4-Bromo-3,5-bis-dimethylaminomethyl-benzaldehyde | 312304-55-5

• 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: 4-Bromo-3,5-bis-dimethylaminomethyl-benzaldehyde
• 英文别名: 4-Bromo-3,5-bis[(dimethylamino)methyl]benzaldehyde
• CAS: 312304-55-5
• 化学式: C₁₃H₁₉BrN₂O
• 分子量: 299.211
• InChiKey: YFWIVQJWHCLULF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-Bromo-3,5-bis-dimethylaminomethyl-benzaldehyde 在 NaBH₃CN 作用下， 以 甲醇 、 苯 为溶剂， 生成
  参考文献：
  名称：

  Bifunctional Pincer-type Organometallics as Substrates for Organic Transformations and as Novel Building Blocks for Polymetallic Materials

  摘要：

  The reactivity of the bifunctionalized ligand NC(Br)N\ 1 [IC6H2(CH2NMe2)(2)-3,5-Br-4] has been studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M = Pd, Pt, LI) at the C-aryl-1 or C-aryl-Br bonds was achieved by choosing the appropriate metal precursors. In this way a series of Pt-II and Pd-II complexes were prepared that have a second functional group available for further reactions. These Pt-II and Pd-II complexes were subjected to a wide range of organic and organometallic reactions, revealing the remarkable stability of their M-C sigma-bond and opening an easy route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes (2, 3a, 19, 20, and 24) are also reported.

  DOI：

  10.1021/ja0177657
• 作为产物：
  描述：

  5-amino-2-bromo-1,3-((bisdimethylamino)methyl)benzene 在 硫酸 、 叔丁基锂 、 sodium nitrite 作用下， 以 乙醚 为溶剂， 生成 4-Bromo-3,5-bis-dimethylaminomethyl-benzaldehyde
  参考文献：
  名称：

  对位取代的NCN-夹钳式钯和铂配合物的合成和性能。

  摘要：

  多种对位取代的NCN钳夹钯（II）和铂（II）配合物[MX（NCN-Z）]（M = Pd（II），Pt（II）; X = Cl，Br，I; NCN- Z = [2,6-（CH（2）NMe（2））（2）C（6）H（2）-4-Z]（-）; Z = NO（2），COOH，SO（3） H，PO（OEt）（2），PO（OH）（OEt），PO（OH）（2），CH（2）OH，SMe，NH（2））是通过涉及取代反应的途径合成的，或者在或者，特别是在配体金属化之后。对夹配合物的溶解度受对取代基Z的性质支配，这使得几种配合物是水溶性的。通过（195）Pt NMR光谱和DFT计算研究了对位取代基对金属中心电子性能的影响。（195）Pt化学位移和计算得出的铂上自然电荷均与sigma（p）Hammett取代基常数线性相关，因此，可以预测预先设计的钳夹复合物的电子性质。对-PtI基团本身的sigma（p）值在甲醇中确定为-1

  DOI：

  10.1002/chem.200305336

文献信息

• Palladium(II) pincer complexes of α-amino acids: towards the synthesis of catalytically active artificial peptides
  作者：Gabriela Guillena、Gema Rodrı́guez、Gerard van Koten

  DOI：10.1016/s0040-4039(02)00656-1

  日期：2002.5

  NCN palladium(II) complexes have been covalently attached to the N- and C-termini of l-valine and to the N-terminus of the dipeptide l-Phe-l-Val-OMe. Remarkably, the hydrolysis of the NCN-Pd(II) l-Val-OMe compound afforded the corresponding palladated, free amino acid without affecting the metal site. This deprotected amino acid could be coupled to any protein, enzyme or peptidic chain by simple peptide

  NCN钯（II）复合物已共价附于1-缬氨酸的N-和C-末端以及二肽1-Phe-1-Val-OMe的N-末端。显着地，NCN-Pd（II）1-Val-OMe化合物的水解提供了相应的有palpalated的游离氨基酸，而不影响金属位点。该脱保护的氨基酸可以通过简单的肽化学偶联到任何蛋白质，酶或肽链上。这些生物有机金属体系在异氰酸甲酯和苯甲醛之间的醛醇缩合反应中起催化剂的作用。
• Synthesis and reaction chemistry of 4-nitrile-substituted NCN-pincer palladium(II) and platinum(II) complexes (NCN=[NC-4-C6H2(CH2NMe2)2-2,6]−)
  作者：Stefan Köcher、Bernhard Walfort、Allison M. Mills、Anthony L. Spek、Gerard P.M. van Klink、Gerard van Koten、Heinrich Lang

  DOI：10.1016/j.jorganchem.2008.02.027

  日期：2008.5

  Nitrile-functionalized NCN-pincer complexes of type [MBr(NC-4-C6H2(CH2NMe2)2-2,6)] (6a, M = Pd; 6b, M = Pt) (NCN = [C6H2(CH2NMe2)2-2,6]−) are accessible by the reaction of Br-1-NC-4-C6H2(CH2NMe2)2-2,6 (2b) with [Pd2(dba)3 · CHCl3] (5a) (dba = dibenzylidene acetone) and [Pt(tol-4)2(SEt2)]2 (5b) (tol = tolyl), respectively. Complex 6b could successfully be converted to the linear coordination polymer

  [MBr（NC-4-C 6 H 2（CH 2 NMe 2）2 -2,6）]型的腈官能化NCN钳配合物（6a，M = Pd; 6b，M = Pt）（NCN = [ C 6 H 2（CH 2 NMe 2）2 -2,6] -）可通过Br-1-NC-4-C 6 H 2（CH 2 NMe 2）2 -2,6（2b）反应获得与[Pd 2（dba）3  ·CHCl 3 ]（5a）（dba =二亚苄基丙酮）和[Pt（tol-4）2（SEt 2）] 2（5b）（tol =甲苯基）。配合物6b与环氧化物反应后，可以成功地将其转化为线性配位聚合物[Pt（NC-4-C 6 H 2（CH 2 NMe 2）2 -2,6）]（ClO 4）} n（8）。有机金属的异π-镊子化合物钛[Ti]（μ-σ，π-CCSiMe 3）2 } AgOClO 3（7）（钛[Ti] =（η 5 -C 5 H ^ 4SiMe 3）2 Ti）。
• Covalently Bonded Platinum(II) Complexes of -Amino Acids and Peptides as a Potential Tool for Protein Labeling
  作者：Gabriela Guillena、Gema Rodríguez、Martin Albrecht、Gerard van Koten

  DOI：10.1002/1521-3765(20021202)8:23<5368::aid-chem5368>3.0.co;2-d

  日期：2002.12.2

  Arylplatinum(II) complexes have been covalently bonded to the N and C termini and to the a-carbon of various amino acid derivatives. These organometallic-functionalized amino acid compounds can be converted into the corresponding free amino acids under both basic and acidic conditions; this demonstrates the excellent stability properties of these biomolecules. Due to the NMR activity displayed by the Pt-195 nucleus (natural abundance 33.8%, I = 1/2) these compounds are functional biomarkers. Furthermore, the ability of the arylplatinum functional group to bind SO2 gas, selectively and reversibly as indicated by changes in the spectroscopic properties (H-1, C-13, Pt-115 NMR and UV spectra) of these compounds, allows for the potential use of these complexes as in vitro biosensors.
• New Peptide Labels Containing Covalently Bonded Platinum(II) Centers as Diagnostic Biomarkers and Biosensors
  作者：Martin Albrecht、Gema Rodríguez、Jeroen Schoenmaker、Gerard van Koten

  DOI：10.1021/ol006484l

  日期：2000.11.1

  [GRAPHICS]Water and acid resistant arylplatinum(ll) complexes have been covalently bonded to the N-terminus of L-valine, thus providing organometallic biomolecules with excellent stability properties. Owing to the Pt-195 nucleus (I = 1/2), these building blocks are potentially versatile biomarkers (e.g., MRI), Moreover, they display efficient in vitro biosensor characteristics since they detect SO2 gas selectively and fully reversibly by an instantaneous change of the spectroscopic properties including a diagnostic Pt-195 NMR signal.
• Oxime-substituted NCN-pincer palladium and platinum halide polymers through non-covalent hydrogen bonding (NCN=[C6H2(CH2NMe2)2-2,6]−)
  作者：Stefan Köcher、Martin Lutz、Anthony L. Spek、Bernhard Walfort、Tobias Rüffer、Gerard P.M. van Klink、Gerard van Koten、Heinrich Lang

  DOI：10.1016/j.jorganchem.2008.03.020

  日期：2008.6

  The oxime-substituted NCN-pincer molecules HON=CH-1-C6H3(CH2NMe2)(2)-3,5 ( 2a) and HON=CH-4-C6H2( CH2NMe2)(2)-2,6-Br-1 ( 2b) were accessible by treatment of the benzaldehydes H(O)C-4-C6H3( CH2NMe2)(2)-3,5 (1a) and H(O)C-4-C6H2(CH2NMe2)(2)-2,6-Br-1 (1b) with an excess of hydroxylamine. In the solid state both compounds are forming polymers with intermolecular O-H center dot center dot center dot N connectivities between the Me2NCH2 substituents and the oxime entity of further molecules of 2a and 2b, respectively. Characteristic for 2a and 2b is a helically arrangement involving a crystallographic 21 screw axis of the HON=CH-1-C6H3(CH2NMe2)(2)-3,5 and HON=CH-4-C6H2(CH2NMe2)(2)-2,6-Br-1 building blocks. The reaction of 2b with equimolar amounts of [Pd-2(dba)(3)center dot CHCl3] ( 3) ( dba = dibenzylidene acetone) or [Pt(tol)(2)(SEt2)](2) (4) (tol=4-tolyl) gave by an oxidative addition of the C-Br unit to M coordination polymers with a [( HON=CH-4-C6H2(CH2NMe2)(2)-2,6)MBr] repeating unit (5:M = Pd, 6: M = Pt). Complexes 5 and 6 are in the solid state linear hydrogen-bridged polymers with O-H center dot center dot center dot Br contacts between the oxime entities and the metal-bonded bromide. (C) 2008 Elsevier B. V. All rights reserved.