dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate | 917110-64-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate
• 英文别名: Dimethyl 3-methyl-9-oxo-2,4-dipyridin-2-yl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate
• CAS: 917110-64-6
• 化学式: C₂₈H₂₉N₅O₅
• 分子量: 515.569
• InChiKey: LVQMWOWPMUXJJQ-UHFFFAOYSA-N

物化性质

• 沸点：
  654.8±55.0 °C(Predicted)
• 密度：
  1.320±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  115
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate 在 sodium tetrahydroborate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 Dimethyl 9-hydroxy-3-methyl-2,4-dipyridin-2-yl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate
  参考文献：
  名称：

  Optimization of Pentadentate Bispidines as Bifunctional Chelators for⁶⁴Cu Positron Emission Tomography (PET)

  摘要：

  Pentadentate bispidine ligands (3,7-diazabicyclo[3.3.1]nonanes) are optimized for maximum complex stability and facile functionalization with respect to their coupling to biological vector molecules and/or fluorescence markers for PET (positron emission tomography) and multimodal imaging (i.e., PET and optical imaging). The pentadentate ligand with two tertiary amine donors, two p-methoxy substituted pyridines, and one unsubsituted pyridine group is shown to best fulfill important conditions for PET applications, i.e., fast complexation with Cu-II and high in vivo stability, and this was predicted from the solution chemistry, in particular the Cu-II/I redox potentials. Also, solvent partition experiments to model the lipophilicity of the Cu-II complexes indicate that the bis p-methoxy substituted ligand leads to cationic complexes with an appreciable lipophilicity. This is supported by the biodistribution experiments that show that the complex with the p-methoxy substituted ligand is excreted very quickly and primarily via the renal route and therefore is ideally suited for the development of PET tracers with ligands of this type coupled to biomolecules.

  DOI：

  10.1021/ic4008685
• 作为产物：
  描述：

  2-氨甲基吡啶 、 聚合甲醛 、 dimethyl 4-hydroxy-1-methyl-2,6-dipyridin-2-yl-3,6-dihydro-2H-pyridine-3,5-dicarboxylate 以 四氢呋喃 为溶剂， 生成 dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate
  参考文献：
  名称：

  Optimization of Pentadentate Bispidines as Bifunctional Chelators for⁶⁴Cu Positron Emission Tomography (PET)

  摘要：

  Pentadentate bispidine ligands (3,7-diazabicyclo[3.3.1]nonanes) are optimized for maximum complex stability and facile functionalization with respect to their coupling to biological vector molecules and/or fluorescence markers for PET (positron emission tomography) and multimodal imaging (i.e., PET and optical imaging). The pentadentate ligand with two tertiary amine donors, two p-methoxy substituted pyridines, and one unsubsituted pyridine group is shown to best fulfill important conditions for PET applications, i.e., fast complexation with Cu-II and high in vivo stability, and this was predicted from the solution chemistry, in particular the Cu-II/I redox potentials. Also, solvent partition experiments to model the lipophilicity of the Cu-II complexes indicate that the bis p-methoxy substituted ligand leads to cationic complexes with an appreciable lipophilicity. This is supported by the biodistribution experiments that show that the complex with the p-methoxy substituted ligand is excreted very quickly and primarily via the renal route and therefore is ideally suited for the development of PET tracers with ligands of this type coupled to biomolecules.

  DOI：

  10.1021/ic4008685

文献信息

• Synthesis and Oxidation of Vanadyl Complexes Containing Bispidine Ligands
  作者：Peter Comba、Shigemasa Kuwata、Gerald Linti、Máté Tarnai、Hubert Wadepohl

  DOI：10.1002/ejic.200600927

  日期：2007.2

  3.1]nonane -1,5 -dicarboxylate (L 2 ) with vanadyl sulfate in methanol yields the purple complex [V IV =O(L 2' )](ClO 4 ) 2 , where L 2 is hydrated to the corresponding 9-diol L 2' . The crystal structure of [V IV =O(L 2' )](ClO 4 ) 2 has a saturated coordination sphere with a long bond to the tertiary amine N7 trans to the oxido group (2.36 A). Oxidation of [V IV =O(L 2' )](ClO 4 ) 2 with an excess

  3-methyl-9-oxo-7-picolyl-2,4-di(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane -1,5-dicarboxylate (L 2 ) 与硫酸氧钒的反应在甲醇中产生紫色复合物 [V IV =O(L 2' )](ClO 4 ) 2 ，其中 L 2 水合为相应的 9-二醇 L 2' 。[V IV =O(L 2' )](ClO 4 ) 2 的晶体结构具有饱和配位球，具有与叔胺 N7 反式到氧化基团 (2.36 A) 的长键。[V IV =O(L 2' )](ClO 4 ) 2 用过量的过氧化氢水溶液氧化产生橙色络合物[VV =O(O 2 )(L 2' )]ClO 4 。这可以在-40°C 下用 MeCN 中的 Ce 4+ 进一步氧化为不稳定的钒 (V)-氧化超氧化物复合物 [VV =O(O 2 )(L 2' )] 2+ ，如 EPR 光谱所示。[VV
• Trinuclear {M¹}CN{M²}₂ Complexes (M¹ = Cr^III, Fe^III, Co^III; M² = Cu^II, Ni^II, Mn^II). Are Single Molecule Magnets Predictable?
  作者：Mihail Atanasov、Christoph Busche、Peter Comba、Fadi El Hallak、Bodo Martin、Gopalan Rajaraman、Joris van Slageren、Hubert Wadepohl

  DOI：10.1021/ic800556c

  日期：2008.9.15

  trinuclear complexes with cis- or trans-arrangement of the bispidine-capped divalent metal centers around the hexacyanometalate. X-ray structural analyses of five members of this family of complexes (cis-Fe[CuL(2)]2, trans-Fe[CuL(1)]2, cis-Co[CuL(2)]2, trans-Cr[MnL(1)]2, trans-Fe[MnL(1)]2) and the magnetic data of the entire series are reported. The magnetic data of the cyanide bridged, ferromagnetically

  六氰基金属盐K3 [M（1）（CN）6]（M（1）= Cr（III），Fe（III），Co（III））与联吡啶化合物[M（2）（L（1） ））（X）]（n +）和[M（2）（L（2））（X）]（n +）（M（2）= Mn（II），Ni（II），Cu（II）; （1）= 3-甲基-9-氧代-2,4-二-（2-吡啶基）-7-（2-吡啶基甲基）-3,7-二氮杂双环[3.3.1]壬娜-1,5-二羧酸酸二甲酯; L（2）= 3-甲基-9-氧代-7-（2-吡啶基甲基）-2,4-二-（2-喹啉基）-3,7-二氮杂双环[3.3.1]非烷-在水-甲醇混合物中的1，5-二羧酸二甲酯； X =阴离子或溶剂）可得到三核配合物，其在六氰基金属酸盐周围具有双环吡啶封端的二价金属中心的顺式或反式排列。X射线结构分析此复合物家族的五个成员（顺式Fe [CuL（2）] 2，反式Fe [CuL（1）] 2，顺式Co [CuL（2）]
• Process For Producing 3,7-Diaza-Bicyclo[3.3.1]Nonane-Metal Complexes
  申请人：Reinhardt Gerd

  公开号：US20130072685A1

  公开（公告）日：2013-03-21

  The invention describes a process for producing metal complexes of the general formula (2): [M a L x X n ]Y m (2), where M is a metal from the group comprising Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III) or Fe(IV), X is a coordinated compound selected from mono- bi- or tri-charged anions or neutral molecules which are able to coordinate with a metal mono- bi- or tri-dentate, Y represents a non-coordinated counter-ion which ensures charge equalization of the complex, L represents a ligand of the general formula (1) or the protonized or de-protonized form thereof, and a, x, n, m, R, R 1 , R 2 , R 3 and z have the meaning specified in claim 1. Said process is characterized in that the reaction of a ligand of the formula (1) with an iron or manganese salt in a heterogeneous reaction is carried out in water, where the reaction is carried out in a temperature range of 35 to 50° C. and the pH value of the reaction mixture is from 1 to 3 after the addition of the iron or manganese salt.

  该发明描述了一种制备通式（2）的金属配合物的过程：[MaLxXn]Ym(2)，其中M是来自包括Mn(II)、Mn(III)、Mn(IV)、Fe(II)、Fe(III)或Fe(IV)的金属，X是一种配位化合物，选择从单、双或三价阴离子或能够与金属单、双或三齿配位的中性分子中，Y代表非配位的反离子，保证配合物的电荷平衡，L代表通式（1）或其质子化或去质子化形式的配体，a、x、n、m、R、R1、R2、R3和z的含义如权利要求书中所述。所述过程的特点在于，在水中进行一种配体的通式（1）与铁或锰盐的杂化反应，反应温度在35到50℃的范围内进行，加入铁或锰盐后，反应混合物的pH值为1到3。
• Polyetheramine production method
  申请人：Wessling Michael

  公开号：US20090234124A1

  公开（公告）日：2009-09-17

  The present invention relates to a process for the preparation of 3,7-diazabicyclo[3.3.1]nonane compounds. According to the invention, in a first step, a dicarboxylic acid ester is reacted with a pyridine aldehyde and a primary amine. The piperidone which forms is reacted in a second stage with formaldehyde and a further primary amine. It is essential to the invention that, in the first reaction stage, a C2-C4-alcohol is used as solvent and, in the second reaction stage, a C3-C4-alcohol is used as solvent.

  本发明涉及一种制备3,7-二氮杂双环[3.3.1]壬烷化合物的方法。根据本发明，在第一步中，将二羧酸酯与吡啶醛和一种初级胺反应。形成的哌啶酮在第二阶段与甲醛和另一种初级胺反应。本发明的关键在于，在第一反应阶段中使用C2-C4醇作为溶剂，在第二反应阶段中使用C3-C4醇作为溶剂。
• Catalytic Aziridination of Styrene with Copper Complexes of Substituted 3,7‐Diazabicyclo[3.3.1]nonanones
  作者：Peter Comba、Michael Merz、Hans Pritzkow

  DOI：10.1002/ejic.200200618

  日期：2003.5

  The copper(II) complexes of five bispidine-type ligands 3,7-diazabicyclo[3.3.1]nonanone; three tetradentate ligands with 2-pyridyl (L1), 6-methyl-2-pyridyl (L2) or 2-imidazolyl-3-methyl (L3) substituents in 2,4-positions; two pentadentate derivatives of L1 with an additional 2-methylpyridine substituent at N3 (L4) or N7 (L5)} have, with one co-ligand (Cl−), a ligand-enforced square pyramidal (L1,2

  五种双吡啶型配体3,7-二氮杂双环[3.3.1]壬酮的铜(II)配合物；在 2,4-位具有 2-吡啶基 (L1)、6-甲基-2-吡啶基 (L2) 或 2-咪唑基-3-甲基 (L3) 取代基的三个四齿配体；L1 的两个五齿衍生物在 N3 (L4) 或 N7 (L5)} 处具有额外的 2-甲基吡啶取代基}，具有一个共配体 (Cl−)，配体强制的四角锥体 (L1,2,3) 或八面体(L4,5) 几何。五种 [Cu(L)(Cl)]+ 络合物中的三种 (L1,2,3) 的主要结构特性非常相似，Cu−N3 < Cu−N7 和 Cu−Cl ≈ 2.25 A（转换为 N3 ); L2 Cu−N3 ≈ Cu−N7 和 Cu−Cl = 2.22 A（转换为 N7）；L5 Cu−N3 < Cu−N7 和 Cu−Cl = 2.72 A（转换为 N7）。这些结构模式导致配体场和电化学性质的显着差异（E°范围约为