯 、 N-(2,2,2-trifluoro-1-ethoxyethyl)tosylamide 在 四氯化钛 、 sodium hydride 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 以86%的产率得到N-<1-(trifluoromethyl)-3-undecenyl>tosylamide
  参考文献：
  名称：

  N-（对甲苯磺酰基）三氟乙醛亚胺的烯型反应合成有机氟化合物

  摘要：

  N-甲苯磺酰基三氟乙醛亚胺（4）作为亲热剂反应，但是它对水分非常敏感并且烯产物的收率很低。发现N-（2,2,2-三氟-1-乙氧基乙基）甲苯磺酰胺（11），是通过三氟乙醛乙基半缩醛（1）与甲苯磺酰胺（3）在TiCl 4的存在下反应，然后添加乙醇而获得的可以作为4的良好替代物进行反应，从而以更好的收率得到4的烯反应得到的相同产物。

  DOI：

  10.1016/s0022-1139(99)00027-5
• 作为产物：
  描述：

  对甲苯磺酰胺 、 1-乙氧基-2,2,2-三氟乙醇 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以25%的产率得到1,1,1-Trifluor-2-p-toluolsulfonamino-2-hydroxy-ethan
  参考文献：
  名称：

  Diastereoselective synthesis of trans-trifluoromethyl-β-lactams and α-alkyl-β-trifluoromethyl-β-amino esters

  摘要：

  The diastereoselective synthesis of beta-lactams was examined from N-tosyl-1-chloro-2,2,2-trifluoroethylamine 3 and various nonactivated aliphatic acid chlorides in the presence of a Bronsted base. The mild reaction conditions allowed to get trifluoromethyl-beta-lactams in good yields with high trans-diastereo selectivity. In addition, we also demonstrated that ring-opening of beta-lactams easily provided alpha-alkyl-beta-trifluoromethyl-beta-amino esters. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.03.001

文献信息

• One-Pot Three-Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination
  作者：Ugo Orcel、Jerome Waser

  DOI：10.1002/anie.201607318

  日期：2016.10.4

  A synthesis of vicinal diamines via in situ aminal formation and carboamination of allyl amines is reported. Employing highly electron‐poor trifluoromethyl aldimines in their stable hemiaminal form was key to enable both a fast and complete aminal formation as well as the palladium‐catalyzed carboamination step. The conditions developed allow the introduction of a wide variety of alkynyl, vinyl, aryl

  据报道，邻位二胺通过原位氨基形成和烯丙基胺的碳氨化而合成。采用稳定的血红素形式的高度贫电子的三氟甲基亚胺是实现快速，完整的氨基形成以及钯催化的碳氨化步骤的关键。所开发的条件允许引入具有完全区域选择性和高非对映选择性的各种炔基，乙烯基，芳基和杂芳基。该反应表现出较高的官能团耐受性。重要的是，咪唑烷产物中的任何一个氮原子都可以被选择性地脱保护，而在温和的条件下一步一步去除氨基链则可以显示出游离的二胺。我们希望这项工作将促进在有机合成中进一步使用混合的氨基系链。
• Synthesis of Organofluorine Compounds Using the Ene Reaction of N-(p-Toluenesulfonyl)trifluoroacetaldehyde Imine.
  作者：Shuichi JONOSHITA、Atsuhiro HARADA、Masaaki OMOTE、Akira ANDO、Itsumaro KUMADAKI

  DOI：10.1248/cpb.47.656

  日期：——

  N-Tosyltrifluoroacetaldehyde imine (4) reacted with terminal olefins by only heating together to give the ene reactin products. This means the imine is much more reactive than trifluoroacetaldehyde (2) itself as an enophile. However, 4 was very sensitive to moisture and the yields were low even if it was used without isolation. Further, it did not react with non-terminal olefins. In the course on study of the mechanism of this reaction, we found that N-(2, 2, 2-trifluoro-1-ethoxyethyl)tosylamide (12), obtained by the reaction of trifluoroacetaldehyde ethyl hemiacetal (1) with tosylamide (3) in the presence of titanium(IV) chloride followed by addition of ethanol, reacted in the presence of sodium hydride and titanium(IV) chloride to give the same products from the ene reaction of 4 in much better yields. Interestingly, this reaction proceeded with non-terminal olefins.

  N-Tosyltrifluoroacetaldehyde亚胺（4）仅通过加热即可与末端烯烃反应，生成烯反应产物。这意味着作为亲电试剂，该亚胺比三氟乙醛（2）本身更具反应活性。然而，4对湿气非常敏感，即使不经分离使用，产率也很低。此外，它不与非末端烯烃反应。在研究该反应机理的过程中，我们发现，通过三氟乙醛乙基半缩醛（1）与甲苯磺酰胺（3）在四氯化钛存在下反应，随后加入乙醇得到的N-(2,2,2-三氟-1-乙氧基乙基)甲苯磺酰胺（12），在氢化钠和四氯化钛存在下反应，以更高产率得到与4进行烯反应相同的产物。有趣的是，此反应还能与非末端烯烃进行反应。
• Expedient Synthesis of Perhaloaldehyde N-Acyl Hemiaminals
  作者：Laurent Ingrassia

  DOI：10.1055/s-1999-3586

  日期：1999.10
• Synthesis of organofluorine compounds using ene type reaction of N-(p-toluenesulfonyl)trifluoroacetaldehyde imine
  作者：Itsumaro Kumadaki、Shuichi Jonoshita、Atsuhiro Harada、Masaaki Omote、Akira Ando

  DOI：10.1016/s0022-1139(99)00027-5

  日期：1999.7

  very sensitive to moisture and the yields of ene products were low. N-(2,2,2-Trifluoro-1-ethoxyethyl)tosylamide (11), obtained by the reaction of trifluoroacetaldehyde ethyl hemiacetal (1) with tosylamide (3) in the presence of TiCl4 followed by addition of ethanol, was found to react as a good substitute for 4 to give the same products from the ene reaction of 4 in much better yields.

  N-甲苯磺酰基三氟乙醛亚胺（4）作为亲热剂反应，但是它对水分非常敏感并且烯产物的收率很低。发现N-（2,2,2-三氟-1-乙氧基乙基）甲苯磺酰胺（11），是通过三氟乙醛乙基半缩醛（1）与甲苯磺酰胺（3）在TiCl 4的存在下反应，然后添加乙醇而获得的可以作为4的良好替代物进行反应，从而以更好的收率得到4的烯反应得到的相同产物。
• Diastereoselective synthesis of trans-trifluoromethyl-β-lactams and α-alkyl-β-trifluoromethyl-β-amino esters
  作者：Vitaliy Petrik、Gerd-Volker Röschenthaler、Dominique Cahard

  DOI：10.1016/j.tet.2011.03.001

  日期：2011.5

  The diastereoselective synthesis of beta-lactams was examined from N-tosyl-1-chloro-2,2,2-trifluoroethylamine 3 and various nonactivated aliphatic acid chlorides in the presence of a Bronsted base. The mild reaction conditions allowed to get trifluoromethyl-beta-lactams in good yields with high trans-diastereo selectivity. In addition, we also demonstrated that ring-opening of beta-lactams easily provided alpha-alkyl-beta-trifluoromethyl-beta-amino esters. (C) 2011 Elsevier Ltd. All rights reserved.