2-bromo-N-(1-adamantyl)aniline | 208262-14-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-bromo-N-(1-adamantyl)aniline
• 英文别名: N-(2-bromophenyl)adamantan-1-amine
• CAS: 208262-14-0
• 化学式: C₁₆H₂₀BrN
• 分子量: 306.245
• InChiKey: YIIWCLNBZZEOMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-N-(1-adamantyl)aniline 在 盐酸 、 barium hydroxide octahydrate 、 palladium diacetate 、 三乙胺 、 2-(二环己基膦基)联苯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 水 、 苯 为溶剂， 反应 25.67h， 生成
  参考文献：
  名称：

  Investigations into Asymmetric Post-Metallocene Group 4 Complexes for the Synthesis of Highly Regioirregular Polypropylene

  摘要：

  A series of asymmetric post-metallocene group 4 complexes based on a modular anilide(pyridine)phenoxide framework have been synthesized and tested for propylene polymerization activity. These complexes, upon activation with methylaluminoxane (MAO), produce highly regioirregular and stereoirregular polypropylene with moderate to good activities. Surprisingly, modification of the anilide R-group substituent from 1-phenethyl to benzyl or adamantyl did not significantly change the polymer microstructure as determined by C-13 NMR spectroscopy. Although polymer molecular weights and poly-dispersities vary with propylene pressure, temperature, and activator, regio- and stereoirregularity were also found to be relatively insensitive to these variables. When the polymerization is conducted at 70 degrees C under dihydrogen, partial decomposition to a highly active catalyst that produces an isotactic microstructure occurs; the undecomposed catalyst continues to produce highly regioirregular and stereoirregular polypropylene under these conditions.

  DOI：

  10.1021/ma500453t
• 作为产物：
  描述：

  金刚烷胺 、 1,2-二溴苯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 双(2-二苯基磷苯基)醚 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以39%的产率得到2-bromo-N-(1-adamantyl)aniline
  参考文献：
  名称：

  庞大的CCC-P型N-杂环碳烯配体的铱配合物：配位数和催化烯烃异构化的立体控制

  摘要：

  合成并表征了三种新的间亚苯基桥联的双-N-杂环卡宾CCC-钳位配体的铱配合物。对于具有2，6-二异丙基苯基N-取代基的钳位配体，形成了具有式Ir（CCC）HCl（MeCN）的六配位铱（III）配合物。相反，具有叔丁基或金刚烷基N-取代基的配体给出了五配位式Ir（CCC）HCl的铱（III）配合物。测试了这些铱配合物以及两个先前描述的铱配合物在150°C下对正辛烷的催化转移脱氢活性。新的配合物对该反应无活性，而先前报道的两种催化剂则具有中等活性：1，3，5-二-叔丁基苯基取代的变体产生了10个周转率。相反，在比转移脱氢所要求的条件温和得多的条件下，这些络合物被证明是用于末端烯烃异构化的高活性催化剂。

  DOI：

  10.1021/om300468d

文献信息

• Pd-Catalyzed Aryl Amination Mediated by Well Defined, N-Heterocyclic Carbene (NHC)–Pd Precatalysts, PEPPSI
  作者：Michael G. Organ、Mirvat Abdel-Hadi、Stephanie Avola、Igor Dubovyk、Niloufar Hadei、Eric Assen B. Kantchev、Christopher J. O'Brien、Mahmoud Sayah、Cory Valente

  DOI：10.1002/chem.200701621

  日期：2008.3.7

  Pd-N-heterocyclic carbene (NHC)-catalyzed Buchwald-Hartwig amination protocols mediated by Pd-PEPPSI precatalysts is described. These protocols provide access to a range of hindered and functionalized drug-like aryl amines in high yield with both electron-deficient and electron-rich aryl- and heteroaryl chlorides and bromides. Variations in solvent polarity, base and temperature are tolerated, enhancing

  描述了由Pd-PEPPSI预催化剂介导的Pd-N-杂环卡宾（NHC）催化的Buchwald-Hartwig胺化方案。这些方案可提供高收率的一系列受阻和功能化的药物样芳基胺，以及缺电子和富电子的芳基氯化物和杂芳基氯化物和溴化物。溶剂极性，碱和温度的变化是可以容忍的，从而增强了该协议的范围和实用性。还提供了对基础强度（pKb）要求的机械合理性。
• Palladium-catalyzed amination of isomeric dihalobenzenes with 1- and 2-aminoadamantanes
  作者：A. D. Averin、M. A. Ulanovskaya、V. V. Kovalev、A. K. Buryak、B. S. Orlinson、I. A. Novakov、I. P. Beletskaya

  DOI：10.1134/s1070428010010069

  日期：2010.1

  Palladium-catalyzed amination of isomeric bromochloro- and dibromobenzenes with 1- and 2-aminoadamantanes was studied. The best yields of the corresponding monoamination products were obtained in the reactions of 2-aminoadamantane with bromochlorobenzenes. The arylation of 1-aminoadamantane was successful in the presence of donor phosphine ligand. The amination of o- and m-dibromobenzenes was strongly complicated by formation of diamination products. Conditions ensuring predominant formation of the latter were found. The arylation of 2-aminoadamantane was accompanied by oxidation of the initial amine and reduction of aryl halide.
• Iridium Complexes of Bulky CCC-Pincer N-Heterocyclic Carbene Ligands: Steric Control of Coordination Number and Catalytic Alkene Isomerization
  作者：Anthony R. Chianese、Sarah E. Shaner、Jennifer A. Tendler、David M. Pudalov、Dimitar Y. Shopov、Daniel Kim、Scott L. Rogers、Allen Mo

  DOI：10.1021/om300468d

  日期：2012.11.12

  Three new iridium complexes of meta-phenylene-bridged bis-N-heterocyclic carbene CCC-pincer ligands were synthesized and characterized. For a pincer ligand with 2,6-diisopropylphenyl N-substituents, a six-coordinate iridium(III) complex of the formula Ir(CCC)HCl(MeCN) was formed. In contrast, ligands with t-butyl or adamantyl N-substituents gave five-coordinate iridium(III) complexes of the formula

  合成并表征了三种新的间亚苯基桥联的双-N-杂环卡宾CCC-钳位配体的铱配合物。对于具有2，6-二异丙基苯基N-取代基的钳位配体，形成了具有式Ir（CCC）HCl（MeCN）的六配位铱（III）配合物。相反，具有叔丁基或金刚烷基N-取代基的配体给出了五配位式Ir（CCC）HCl的铱（III）配合物。测试了这些铱配合物以及两个先前描述的铱配合物在150°C下对正辛烷的催化转移脱氢活性。新的配合物对该反应无活性，而先前报道的两种催化剂则具有中等活性：1，3，5-二-叔丁基苯基取代的变体产生了10个周转率。相反，在比转移脱氢所要求的条件温和得多的条件下，这些络合物被证明是用于末端烯烃异构化的高活性催化剂。
• Investigations into Asymmetric Post-Metallocene Group 4 Complexes for the Synthesis of Highly Regioirregular Polypropylene
  作者：Rachel C. Klet、Curt N. Theriault、Jerzy Klosin、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/ma500453t

  日期：2014.5.27

  A series of asymmetric post-metallocene group 4 complexes based on a modular anilide(pyridine)phenoxide framework have been synthesized and tested for propylene polymerization activity. These complexes, upon activation with methylaluminoxane (MAO), produce highly regioirregular and stereoirregular polypropylene with moderate to good activities. Surprisingly, modification of the anilide R-group substituent from 1-phenethyl to benzyl or adamantyl did not significantly change the polymer microstructure as determined by C-13 NMR spectroscopy. Although polymer molecular weights and poly-dispersities vary with propylene pressure, temperature, and activator, regio- and stereoirregularity were also found to be relatively insensitive to these variables. When the polymerization is conducted at 70 degrees C under dihydrogen, partial decomposition to a highly active catalyst that produces an isotactic microstructure occurs; the undecomposed catalyst continues to produce highly regioirregular and stereoirregular polypropylene under these conditions.