1-isopropylamino-7-isopropylimino-1,3,5-cycloheptatriene | 3337-06-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-isopropylamino-7-isopropylimino-1,3,5-cycloheptatriene
• 英文别名: N-isopropyl-2-(isopropylamino)(troponimine)；N-isopropyl-2-(isopropylamino)troponiminate；N-isopropyl-2-(isopropylamino)troponimine；N-isopropyl-2-(isopropylimino)troponimine；N,N′-diisopropylaminotroponimine；2-isopropylamino-N-isopropyltroponimine；N-propan-2-yl-7-propan-2-yliminocyclohepta-1,3,5-trien-1-amine
• CAS: 3337-06-2
• 化学式: C₁₃H₂₀N₂
• mdl: MFCD01855326
• 分子量: 204.315
• InChiKey: AELLFKPPLQHPRV-UHFFFAOYSA-N

物化性质

• 熔点：
  62 °C
• 沸点：
  104-106 °C(Press: 0.35 Torr)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.461
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-isopropylamino-7-isopropylimino-1,3,5-cycloheptatriene 在 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以52%的产率得到2-chloro-1,3-diisopropyl-2,3-dihydrocyclohepta[d][1,3,2]diazaphosphol-1-ium chloride
  参考文献：
  名称：

  N,N′ and N,O chelated phosphenium cations containing aminotroponiminate or aminotroponate units

  摘要：

  New phosphenium cations stabilized by bidentate monoanionic N-isopropyl-2-(isopropylamino)troponiminate or 2-(isopropylamino)troponate units have been synthesized. These complexes were characterized by P-31, H-1 and C-13 NMR spectroscopies, and the molecular structures were determined by X-ray crystallography. These data indicate the formation of N,N'- and N,O-chelate derivatives having three-coordinate phosphorous atoms included in planar heterobicycles. Moreover, computational studies support the presence of high delocalization of the positive charge into the pi-conjugated carbon backbone and of the high-lying phosphorus lone-pair orbital. (c) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.01.022
• 作为产物：
  描述：

  cyclohepta<1,4>benzoxazine 以21%的产率得到
  参考文献：
  名称：

  Mimata Yuzo, Saisho Tomoko, Hamada Masaharu, Imafuku Kimiaki, J. Chem. Res. Synop, (1995) N 4, S 156

  摘要：

  DOI：

文献信息

• Studies on Seven-membered Ring Compounds. XX. Reactions of Troponeimine Derivatives. (2)
  作者：Hideo Nakao、Nobuo Soma、Genshun Sunagawa

  DOI：10.1248/cpb.13.828

  日期：——

  The reaction of 2-methoxytroponeimine (I) and its N-methyl derivative (II) with active methylene compounds were carried out. The reaction of I with malononitrile, ethyl cyanoacetate or cyanoacetamide in the presence of sodium ethoxide afforded rearrangemet products, that is 3-phenylacrylic acid derivatives. The same reaction in the absence of sodium ethoxide gave mainly 2-imino-1, 2-dihydrocyclohepta[b]pyrrole derivatives. However, the reaction of I with diethyl malonate afforded ethyl 2-oxo-8-methoxy-1, 2-dihydrocyclohepta[b]pyrrole-3-carboxylate. II showed some different reactivity from I. Namely, the reaction of II with active methylene compounds in the presence of sodium ethoxide afforded 2-imino-1, 2-dihydrocyclohepta[b]pyrrole derivatives besides rearrangement products.

  2-甲氧基托品酮亚胺（I）及其N-甲基衍生物（II）与活性甲基酮化合物的反应进行了研究。I与丙二腈、氰乙酸乙酯或氰乙酰胺在乙醇钠存在下反应，得到了重排产物，即3-苯基丙烯酸衍生物。同样条件下，在无乙醇钠时主要生成2-亚胺基-1,2-二氢环庚[b]吡咯衍生物。然而，I与丙二酸二乙酯反应生成了乙酯2-氧代-8-甲氧基-1,2-二氢环庚[b]吡咯-3-羧酸酯。II显示出与I不同的反应活性，在乙醇钠存在下，II与活性甲基酮化合物的反应除了重排产物外，还主要生成2-亚胺基-1,2-二氢环庚[b]吡咯衍生物。
• Intramolecular Hydroamination with Homogeneous Zinc Catalysts: Evaluation of Substituent Effects inN,N′-Disubstituted Aminotroponiminate Zinc Complexes
  作者：Maximilian Dochnahl、Karolin Löhnwitz、Jens-Wolfgang Pissarek、Mustafa Biyikal、Sabrina R. Schulz、Sebastian Schön、Nils Meyer、Peter W. Roesky、Siegfried Blechert

  DOI：10.1002/chem.200601765

  日期：2007.8.6

  ethers, and aryl groups were employed. The corresponding aminotroponiminate zinc complexes were then synthesized and characterized by a number of techniques, including by X-ray crystallography. Herein we report on the investigations into their activity in the intramolecular hydroamination of nonactivated alkenes. We also demonstrate that complexes bearing ligands with cyclic alkyl groups show superior

  已经制备了一系列对称和不对称的N，N′-二取代的氨基troponimines（ATIHs）。使用从直链至环状烷基，螯合醚和芳基的取代基。然后，通过多种技术，包括通过X射线晶体学，合成并表征了相应的氨基troponiminate锌配合物。在此，我们报告了对它们在未活化烯烃的分子内加氢胺化中的活性的研究。我们还证明了带有环烷基配体的配合物在许多与官能化的氨基烯烃的选定反应中显示出优异的活性。
• π-Complexes of Tropolone and Its N-Derivatives: Ambidentate [O,O]/[N,O]/[N,N]-Cycloheptatrienyl Pentamethylcyclopentadienyl Ruthenium Sandwich Complexes
  作者：Michael Pittracher、Ulla Frisch、Holger Kopacka、Klaus Wurst、Thomas Müller、Luciano Oehninger、Ingo Ott、Evelyn Wuttke、Stefan Scheerer、Rainer F. Winter、Benno Bildstein

  DOI：10.1021/om401200t

  日期：2014.4.14

  acetylacetonates by in situ deprotonation and complex formation gives access to trimetallic (M = Cu2+, 10–12) or tetrametallic (M = Fe3+, 13) complex cations. Their single-crystal structure analyses show square-planar or square-pyramidal (M = Cu2+) or octahedral (M = Fe3+) coordination motifs with peripheral, η5-coordinated Cp*Ru moieties. Electrochemical studies on the trorucenes 4–6 showed a likely

  Tropolone及其N衍生物异丙丙基氨基tropone和二异丙基氨基troponimine与[Cp * Ru（CH 3 CN）3 ] PF 6作为富电子Cp * Ru +合成子的来源，通过简单的“封端反应”与第一个环戊二烯基/环庚三烯基反应含有两个邻位羰基或氨基取代基的三明治复合物。这些杂，阳离子Ç 5 / C 7 π络合物，混合[Cp *茹（C 7 H ^ 5）O 2 H] +（4），混合[Cp *茹（C 7 H ^ 5）O（N我PR）H] +（5）和[Cp * Ru（C7 H 5）（N i Pr）2 H] +（6）是没有任何空气稳定性的18电子茂金属。在溶液中，NMR光谱证明的主π配位的取代的η 7 -cycloheptatrienyl配体，而在固态一个η 5 -cycloheptatrienyl协调模式与弯曲氧代/亚氨基部分盛行，如由X-射线单晶结构分析。化学上，这些化合物是中性[
• Sodium Aminotroponiminates: Ligand-Induced Disproportionation, Mixed-Metal Compounds, and Exceptional Activity in Polymerization Catalysis
  作者：Anna Hanft、Malte Jürgensen、Rüdiger Bertermann、Crispin Lichtenberg

  DOI：10.1002/cctc.201800580

  日期：2018.9.20

  formation of [Na(ATI)2]− sodiate complex anions. The same structural motif has also been found in the first well‐defined mixed‐metal ATI complexes, which have been accessed starting from monometallic sodium and potassium species. The mixed‐metal compounds confirm the possibility of ATIs to act as ditopic ligands. Using the polymerization of ϵ‐caprolactone as a model system, structure‐reactivity‐relationships

  氨基troponiminate（ATI）配体的钠配合物已经与一系列中性供体配体反应。添加冠醚后，它们会发生不寻常的配体诱导歧化反应，并形成[Na（ATI）2 ] -磺酸根复合阴离子。在第一个定义明确的混合金属ATI配合物中也发现了相同的结构基序，这些配合物是从单金属钠和钾物种开始获得的。混合金属化合物证实了ATIs可以用作双位配体的可能性。使用ϵ-己内酯的聚合反应作为模型系统，通过比较[Na（ATI）]和[Na（ATI）2 ]的反应性，研究了钠和混合金属ATI化合物中的结构-反应性关系-结构图案。这些研究揭示了催化剂活性的趋势，取决于络合物的核数和ATI配体处的取代模式。对于[Na（crown）2 ] [Na（ATI）2 ]型双核钠酸钠，获得了极高的活性，使其成为该反应最活跃的碱金属引发剂。本文中介绍的有机金属和高分子化合物已通过（VT‐）NMR光谱，单晶X射线衍射，凝胶渗透色谱，质谱和DFT计算等技术进行了表征。
• Catalytic Epoxidation of Enones Mediated by Zinc Alkylperoxide/<i>tert-</i>BuOOH Systems
  作者：Marcin Kubisiak、Karolina Zelga、Iwona Justyniak、Ewa Tratkiewicz、Tomasz Pietrzak、Abdul R. Keeri、Zbigniew Ochal、Larissa Hartenstein、Peter W. Roesky、Janusz Lewiński

  DOI：10.1021/om400830e

  日期：2013.10.14

  The epoxidation of enones by zinc alkylperoxides is a challenging task receiving considerable attention in contemporary research; however, until now no well-defined zinc alkylperoxide based systems have been described. Here, a new catalytic method of epoxidation of enones in the presence of zinc alkylperoxides supported by N,N-bidentate ligands and tert-butyl hydroperoxide is reported. A new dimeric

  烷基过氧化锌对烯酮的环氧化是一项具有挑战性的任务，在当代研究中受到了广泛关注。然而，到目前为止，还没有描述明确的基于烷基过氧化锌的体系。在此，报道了在由N，N-二齿配体和叔丁基过氧化氢负载的烷基过氧化锌存在下烯酮环氧化的新催化方法。还提出了一种新的二氨基烷基过氧化锌配体负载的烷基过氧化锌配合物。所研究的催化体系在反式查尔酮的环氧化中表现出高活性，并且在具有（S，S）-N，N的手性催化剂的情况下′-双（1-苯乙基）氨基对苯二酸酯配体实现中等的对映选择性。