4-phenyl-N-tosyl-1-(trifluoromethyl)-3-butenylamine | 235418-60-7

• 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: 4-phenyl-N-tosyl-1-(trifluoromethyl)-3-butenylamine
• 英文别名: N-<4-phenyl-1-(trifluoromethyl)-3-butenyl>tosylamide；(E)-N-[4-phenyl-1-(trifluoromethyl)-3-butenyl]tosylamide；4-methyl-N-[(E)-1,1,1-trifluoro-5-phenylpent-4-en-2-yl]benzenesulfonamide
• CAS: 235418-60-7
• 化学式: C₁₈H₁₈F₃NO₂S
• 分子量: 369.408
• InChiKey: WWDZXXIRJWAKEV-VMPITWQZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  54.6
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-phenyl-N-tosyl-1-(trifluoromethyl)-3-butenylamine 在 高氯酸 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以100%的产率得到cis-2-phenyl-N-tosyl-5-(trifluoromethyl)pyrrolidine
  参考文献：
  名称：

  Synthesis of α-(Trifluoromethyl)pyrrolidines by Cyclization of N-Tosyl-α-(trifluoromethyl)homoallylamine Derivatives

  摘要：

  Treatment of N-tosyl-alpha-(trifluoromethyl)homoallylamines (4), obtained by the ene type reaction of N-(2,2,2-trifluoro-1-ethoxyethyl)tosylamide (3), with a protic acid afforded N-tosyl-a-(trifluoromethyl)pyrrolidine derivatives (5 and 6). For example, 4-phenyl-N-tosyl-1-(trifluoromethyl)-3-butenylamine (4a) gave cis- and trans-2-phenyl-N-tosyl-5-(trifluoromethyl (5a and de). Interestingly, 6a was a major product in a moderate reaction condition, while 5a was a major product in more drastic conditions. The mechanism of these reactions is speculated. Treatment of 4a with iodine in the presence of sodium hydrogencarbonate brought about iodocyclization to give 3-iodo-2-phenyl-5-(trifluoromethyl)-N-tosylpyrrolidines (7 and 8).

  DOI：

  10.3987/com-00-s(i)80
• 作为产物：
  描述：

  烯丙苯 、 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， 以70%的产率得到4-phenyl-N-tosyl-1-(trifluoromethyl)-3-butenylamine
  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

文献信息

• 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。
• 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。
• Synthesis of α-(Trifluoromethyl)pyrrolidines by Cyclization of N-Tosyl-α-(trifluoromethyl)homoallylamine Derivatives
  作者：Itsumaro Kumadaki、Shuichi Jonoshita、Kazuyuki Sato、Masaaki Omote、Akira Ando

  DOI：10.3987/com-00-s(i)80

  日期：——

  Treatment of N-tosyl-alpha-(trifluoromethyl)homoallylamines (4), obtained by the ene type reaction of N-(2,2,2-trifluoro-1-ethoxyethyl)tosylamide (3), with a protic acid afforded N-tosyl-a-(trifluoromethyl)pyrrolidine derivatives (5 and 6). For example, 4-phenyl-N-tosyl-1-(trifluoromethyl)-3-butenylamine (4a) gave cis- and trans-2-phenyl-N-tosyl-5-(trifluoromethyl (5a and de). Interestingly, 6a was a major product in a moderate reaction condition, while 5a was a major product in more drastic conditions. The mechanism of these reactions is speculated. Treatment of 4a with iodine in the presence of sodium hydrogencarbonate brought about iodocyclization to give 3-iodo-2-phenyl-5-(trifluoromethyl)-N-tosylpyrrolidines (7 and 8).