1H-pyrrole-4,5-diisopropyl-2-carbaldehyde

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1H-pyrrole-4,5-diisopropyl-2-carbaldehyde
• 英文别名: 4,5-di(propan-2-yl)-1H-pyrrole-2-carbaldehyde
• 化学式: C₁₁H₁₇NO
• 分子量: 179.262
• InChiKey: WLVBGQDLRZOZSM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  32.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-叔丁基苯胺 、 1H-pyrrole-4,5-diisopropyl-2-carbaldehyde 以 甲苯 为溶剂， 反应 16.0h， 以80%的产率得到[(4,5-diisopropyl-1H-pyrrole-2-yl)methylene]-4-(tert-butyl)aniline
  参考文献：
  名称：

  Molybdenum Complex with Bulky Chelates as a Functional Model for Molybdenum Oxidases

  摘要：

  The novel bulky Schiff base chelate ligand [(4,5-diisopropyl-1H-pyrrole-2-yl)methylene]-4-(tert-butyl)aniline ((HL)-H-iPr2) bearing two isopropyl groups close to the pyrrole nitrogen atom reacts with MoCl2(dme)O-2 (dme = 1,2-dimethoxyethane) to give the sterically congested complex Mo(VI)(L-iPr2)O-2(2) ((iPr2)1; OC-6-4-4 configuration). In spite of the increased steric shielding of the [MoO2] unit (iPr2)1 is active in oxygen-atom transfer to PMe3 and PPh3 to give OPMe3 and OPPh3, respectively. Because of the increased steric bulk of the chelate ligand, formation of dinuclear complexes [Mo-ViPr2)L)O-2](2)(mu-O) ((iPr2)3) by comportionation is effectively prevented in contrast to the highly favored formation of [(MoH2)-H-v)L)(2)O](2)(mu-O) (H(2)3) with the less bulky ligand (H-2)HL. Instead, the smaller PMe3 ligand coordinates to the resulting pentacoordinate intermediate Mo-IViPr2)L)O-2 ((iPr2)5), giving the hexacoordinate complex Mo((IViPr2))L)O-2(PMe3) ((iPr2))(2)) with OC-6-3-3 configuration. The larger potential ligands PPh3 and OPPh3 are only able to weakly coordinate to (iPr2))5, giving labile and sensitive Mo((IViPr2))L)O-2(L) complexes ((iPr2))(6), L = PPh3; (iPr2))7, L = OPPh3). Traces of water and dioxygen in solutions of (iPr2))6/(iPr2))7 yield the di(mu-oxido) complex [Mo-V((iPr2))L)O](2)(mu-O)(2) ((iPr2))(4)) with reduced steric congestion due to dissociation of the bulky chelate ligands. According to electron paramagnetic resonance studies, the much more strongly bound small PMe3 ligand in (iPr2))2 can be slowly liberated by one-electron oxidation to Mo-V, with Ag+ leaving a free coordination site at Mo-V. Hence, essentially pentacoordinate Mo-IV and Mo-V complexes are accessible as a result of the increased steric bulk.

  DOI：

  10.1021/ic501751p
• 作为产物：
  描述：

  2-吡咯甲醛 、 2-氯丙烷 在 aluminum (III) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.5h， 以1.04 g的产率得到1H-pyrrole-4,5-diisopropyl-2-carbaldehyde
  参考文献：
  名称：

  Molybdenum Complex with Bulky Chelates as a Functional Model for Molybdenum Oxidases

  摘要：

  The novel bulky Schiff base chelate ligand [(4,5-diisopropyl-1H-pyrrole-2-yl)methylene]-4-(tert-butyl)aniline ((HL)-H-iPr2) bearing two isopropyl groups close to the pyrrole nitrogen atom reacts with MoCl2(dme)O-2 (dme = 1,2-dimethoxyethane) to give the sterically congested complex Mo(VI)(L-iPr2)O-2(2) ((iPr2)1; OC-6-4-4 configuration). In spite of the increased steric shielding of the [MoO2] unit (iPr2)1 is active in oxygen-atom transfer to PMe3 and PPh3 to give OPMe3 and OPPh3, respectively. Because of the increased steric bulk of the chelate ligand, formation of dinuclear complexes [Mo-ViPr2)L)O-2](2)(mu-O) ((iPr2)3) by comportionation is effectively prevented in contrast to the highly favored formation of [(MoH2)-H-v)L)(2)O](2)(mu-O) (H(2)3) with the less bulky ligand (H-2)HL. Instead, the smaller PMe3 ligand coordinates to the resulting pentacoordinate intermediate Mo-IViPr2)L)O-2 ((iPr2)5), giving the hexacoordinate complex Mo((IViPr2))L)O-2(PMe3) ((iPr2))(2)) with OC-6-3-3 configuration. The larger potential ligands PPh3 and OPPh3 are only able to weakly coordinate to (iPr2))5, giving labile and sensitive Mo((IViPr2))L)O-2(L) complexes ((iPr2))(6), L = PPh3; (iPr2))7, L = OPPh3). Traces of water and dioxygen in solutions of (iPr2))6/(iPr2))7 yield the di(mu-oxido) complex [Mo-V((iPr2))L)O](2)(mu-O)(2) ((iPr2))(4)) with reduced steric congestion due to dissociation of the bulky chelate ligands. According to electron paramagnetic resonance studies, the much more strongly bound small PMe3 ligand in (iPr2))2 can be slowly liberated by one-electron oxidation to Mo-V, with Ag+ leaving a free coordination site at Mo-V. Hence, essentially pentacoordinate Mo-IV and Mo-V complexes are accessible as a result of the increased steric bulk.

  DOI：

  10.1021/ic501751p

文献信息

• Molybdenum Complex with Bulky Chelates as a Functional Model for Molybdenum Oxidases
  作者：Jana Leppin、Christoph Förster、Katja Heinze

  DOI：10.1021/ic501751p

  日期：2014.12.1

  The novel bulky Schiff base chelate ligand [(4,5-diisopropyl-1H-pyrrole-2-yl)methylene]-4-(tert-butyl)aniline ((HL)-H-iPr2) bearing two isopropyl groups close to the pyrrole nitrogen atom reacts with MoCl2(dme)O-2 (dme = 1,2-dimethoxyethane) to give the sterically congested complex Mo(VI)(L-iPr2)O-2(2) ((iPr2)1; OC-6-4-4 configuration). In spite of the increased steric shielding of the [MoO2] unit (iPr2)1 is active in oxygen-atom transfer to PMe3 and PPh3 to give OPMe3 and OPPh3, respectively. Because of the increased steric bulk of the chelate ligand, formation of dinuclear complexes [Mo-ViPr2)L)O-2](2)(mu-O) ((iPr2)3) by comportionation is effectively prevented in contrast to the highly favored formation of [(MoH2)-H-v)L)(2)O](2)(mu-O) (H(2)3) with the less bulky ligand (H-2)HL. Instead, the smaller PMe3 ligand coordinates to the resulting pentacoordinate intermediate Mo-IViPr2)L)O-2 ((iPr2)5), giving the hexacoordinate complex Mo((IViPr2))L)O-2(PMe3) ((iPr2))(2)) with OC-6-3-3 configuration. The larger potential ligands PPh3 and OPPh3 are only able to weakly coordinate to (iPr2))5, giving labile and sensitive Mo((IViPr2))L)O-2(L) complexes ((iPr2))(6), L = PPh3; (iPr2))7, L = OPPh3). Traces of water and dioxygen in solutions of (iPr2))6/(iPr2))7 yield the di(mu-oxido) complex [Mo-V((iPr2))L)O](2)(mu-O)(2) ((iPr2))(4)) with reduced steric congestion due to dissociation of the bulky chelate ligands. According to electron paramagnetic resonance studies, the much more strongly bound small PMe3 ligand in (iPr2))2 can be slowly liberated by one-electron oxidation to Mo-V, with Ag+ leaving a free coordination site at Mo-V. Hence, essentially pentacoordinate Mo-IV and Mo-V complexes are accessible as a result of the increased steric bulk.