ethyl N-(2,6-diisopropylphenyl)formimidate | 1063677-30-4

• 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: ethyl N-(2,6-diisopropylphenyl)formimidate
• 英文别名: ethyl N-(2,6-diisopropylphenyl)formamidinate；ethyl N-[2,6-di(propan-2-yl)phenyl]methanimidate
• CAS: 1063677-30-4
• 化学式: C₁₅H₂₃NO
• 分子量: 233.354
• InChiKey: CFGMXQFXMJZWLI-UHFFFAOYSA-N

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：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl N-(2,6-diisopropylphenyl)formimidate 在 硼烷铵络合物 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  抗勃氏idi盐的实验和计算研究

  摘要：

  提出了抗布雷德am盐的实验和计算研究。计算表明，由于减少的π捐赠，氨基的金字塔化会严重破坏idi的正式碳正离子中心。在某些情况下，氮的不利I效应超过其有益的+ M效应，,鎓的稳定性低于亚胺鎓。结果表明，虽然可以分离出1-氮杂-3-氮杂[3.3.1]双环-非2-烯，但它们具有非经典的反应性，对于亚胺盐而言，比typical盐更典型，如明显的亲电性和偶氮甲亚胺。而不是卡宾形成。

  DOI：

  10.1002/chem.201302474
• 作为产物：
  描述：

  2,6-二异丙基苯胺 在 原甲酸三乙酯 作用下， 反应 18.0h， 以78%的产率得到ethyl N-(2,6-diisopropylphenyl)formimidate
  参考文献：
  名称：

  第一行过渡金属和锂吡啶-烯-酰胺络合物，具有N-和C-异构体以及基于苄基CH键的配体活化

  摘要：

  Ene-amines Z-3-(2-pyridyl)-1-aza(2,6-Pr-i(2)-Ph)propene, (pynac)H, and 2-(2-pyridy1)-1-aza(2,6-R,R'-Ph)propene, (pyEA-ArRR')H, were synthesized by condensation procedures; corresponding lithium or potassium ene-amides were prepared via standard deprotonation protocols. Addition of 2 equiv of (pynac)H to {(Me3Si)(2)N}(2)Fe(THF) or 2 Li(pynac) to FeBr2(THF)(2) afforded (pynac)(2)Fe (1), while treatment of CrCl2(THE)(2), MnCl2, FeBr2(THF)(2), and CoCl(2)py(4) with 2 equiv of (pyEA-(ArPr2)-Pr-i)K afforded pseudotetrahedral (pyEA-(ArPr2)-Pr-i)(2)M (2-M, M = Cr, Mn, Fe) and (pyEA-(ArPr2)-Pr-i)(2)Co-py (2-Co-py). Diamagnetic (kappa-C,N-pyEA-(ArPr2)-Pr-i)(3)Co (3) was prepared in low yield (similar to 7%) from CoCl2, and its Co-C(sp(3)) linkages are unusually low in field strength. Reactivity studies yielded little clean reactivity, but thermolysis of 2-Co-py afforded the bis-indolamide derivative -{kappa-N,N-N(C6H3(2-Pr-i)CMe2C(Me)(2-py)}(2)Co (5-Co), and related thermolyses of 2-M (M = Cr, Mn, Fe), conducted on NMA. tube scales, generated related 5-M (M = Cr, Mn, Fe) at roughly the same rates. This observation prompted thermolyses of (pyEA-ArRR')Li, which rearrange to their corresponding indolamides in >90% yields. Rate studies, accompanied by KLE and EIE observations, revealed that an initial hydrogen transfer is reversible and is likely to correspond to an anionic rearrangement, whereas C-C bond formation is rate-determining, as suggested by accompanying calculations. X-ray structure determinations of 1, 2-Fe, 2-Co-py, 3, and 5-Co were conducted.

  DOI：

  10.1021/acs.organomet.5b00385

文献信息

• Multicomponent Synthesis of 1-Aryl 1,2,4-Triazoles
  作者：Annie Tam、Ian S. Armstrong、Thomas E. La Cruz

  DOI：10.1021/ol401428x

  日期：2013.7.19

  A multicomponent (single reactor) process for the synthesis of 1-aryl 1,2,4-triazoles was explored and developed. This transformation prepared the 1,2,4-triazole directly from anilines, amino pyridines, and pyrimidines. The reaction scope was explored with 21 different substrates, and the position of the nitrogen atoms in the newly formed ring was established by 15N labeling and NMR spectroscopy.

  探索和开发了一种用于合成1-芳基1,2,4-三唑的多组分（单反应器）工艺。该转化直接从苯胺，氨基吡啶和嘧啶制备1,2,4-三唑。用21种不同的底物探索了反应范围，并通过15 N标记和NMR光谱确定了新形成的环中氮原子的位置。
• A Cyclic Diaminocarbene with a Pyramidalized Nitrogen Atom: A Stable N-Heterocyclic Carbene with Enhanced Electrophilicity
  作者：David Martin、Nicolas Lassauque、Bruno Donnadieu、Guy Bertrand

  DOI：10.1002/anie.201202137

  日期：2012.6.18

  An anti‐Bredt NHC! Placing one of the adjacent nitrogen atoms of an NHC in the bridgehead position of a bicyclic scaffold prevents the donation of its lone pair. Thus, the π‐electron‐accepting properties of the carbene center are enhanced, while the strong σ‐electron‐donating properties of classical NHCs are retained.

  一个反Bredt NHC！将 NHC 的相邻氮原子之一置于双环支架的桥头位置可防止其孤对的捐赠。因此，卡宾中心的 π 电子接受特性得到增强，而经典 NHC 的强 σ 电子供体特性得以保留。
• Metal-free aminoamidiniumation employing N-iodosuccinimide: facile syntheses of bicyclic imidazolidiniums and cyclic vicinal diamines
  作者：Jun Zhang、Gengtao Zhang、Weijie Wu、Xuejun Zhang、Min Shi

  DOI：10.1039/c4cc07082h

  日期：——

  NIS-mediated aminoamidiniumation has been developed for the syntheses of bicyclic imidazolidinium salts, which could be readily converted into 2-substituted pyrrolidine and indoline diamines.

  NIS介导的氨基铵化反应已被开发用于合成双环咪唑铵盐，这些盐可以方便地转化为2-取代吡咯烷和吲哚二胺。
• NIS/PhI(OAc)₂-Mediated Diamination/Oxidation of<i>N</i>-Alkenyl Formamidines: Facile Synthesis of Fused Tricyclic Ureas
  作者：Jun Zhang、Weijie Wu、Xuejun Zhang、Gengtao Zhang、Sheng Xu、Min Shi

  DOI：10.1002/asia.201403281

  日期：2015.3

  Facile synthesis of bicyclic ureas by NIS/PhI(OAc)2‐mediated diamination/oxidation of N‐alkenyl formamidines is reported. Bulky aromatic groups such as 2,6‐diisopropylphenyl and mesityl and alkyl groups were tolerated towards the process. Several control experiments have been performed, and the reaction outcomes indicate that the oxidation process is probably concerted with the diamination cyclization

  据报道，NIS / PhI（OAc）2介导的N-烯基甲am的氧化/氧化可轻松合成双环脲。宽容的芳香族基团（例如2,6-二异丙基苯基和均三甲苯基和烷基）可耐受该过程。已经进行了一些对照实验，反应结果表明氧化过程可能与氨化环化相一致，并且NIS介导的氨基ami化步骤产生的琥珀酰亚胺促进了PhI（OAc）2介导的氧化步骤。新方法为合成稠合三环脲提供了一种有效的方法。
• Asymmetric Bis(formamidinate) Group 4 Complexes: Synthesis, Structure and Their Reactivity in the Polymerization of α-Olefins.
  作者：Naveen V. Kulkarni、Tatyana Elkin、Boris Tumaniskii、Mark Botoshansky、Linda J. W. Shimon、Moris S. Eisen

  DOI：10.1021/om500345r

  日期：2014.6.23

  N–C–N motif were synthesized. Group 4 bis(formamidinate) dimethylamido, chloride, and benzyl complexes were studied using these asymmetric ligands and their solid-state structures and their behavior in solution were determined. These complexes were activated with MAO (methylalumoxane) or a combination of cocatalysts and tested in the polymerization of ethylene and propylene. A noticeable influence of

  合成了一系列不对称的甲form配体，它们在N–C–N基序的氮上带有不同的取代基，具有不同的空间和电子特性。使用这些不对称配体研究了第4组双（甲酰胺基）二甲基酰胺基，氯化物和苄基配合物，并确定了它们的固态结构和在溶液中的行为。这些配合物用MAO（甲基铝氧烷）或助催化剂的组合活化，并在乙烯和丙烯的聚合反应中进行了测试。观察到甲am氮取代基对催化剂的活性和所得聚合物的性质有显着影响。此外，还提出了一种由ESR-C 60的组合衍生而来的丙烯聚合机理。 MALDI-TOF捕集实验揭示了活性催化物质的性质。