N-benzyl-2,2,2-trichloro-N-(2-cyclohex-2-enyl)acetamide | 145593-40-4

• 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: N-benzyl-2,2,2-trichloro-N-(2-cyclohex-2-enyl)acetamide
• 英文别名: N-benzyl-2,2,2-trichloro-N-cyclohex-2-en-1-yl-acetamide；N-benzyl-2,2,2-trichloro-N-cyclohex-2-en-1-ylacetamide
• CAS: 145593-40-4
• 化学式: C₁₅H₁₆Cl₃NO
• 分子量: 332.657
• InChiKey: BTTMRZRKCRCPQK-UHFFFAOYSA-N

物化性质

• 沸点：
  409.4±45.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-2,2,2-trichloro-N-(2-cyclohex-2-enyl)acetamide 在 copper diacetate 、 镍 、 溶剂黄146 作用下， 以 叔丁醇 为溶剂， 反应 24.0h， 生成 1-苄基-3H-吲哚-2-酮
  参考文献：
  名称：

  Cassayre, Jérôme; Dauge, Delphine; Zard, Samir Z., Synlett, 2000, # 4, p. 471 - 474

  摘要：

  DOI：
• 作为产物：
  描述：

  cyclohex-2-enyl methyl carbonate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 三乙胺 、 三苯基膦 作用下， 以 乙醚 、 乙腈 为溶剂， 生成 N-benzyl-2,2,2-trichloro-N-(2-cyclohex-2-enyl)acetamide
  参考文献：
  名称：

  Transition metal-catalyzed radical cyclizations: a low-temperature process for the cyclization of N-protected N-allyltrichloroacetamides to trichlorinated .gamma.-lactams and application to the stereoselective preparation of .beta.,.gamma.-disubstituted .gamma.-lactams

  摘要：

  Cyclizations of N-substituted N-allyltrichloroacetamides, where the substituent is an alkyl, Cbz, Boc, Ts, or Ms group, are catalyzed by a 1:1 mixture of CuCl and bipyridine to give the corresponding beta,gamma-trichlorinated gamma-lactams in high yields. The reactions proceed at temperatures from -78-degrees-C to room temperature. Cyclizations of N-allyltrichloroacetamides of acyclic secondary allylic amines are achieved with good selectivity; the cis/trans ratios of the gamma-lactams formed were dependent on the substituents on the nitrogen atom. The stereochemical outcome is compared with that of free-radical cyclization.

  DOI：

  10.1021/jo00054a034

文献信息

• Synthesis of α-Chlorolactams by Cyanoborohydride-Mediated Radical Cyclization of Trichloroacetamides
  作者：Guilhem Coussanes、Harald Jakobi、Stephen Lindell、Josep Bonjoch

  DOI：10.1002/chem.201800210

  日期：2018.6.7

  A cyanoborohydride‐promoted radical cyclization methodology has been developed to access α‐chlorolactams in a simple and efficient way using NaBH3CN and trichloroacetamides easily available from allylic and homoallylic secondary amines. This methodology allowed the synthesis of a library of α‐chlorolactams (mono‐ and bicyclic), which were tested for herbicidal activity, trans‐3‐chloro‐4‐methyl‐1‐(

  已开发出一种氰基硼氢化物促进的自由基环化方法，可使用NaBH 3 CN和三氯乙酰胺（可从烯丙基和均烯丙基仲胺中轻松获得）以简单有效的方式获得α-氯内酰胺。这种方法学允许合成α-氯内酰胺（单环和双环）文库，并对其除草活性进行了测试，反式-3-氯-4-甲基-1-（3-三氟甲基）苯基-2-吡咯烷酮是最活跃。
• Stereoselective preparation of bicyclic lactams by copper- or ruthenium-catalysed cyclization of N-allyltrichloroacetamides: a novel entry to pyrrolidine alkaloid skeletons
  作者：Hideo Nagashima、Ken-ichi Ara、Hidetoshi Wakamatsu、Kenji Itoh

  DOI：10.1039/c39850000518

  日期：——

  Cyclization of certain N-allyltrichloroacetamides provides a stereoselective method for several bicyclic lactams.

  某些N-烯丙基三氯乙酰胺的环化为几种双环内酰胺提供了立体选择方法。
• A versatile radical based synthesis of γ—lactams using nickel powder / acetic acid
  作者：Jean Boivin、Mohammed Yousfi、Samir Z. Zard

  DOI：10.1016/s0040-4039(00)77265-0

  日期：1994.8

  A variety of γ—lactams are obtained from suitable of α-haloamides by a radical cyclisation mediated by a combination of nickel powder and acetic acid.

  通过由镍粉和乙酸的组合介导的自由基环化，可以从合适的α-卤代酰胺中获得各种γ-内酰胺。
• Functional rearrangement of 3-Cl or 3,3-diCl-γ-lactams bearing a secondary 1-chloroalkyl substituent at C-4
  作者：Mariella Pattarozzi、Fabrizio Roncaglia、Luca Accorsi、Andrew F. Parsons、Franco Ghelfi

  DOI：10.1016/j.tet.2009.11.111

  日期：2010.2

  The study of the reaction with MeONa/MeOH of chlorinated gamma-lactams. prepared from the atom transfer radical cyclization of N-allyl-alpha-perchloroamides, has been extended to the case of substiates carrying an exo halogen atom on a branched carbon Only with secondary exo C-Cl groups, that are not located on a fused ring, does the functional rearrangement follow the typical transformation route, Which With trichloro-lactams can proceed further to give 4-alkylidene derivatives From a practical point of view, the outcome of the reaction with di- or trichloio N-cinnamylamides is synthetically valuable, affording the 5-methoxy-IH-pyrrol-2(5H)-one or 3-benzylidenepyrrlidine-2.5-dione. respectively. in good to excellent yield (C) 2009 Elsevier Ltd All rights reserved
• A green way to γ-lactams through a copper catalyzed ARGET-ATRC in ethanol and in the presence of ascorbic acid
  作者：Roberto Casolari、Fulvia Felluga、Vincenzo Frenna、Franco Ghelfi、Ugo M. Pagnoni、Andrew F. Parsons、Domenico Spinelli

  DOI：10.1016/j.tet.2010.11.025

  日期：2011.1

  A 'green' ARGET-ATRC, for the CuCl[PMDETA] catalysed cyclo-isomerization of N-allyl-alpha-polychloroamides to gamma-lactams is described. The process works efficiently (yields 78-96%), uses a bio-solvent, as ethanol, and exploits the reducing feature of ascorbic acid to limit, at a low level (2-4%), the amount of catalyst. To preserve the efficacy of the catalytic cycle, addition of Na2CO3 is essential, which quenches the HCl released during the CuCl[PMDETA] regeneration step. Profitable features of the process are: mild reaction temperatures (25-37 degrees C), relatively short reaction times (usually 5 h) and low solvent volumes (2 mmol of substrate/mL of ethanol). The method, upon stoichiometric adjustment, was also used for the synthesis of alpha,beta-unsaturated-gamma-lactams from N-(2-chloroallyl)-alpha-polychloroamides, via a tandem process involving an ATRC and a reductive [1,2]-elimination. (C) 2010 Elsevier Ltd. All rights reserved.