N-((6-(1H-pyrrol-2-yl)pyridin-2-yl)methyl)-2,6-diisopropylbenzeneamine | 1174286-81-7

• 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-((6-(1H-pyrrol-2-yl)pyridin-2-yl)methyl)-2,6-diisopropylbenzeneamine
• 英文别名: 2,6-di(propan-2-yl)-N-[[6-(1H-pyrrol-2-yl)pyridin-2-yl]methyl]aniline
• CAS: 1174286-81-7
• 化学式: C₂₂H₂₇N₃
• 分子量: 333.476
• InChiKey: PIFQQVNLQRXVTR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  40.7
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-((6-(1H-pyrrol-2-yl)pyridin-2-yl)methyl)-2,6-diisopropylbenzeneamine 、 tetrakis(dimethylamido)hafnium 以 苯 为溶剂， 反应 0.5h， 以98%的产率得到(N-((6-(1H-pyrrol-2-yl)pyridin-2-yl)methyl)-2,6-diisopropylbenzeneamine(2-))Hf(IV)(dimethylamido)₂
  参考文献：
  名称：

  New Titanium and Hafnium Complexes Bearing [⁻NNN^–] Pyrrolylpyridylamido Ligands as Olefin Polymerization Catalysts

  摘要：

  Four new complexes bearing either unsubstituted or substituted pyrrolylpyridylanilido ligands, with the general formula [-NNN-]M(NMe2)(2) (M = Ti(IV), Hf(IV)), were synthesized and fully characterized by NMR spectroscopy and elemental analyses. The solid-state structures of one Ti and one Hf complex (both bearing the 2-isopropylphenyl substituent on the carbon bridging the pyridine and the aniline moieties) were obtained by single-crystal X-ray diffraction analyses, showing in both cases slightly distorted square pyramidal geometries, with the [-NNN-] ligand and one Me2N forming the base plane and the second Me2N as the apex. The new complexes and, for comparison, their zirconium analogues were tested as precatalysts for olefin polymerization, after activation with (AlBu2H)-Bu-i/methylalumoxane. Polymerization of ethylene under mild conditions (25 degrees C and 1 atm) was promoted by all catalysts with high activities, resulting in highly linear polyethylenes with ultrahigh molecular weights (M-w to 2.7 MDa). Polymerization of propylene (at 25 degrees C and 6 atm) was promoted by all complexes, with activities decreasing in the order Ti > Zr > Hf for the C-s-symmetric complexes and in the order Zr >> Ti > Hf for the C-1-symmetric complexes. Concerning stereoselectivity, catalysts based on Zr and Hf complexes behave similarly, with the C-1-symmetric species of both metals affording much more isotactic polymers than the C-5-symmetric species ([mmmm] 95% vs 73-79%) and performing better also in terms of activities and production of high-molecular-weight polypropylenes (M-w to 1.8 MDa for He. The Ti-based catalysts are less stereospecific and produce polypropylenes having very high molecular weights and rather broad molecular weight distributions. Solvent extraction of the raw samples showed the presence, in both cases, of an isotactic and an atactic fraction, also having different regioerrors, suggesting the formation of at least two active species.

  DOI：

  10.1021/om300519s

文献信息

• Random Copolymerization of ε-Caprolactone and Lactides Promoted by Pyrrolylpyridylamido Aluminum Complexes
  作者：Gang Li、Marina Lamberti、Daniela Pappalardo、Claudio Pellecchia

  DOI：10.1021/ma3019848

  日期：2012.11.13

  The monomethylaluminum complexes 1 and 2, bearing pyrrolylpyridylamido as dianionic [-NNN-] tridentate ligands with general formula [NNN]AIMe, were synthesized and tested as initiators in the ring-opening polymerization (ROP) of epsilon-caprolactone, L-lactide, and D,L-lactide. In the presence of 1 equiv of alcohol, compounds 1 and 2 were highly active initiators in the ROP of epsilon-CL (TOF up to 4000 mol(CL) mol(Al-1) h(-1)), and they showed moderate activity in the ROP of lactides (TOF up to 1.7 mol(LA) mol(AL)(-1) h(-1)) The polymerization processes proceeded with a living mechanism; moreover, the obtained PLAs resulted isotactic-enriched with P-m values up to 76%. More interestingly, this class of catalysts promoted the random copolymerization of epsilon-caprolactone and lactides. In particular, compound 1 allowed excellently controlled random copolymerization of epsilon-caprolactone and D,L-lactide as indicated by both the values of the reactivity ratios of the two monomers (r(LA) = 1.17; r(CL) = 1.36) and the average lengths of the caproyl and lactidyl sequences (L-CL = 2.0; L-LA = 2.5).