C4H2NH(2-CH2NHtBu)(5-CH2NMe2) | 1202460-28-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: C4H2NH(2-CH2NHtBu)(5-CH2NMe2)
• 英文别名: N-[[5-[(dimethylamino)methyl]-1H-pyrrol-2-yl]methyl]-2-methylpropan-2-amine
• CAS: 1202460-28-3
• 化学式: C₁₂H₂₃N₃
• 分子量: 209.335
• InChiKey: QKADPGMHUQVUBV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  31.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  C4H2NH(2-CH2NHtBu)(5-CH2NMe2) 、 Dimethylzinc 以 乙醚 、 甲苯 为溶剂， 反应 6.0h， 以80%的产率得到
  参考文献：
  名称：

  Zinc complexes incorporating with symmetrical and asymmetrical polydentate nitrogen-donor pyrrolyl ligands: Synthesis, characterization, and ring-opening polymerization

  摘要：

  The reactions of Zn-alkyls with bidentate as well as symmetrical and asymmetrical tridentate pyrrolyl ligands, have been carried out and characterized. Reacting ZnR2 with 1 equiv of C4H3NH(2-(CH2NHBu)-Bu-t) in diethyl ether yields [Zn{C4H3N(2-(CH2NHBu)-Bu-t)}R] (1, R Me; 2, R Et) in high yield. Similarly, the reactions of 2 equiv of C4H3NH(2-(CH2NHBu)-Bu-t) and ZnR2 (R Me, Et) in toluene both produce [Zn {C4H3N(2-(CH2NHBu)-Bu-t)} 2] (3). Furthermore, while subjecting 2 equiv of C4H2NH(2-(CH2NHBu)-Bu-t) (5-CH2NMe2) with ZnMe2 in diethyl ether, affords [Zn{C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)} 2] (4) and additionally, reacting C4H2NH(2,5-(CH2NHBu)-Bu-t) 2 with ZnMe2 generates [Zn{C4H2N(2,5-(CH2NHBu)-Bu-t)(2)}(2)] (5) in satisfactory yield. All the aforementioned compounds were characterized by H-1 and C-13 NMR spectrometry and the molecular structures were determined by single crystal X-ray diffractometry. Compounds 1, 3, 4 and 5 are moderate catalysts for the ring-opening polymerization of e-caprolactone in toluene. (C) 2012 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2012.08.016
• 作为产物：
  描述：

  聚合甲醛 、 盐酸二甲胺 、 2-(tert-butylaminomethyl)pyrrole 以 乙醚 、 水 为溶剂， 反应 0.5h， 以74.5%的产率得到C4H2NH(2-CH2NHtBu)(5-CH2NMe2)
  参考文献：
  名称：

  A New Type of Asymmetric Tridentate Pyrrolyl-Linked Pincer Ligand and Its Aluminum Dihydride Complexes

  摘要：

  The new pyrrolyl-linked pincer-type ligand, [C4H2NH(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)] (1), that has been employed conveniently in high yield by treatment of (2-t-butylaminomethyl)pyrrole with 1 equiv of formaldehyde and dimethyl-amine hydrochloride each in diethylether and its corresponding aluminum derivative, [C4H2N(2-(CH2NHBu)-Bu-t)-(5-CH2NMe2)]AlH2 (2), that has been generated from Me3N center dot AlH3 using diethylether as a solvent are described. Furthermore, reactions of 2 with 2 equiv of either 1,3-diphenylpropane-1,3-dione in diethylether or phenyl thioisocyanate in dichloromethane interestingly formed [C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)]Al(PhCOCHCOPh)(2) (3) and [C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)]Al(SCHNPh)(2) (4), respectively, following deprotonation or hydroalumination reaction kinetics under a dry nitrogen environment. All of the compounds have been subjected to the X-ray diffraction technique in the solid state as well as characterized by NMR spectra.

  DOI：

  10.1021/ic9016189

文献信息

• Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands: synthesis, characterization and reactivity study
  作者：Pei-Hsin Liu、Fu-Jung Chuang、Cheng-Yi Tu、Ching-Han Hu、Tzu-Wei Lin、Yu-Tang Wang、Chia-Her Lin、Amitabha Datta、Jui-Hsien Huang

  DOI：10.1039/c3dt51133b

  日期：——

  A series of aluminum complexes incorporating substituted symmetrical and asymmetrical tridentate pyrrolyl ligands are synthesized conveniently and the treatment of the derivatives with small organic molecules are analyzed. The reaction of lithiated [C4H2NH(2-CH2NHtBu)(5-CH2NR1R2)], where for 1, R1 = R2 = Me; 2, R1 = H, R2 = tBu, with AlCl3 in diethyl ether affords Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Cl2 (3) and Al[C4H2N(2,5-CH2NHtBu)2]Cl2 (4), respectively, in high yields. Furthermore, subjecting 3 and 4 to reaction with one equiv. of LiNMePh in diethyl ether generates Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][NMePh]Cl (5) and Al[C4H2N(2,5-CH2NHtBu)2][NMePh]Cl (6), respectively, while eliminating one equiv. of LiCl. The reaction between compound 4 with two equiv. of LiO-Ph-4-Me in diethyl ether yields the aluminum di-phenoxide compound Al[C4H2N(2,5-CH2NHtBu)2](O-Ph-4-Me)2 (7) whereas the combination of 3 and two equiv. of LiNHtBu, produces Al[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NHtBu)(NH2tBu) (8). Additionally, the mixing of 1 and one equiv. of AlMe3 renders Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Me2 (9). Adding one more equiv. of AlMe3 with 9 affords Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)AlMe3]Me2} (10), which can also be obtained by treating 1 with two equiv. of AlMe3 directly. The treatment of 9 with one equiv. of 2,6-dimethylphenol in diethyl ether gives the aluminum alkoxide derivative, Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)](O-C6H3-2,6-Me2)Me (11). Furthermore, the reaction between 9 and one equiv. of 1-ethyl-1-phenyl ketene, initiates the aluminum dimethyl complex AlC4H2N[2-CH2CEtPh-C(O)-NHtBu](5-CH2NMe2)}Me2 (12) with a C–N bond breakage and a C–C bond formation. All the Al-derivatives are characterized by 1H and 13C NMR spectroscopy and the molecular structures are determined by single crystal X-ray diffractometry in solid state.

  一系列包含取代对称和非对称三齿吡咯烷配体的铝配合物被方便地合成,其与小有机分子的反应被分析。在二乙醚中,与AlCl3反应,lithiated [C4H2NH(2-CH2NHtBu)(5-CH2NR1R2)]分别高产率地生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Cl2(3)和Al[C4H2N(2,5-CH2NHtBu)2]Cl2(4),其中1, R1 = R2 = Me;2, R1 = H, R2 = tBu。此外,在二乙醚中,3和4分别与一份当量的LiNMePh反应,生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][NMePh]Cl(5)和Al[C4H2N(2,5-CH2NHtBu)2][NMePh]Cl(6),同时释放一份当量的LiCl。4与两份当量的LiO-Ph-4-Me在二乙醚中反应生成双苯氧基铝化合物Al[C4H2N(2,5-CH2NHtBu)2](O-Ph-4-Me)2(7),而3与两份当量的LiNHtBu反应生成Al[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NHtBu)(NH2tBu)(8)。此外,1与一份当量的AlMe3混合生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Me2(9)。9再与一份当量的AlMe3反应生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)AlMe3]Me2}(10),这也可以通过1与两份当量的AlMe3直接反应得到。9与一份当量的2,6-二甲基苯酚在二乙醚中反应生成铝醇盐衍生物Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)](O-C6H3-2,6-Me2)Me(11)。此外,9与一份当量的1-乙基-1-苯基乙烯酮反应,引发铝二甲基配合物AlC4H2N[2-CH2CEtPh-C(O)-NHtBu](5-CH2NMe2)}Me2(12)的生成,伴随着C-N键的断裂和C-C键的形成。所有铝衍生物通过1H和13C NMR谱表征,分子结构通过单晶X射线衍射法在固态中测定。
• Zirconium complexes incorporated with asymmetrical tridentate pincer type mono- and di-anionic pyrrolyl ligands: mechanism and reactivity as catalytic precursors
  作者：Jia-Wei Hsu、Yu-Chun Lin、Ching-Sheng Hsiao、Amitabha Datta、Chia-Her Lin、Jui-Hsien Huang、Jing-Cherng Tsai、Wei-Che Hsu

  DOI：10.1039/c2dt30417a

  日期：——

  The reactions of Zr(NR2)4 (1, R = Me; 2, R = Et) with an asymmetrical tridentate pincer type pyrrole ligand precursor [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)] and treatment of the derivatives with either PhNCS or PhNCO have been carried out and characterized. Reacting Zr(NR2)4 (1, R = Me; 2, R = Et) with [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)] generates Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NR2)2 (3, R = Me; 4, R = Et) in high yield along with the elimination of 2 equiv of dimethylamine or diethylamine, respectively. Interestingly, while changing the solvent from Et2O to CH2Cl2, the complex Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Cl (5) is produced by undergoing C–Cl bond cleavage. Furthermore, reaction of either 3 or 4 with 1 or 2 equiv of PhNCS or PhNCO yields Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NMe2)[PhNC(NMe2)S] (6), Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NEt2)[PhNC(NEt2)O] (7) and Zr[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][PhNC(NEt2)O]3 (8), respectively. All the aforementioned complexes were characterized by 1H and 13C NMR spectrometry and the molecular structures of 5, 6, and 8 have been determined by single-crystal X-ray diffractometry. Complexes 4, 5, and 7 initiated the ethylene polymerization in the presence of MAO as the co-catalyst.

  Zr(NR2)4 （1，R = Me；2，R = Et）与不对称三叉钳型吡咯配体前体 [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)]的反应以及衍生物与 PhNCS 或 PhNCO 的处理均已完成，并对其进行了表征。Zr(NR2)4（1，R = Me；2，R = Et）与 [C4H2NH(2-CH2NHtBu)(5-CH2NMe2)]反应生成 Zr[C4H2N(2-CH2NHtBu)(5-CH2NMe2)](NR2)2 （3，R = Me；4，R = Et），产量很高，同时还分别消除了 2 个等量的二甲胺或二乙胺。有趣的是，当溶剂从 Et2O 变为 CH2Cl2 时，复合物 Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)][C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Cl (5) 通过 C-Cl 键裂解生成。此外，将 3 或 4 与 1 或 2 等当量的 PhNCS 或 PhNCO 反应，可生成 Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NMe2)[PhNC(NMe2)S] (6)、Zr[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NEt2)[PhNC(NEt2)O](7) 和 Zr[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][PhNC(NEt2)O]3(8)。上述所有络合物均通过 1H 和 13C NMR 光谱法进行了表征，5、6 和 8 的分子结构已通过单晶 X 射线衍射测定法确定。络合物 4、5 和 7 在 MAO 作为辅助催化剂存在的情况下启动了乙烯聚合反应。
• Synthesis and structural aspects of gallium compounds containing tridentate pincer type pyrrolyl ligands: Intramolecular hydrogen bonding of gallium aryloxides
  作者：Yu-Tang Wang、Yi-Chien Lin、Shu-Ya Hsu、Ren-Yung Chen、Pei-Hsin Liu、Amitabha Datta、Chia-Her Lin、Jui-Hsien Huang

  DOI：10.1016/j.jorganchem.2013.07.012

  日期：2013.11

  A series of gallium derivatives incorporating with pincer type tridentate symmetric and asymmetric pyrrolyl ligands are conveniently synthesized. Compilation of a symmetrical tridentate pyrrole ligand, [C4H2NH-(2,5-(CH2NHBu)-Bu-t)(2)] (1) with one equiv of n-BuLi in heptane generates lithiated 1 that turns to Ga [C4H2N-(2,5-(CH2NHBu)-Bu-t)(2)]Cl-2 (2) subjecting the addition of GaCl3/ether suspension into diethyl ether. Reacting 2 with two equiv of lithium reagents (LiR) in same solvent originates a series of gallium compounds Ga[C4H2N-(2,5-(CH2NHBu)-Bu-t)(2)]R-2 (3, R = Me; 4, R = O-C6H4-4-Me; 5, R = O-C6H3-2,6-Me-2) in moderate yield through metathesis reactions. Furthermore, the combination of a tridentate asymmetrical pyrrole ligand, [C4H2NH(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)] and n-BuLi initiates the lithiated 6 that undergoes the formation of a penta-coordinated gallium compound GaCl2[C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)] (7) while reacting with GaCl3. Furthermore, reacting 7 with two equivs of MeLi affords the gallium-alkyl compound, GaMe2[C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)] (8) in high yield. The Ga-derivatives are characterized by H-1 and C-13 NMR spectroscopy and the molecular structures of 2, 3, 4, 5 and 7 are determined by single crystal X-ray diffractometry in solid state. (C) 2013 Elsevier B. V. All rights reserved.
• Zinc complexes incorporating with symmetrical and asymmetrical polydentate nitrogen-donor pyrrolyl ligands: Synthesis, characterization, and ring-opening polymerization
  作者：Ching-Sheng Hsiao、Ting-Yin Wang、Amitabha Datta、Fu-Xing Liao、Chin-Han Hu、Chia-Her Lin、Jui-Hsien Huang、Ting-Yu Lee

  DOI：10.1016/j.jorganchem.2012.08.016

  日期：2012.11

  The reactions of Zn-alkyls with bidentate as well as symmetrical and asymmetrical tridentate pyrrolyl ligands, have been carried out and characterized. Reacting ZnR2 with 1 equiv of C4H3NH(2-(CH2NHBu)-Bu-t) in diethyl ether yields [ZnC4H3N(2-(CH2NHBu)-Bu-t)}R] (1, R Me; 2, R Et) in high yield. Similarly, the reactions of 2 equiv of C4H3NH(2-(CH2NHBu)-Bu-t) and ZnR2 (R Me, Et) in toluene both produce [Zn C4H3N(2-(CH2NHBu)-Bu-t)} 2] (3). Furthermore, while subjecting 2 equiv of C4H2NH(2-(CH2NHBu)-Bu-t) (5-CH2NMe2) with ZnMe2 in diethyl ether, affords [ZnC4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)} 2] (4) and additionally, reacting C4H2NH(2,5-(CH2NHBu)-Bu-t) 2 with ZnMe2 generates [ZnC4H2N(2,5-(CH2NHBu)-Bu-t)(2)}(2)] (5) in satisfactory yield. All the aforementioned compounds were characterized by H-1 and C-13 NMR spectrometry and the molecular structures were determined by single crystal X-ray diffractometry. Compounds 1, 3, 4 and 5 are moderate catalysts for the ring-opening polymerization of e-caprolactone in toluene. (C) 2012 Elsevier B. V. All rights reserved.
• A New Type of Asymmetric Tridentate Pyrrolyl-Linked Pincer Ligand and Its Aluminum Dihydride Complexes
  作者：Yu-Ling Lien、Ya-Chi Chang、Nien-Tsu Chuang、Amitabha Datta、Shau-Jiun Chen、Ching-Han Hu、Wen-Yen Huang、Chia-Her Lin、Jui-Hsien Huang

  DOI：10.1021/ic9016189

  日期：2010.1.4

  The new pyrrolyl-linked pincer-type ligand, [C4H2NH(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)] (1), that has been employed conveniently in high yield by treatment of (2-t-butylaminomethyl)pyrrole with 1 equiv of formaldehyde and dimethyl-amine hydrochloride each in diethylether and its corresponding aluminum derivative, [C4H2N(2-(CH2NHBu)-Bu-t)-(5-CH2NMe2)]AlH2 (2), that has been generated from Me3N center dot AlH3 using diethylether as a solvent are described. Furthermore, reactions of 2 with 2 equiv of either 1,3-diphenylpropane-1,3-dione in diethylether or phenyl thioisocyanate in dichloromethane interestingly formed [C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)]Al(PhCOCHCOPh)(2) (3) and [C4H2N(2-(CH2NHBu)-Bu-t)(5-CH2NMe2)]Al(SCHNPh)(2) (4), respectively, following deprotonation or hydroalumination reaction kinetics under a dry nitrogen environment. All of the compounds have been subjected to the X-ray diffraction technique in the solid state as well as characterized by NMR spectra.