2,5-di(tert-butylaminomethyl)pyrrole | 1196685-77-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2,5-di(tert-butylaminomethyl)pyrrole
• 英文别名: C4H2NH-2,5-(CH2NHtBu)2；N-[[5-[(tert-butylamino)methyl]-1H-pyrrol-2-yl]methyl]-2-methylpropan-2-amine
• CAS: 1196685-77-4
• 化学式: C₁₄H₂₇N₃
• 分子量: 237.388
• InChiKey: YEBAHOXNCANSNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  39.8
• 氢给体数：
  3
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,5-di(tert-butylaminomethyl)pyrrole 、 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：

  吡咯 、 聚合甲醛 、 2-氨基-2-甲基丙烷盐酸盐 以 乙醇 、 水 为溶剂， 反应 24.0h， 以40%的产率得到2,5-di(tert-butylaminomethyl)pyrrole
  参考文献：
  名称：

  含2-（叔丁基氨基甲基）吡咯的镍（II）配合物的合成与表征

  摘要：

  合成了两个氨基吡咯，2-（叔丁基氨基甲基）吡咯（HL1）和2，5-二（叔丁基氨基甲基）吡咯（HL2），并在单晶X射线结构中观察到氢键相互作用HL1 ·HCl和HL2。双[2-（叔丁基氨基甲基）吡咯]镍（II）[ Ni（L1）2 ]是通过用2当量的NiCl 2处理而制备的。在THF溶剂中的单去质子化HL1。Ni（L1）2的固态结构显示N 4镍原子，具有对应于正方形平面结构的几何形状，其中两个分子内C–H···Ni相互作用存在于轴向位置，接触距离为2.77Å。该复合物在CH 3 CN中的-0.66 V（vs. Fc + / Fc）下显示不可逆的还原反应。此外，1个H，13在室温下进行C-HSQC NMR试验表明，螯合剂的两个亚甲基质子L1 -1是化学非等价和它们中的一个被耦合到所述氨基质子。观察到的耦合常数（J HH'）接近从邻近的Karplus相关图预测的值。

  DOI：

  10.1002/jccs.200900065

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。
• Aluminium complexes containing bidentate and symmetrical tridentate pincer type pyrrolyl ligands: synthesis, reactions and ring opening polymerization
  作者：Wen-Yen Huang、Sheng-Jie Chuang、Nien-Tsu Chunag、Ching-Sheng Hsiao、Amitabha Datta、Shau-Jiun Chen、Ching-Han Hu、Jui-Hsien Huang、Ting-Yu Lee、Chia-Her Lin

  DOI：10.1039/c1dt10442j

  日期：——

  5-CH2NHtBu)2 with AlH3·NMe3 in diethyl ether generates an aluminium dihydride complex, [C4H2N(2,5-CH2NHtBu)2]AlH2 (8), in high yield. Additionally, treating 8 with one equiv. of HOC6H2(-2,6-tBu2-4-Me) in methylene chloride produces [C4H2N(2,5-CH2NHtBu)2][OC6H2(-2,6-tBu2-4-Me)]AlH (9) with the elimination of one equiv. of H2. The aluminium alkoxide complex 4 shows moderate reactivity toward the ring opening

  将含有系列铝衍生物取代的二齿和三齿对称吡咯基配体，[C 4 H ^ 3 NH（2-CH 2 NH吨丁基）]和[C 4 H ^ 2 NH（2,5-CH 2 NH吨丁基）2 ] ， 在甲苯 或者 乙醚被合成。它们的反应性及在开环聚合中的应用ε-己内酯已被调查。的反应AlMe 3一当量 [C 4 H 3 NH（2-CH 2 NH t Bu）]的摩尔数甲苯在室温下，通过消除一个当量，以70％的收率得到[C 4 H 3 N（2-CH 2 NH t Bu）] AlMe 2（1）。甲烷。有趣的是，在做出反应时AlMe 3一当量 [C 4 H 3 NH（2-CH 2 NH t Bu）]的摩尔数甲苯在0℃然后在100℃，[C回流4 ħ 3 N（2-CH 2 Ñ吨丁基）}阿尔梅] 2（2）已被分离通过在30％的产率分数recrystalliztion。同样地，AlMe 3有两个当量。C 4 H 3 NH（2-CH
• 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.