2,2,2-三氯-n-(1,5-二甲基-1-乙烯基-4-己烯)乙酰胺 | 51479-78-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 2,2,2-三氯-n-(1,5-二甲基-1-乙烯基-4-己烯)乙酰胺
• 英文名称: 3,7-dimethyl-3-trichloroacetamido-1,6-octadiene
• 英文别名: 2,2,2-trichloro-N-(3,7-dimethylocta-1,6-dien-3-yl)acetamide
• CAS: 51479-78-8
• 化学式: C₁₂H₁₈Cl₃NO
• 分子量: 298.64
• InChiKey: OMJPNRPQUNHMOS-UHFFFAOYSA-N

物化性质

• 沸点：
  362.2±42.0 °C(Predicted)
• 密度：
  1.169±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2,2-三氯-n-(1,5-二甲基-1-乙烯基-4-己烯)乙酰胺 在 sodium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 3-isocyanato-3,7-dimethylocta-1,6-diene
  参考文献：
  名称：

  One-Pot Transformation of Trichloroacetamide into Readily Deprotectable Carbamates

  摘要：

  A trichloroacetamide group was converted to an isocyanate, which was in situ captured by a variety of alcohols in the presence of CuCl and n-BuN4Cl to afford the corresponding carbamates. The scope and limitation of this transformation are also described.

  DOI：

  10.1021/ol061123c
• 作为产物：
  描述：

  香叶醇 在 mercury(II) trifluoroacetate 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 2,2,2-三氯-n-(1,5-二甲基-1-乙烯基-4-己烯)乙酰胺
  参考文献：
  名称：

  A general method for the synthesis of amines by the rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions

  摘要：

  DOI：

  10.1021/ja00426a038

文献信息

• Allyl, epoxy and glycosyl perfluoroimidates. One-pot preparation and reaction
  作者：Noriyuki Nakajima、Miho Saito、Masabumi Kudo、Makoto Ubukata

  DOI：10.1016/s0040-4020(02)00305-8

  日期：2002.4

  obtained trifluoroacetimidates were more stable than the trichloro analogue and were easily purified by SiO2 column chromatography and/or distillation. The 3,3-sigmatropic rearrangement of allylic analogues, acid-catalyzed cyclization of the epoxy analogues and glycosylation of sugar analogues were studied comparing with their corresponding trichloroacetimidates. The trifluoroacetimidates were considerably

  描述了烯丙基，环氧和糖基全氟亚氨酸的一锅法制备及其反应。挥发性全氟腈是在-78°C下由具有“活化”二甲基亚砜（DMSO）物种的全氟酰胺生成的。将醇和糖衍生物原位亲核加成腈后，可以制备44-92％的烯丙基，环氧和糖基全氟亚氨酸酯。所获得的三氟乙酰亚氨酸盐比三氯类似物更稳定，并且易于通过SiO 2纯化。柱色谱法和/或蒸馏。与它们相应的三氯乙酰亚胺比较，研究了烯丙基类似物的3,3-σ重排，环氧类似物的酸催化环化和糖类似物的糖基化。由于三氟乙酰基亚胺在亚氨酸酯碳上的吸电子取代基，因此它们的反应性明显低于三氯乙酰基亚胺。
• Directed Dihydroxylation of Cyclic Allylic Alcohols and Trichloroacetamides Using OsO₄/TMEDA
  作者：Timothy J. Donohoe、Kevin Blades、Peter R. Moore、Michael J. Waring、Jon J. G. Winter、Madeleine Helliwell、Nicholas J. Newcombe、Geoffrey Stemp

  DOI：10.1021/jo026161y

  日期：2002.11.1

  The oxidation of a range of cyclic allylic alcohols and amides with OsO4/TMEDA is presented. Under these conditions, hydrogen bonding control leads to the (contrasteric) formation of the syn isomer in almost every example that was examined. Evidence for the bidentate binding of TMEDA to OsO4 is presented and a plausible mechanism described.

  介绍了用OsO4 / TMEDA氧化一系列环状烯丙醇和酰胺的方法。在这些条件下，几乎在每个所研究的实施例中，氢键控制导致顺式异构体的（对映体）形成。提供了TMEDA与OsO4的双齿结合的证据，并描述了一个可能的机制。
• New synthetic route of guanidine from trichloroacetamide for tetrodotoxin and its related compounds
  作者：Toshio Nishikawa、Norio Ohyabu、Noboru Yamamoto、Minoru Isobe

  DOI：10.1016/s0040-4020(99)00140-4

  日期：1999.4

  Trichloroacetamide was transformed into dibenzylguanidinium salt in three steps. Attempted debenzylation was very difficult in the guanidinium form even under high pressure hydrogen and high temperature conditions. On the other hand, the benzyl groups on acetylated guanidine were easily deprotected by hydrogenolysis under 1 atm of hydrogen. These methods were applied to the syntheses of tetrodotoxin-related

  通过三个步骤将三氯乙酰胺转化为二苄基胍盐。即使在高压氢气和高温条件下，胍基形式的脱苄基尝试也非常困难。另一方面，乙酰化胍上的苄基在1atm的氢气下容易通过氢解脱保护。这些方法被用于河豚毒素相关化合物的合成。
• Direct Preparation of Guanidine from Trichloroacetamide. A Potentially Important Method to (−)-Tetrodotoxin
  作者：Noboru Yamamoto、Minoru Isobe

  DOI：10.1246/cl.1994.2299

  日期：1994.12

  Trichloroacetamides obtained via Overman [3,3] sigmatropic rearrangement were converted into dibenzyl guanidines. The key step was conversion of carbodiimide intermediate into guanidine by scandium or ytterbium trifluoromethane-sulfonates. This method was applied to a synthesis of guanidinium ring of (−)-tetrodotoxin.

  通过 Overman [3,3] sigmatropic 重排获得的三氯乙酰胺被转化为二苄基胍。关键步骤是通过三氟甲烷磺酸钪或镱将碳二亚胺中间体转化为胍。这种方法被应用于合成 (-)- 河豚毒素的胍环。
• Transition metal catalyzed radical cyclization: new preparative route to .gamma.-lactams from allylic alcohols via the [3.3]-sigmatropic rearrangement of allylic trichloroacetimidates and the subsequent ruthenium-catalyzed cyclization of N-allyltrichloroacetamides
  作者：Hideo Nagashima、Hidetoshi Wakamatsu、Nobuyasu Ozaki、Tsutomu Ishii、Masakazu Watanabe、Tomonori Tajima、Kenji Itoh

  DOI：10.1021/jo00032a016

  日期：1992.3

  A sequence of reactions including [3.3]-sigmatropic rearrangement of allyl trichloroacetimidates (Overman rearrangement) followed by ruthenium-catalyzed cyclization of N-allyltrichloroacetamides provided a novel method for preparing trichlorinated gamma-lactams from allylic alcohols. No delta-lactam was formed as a byproduct. The cyclization of secondary N-allyltrichloroacetamides proceeded with good diastereoselectivity. Two types of tandem cyclizations to form bicyclic lactams took place in the cyclization of N-allyltrichloroacetamides from geraniol and linalool.