1-bromo-3,5-bis[(dimethylamino)methyl]benzene

• 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: 1-bromo-3,5-bis[(dimethylamino)methyl]benzene
• 英文别名: 3,5-bis(dimethylaminomethyl)-1-bromobenzene；3,5-bis[(dimethylamino)methyl]bromobenzene；1-Br-3,5-bis(CH2NMe2)C6H3；1-[3-bromo-5-[(dimethylamino)methyl]phenyl]-N,N-dimethylmethanamine
• 化学式: C₁₂H₁₉BrN₂
• 分子量: 271.2
• InChiKey: FCXKZNCDJWLPDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-bromo-3,5-bis[(dimethylamino)methyl]benzene 在 双氧水 、 叔丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正戊烷 为溶剂， 反应 4.0h， 生成 tris{3,5-bis[(dimethylamino)methyl]phenyl}phosphane oxide
  参考文献：
  名称：

  Design and synthesis of tris[bis(benzylammonium)aryl]phosphines with bulky meta-substituents

  摘要：

  A novel 3,5,3',5,3",5"-hexakis(dimethylamino)methyl substituted triphenylphosphine analogue has been prepared. The six amine functionalities of the corresponding phosphine oxide and sulfide were alkylated quantitatively with methyl iodide and benzyl bromide, as well as with G I and G2 Frechet dendrons to afford the respective hexa-ammonium triarylphosphine oxides and sulfides. The phosphine sulfide derivatives were deprotected with P(n-Bu)3 to afford a series of hexa-ammonium triarylphosphines that range from small molecules to first and second generation dendrimers (MW up to 5451.44). Upon formation of the hexa-ammonium salt a clear shift in P-31 NMR is observed, indicative for opening of the C-P-C angle of the triaryl phosphine. Calculations on the hexacationic phosphines show an increased barrier of rotation around the P-C(aryl) bond with increasing size of the N-substituents. The calculated structure of the G2-dendron alkylated hexa-ammonium triarylphosphine shows that this dendritic phosphine has a disc-like rather than a cone-like structure, with an estimated cone angle of approximately 180degrees (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00467-8
• 作为产物：
  描述：

  3,5-二甲基溴苯 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 、 苯 为溶剂， 生成 1-bromo-3,5-bis[(dimethylamino)methyl]benzene
  参考文献：
  名称：

  Water-soluble phosphinothiol reagents

  摘要：

  水溶性试剂和方法用于在水介质中形成磷硫酸酯和叠氮基之间的酰胺键。磷硫酸酯是使用水溶性磷硫醇试剂生成的。该反应允许在水溶液中形成各种化学物种之间的酰胺键，包括氨基酸、肽或蛋白质片段。特别值得注意的是，该反应允许在生理环境中形成酰胺键。在一个特定实施例中，该发明提供了在水介质中进行肽连接的试剂和方法。该反应消除了对半胱氨酸残基的需求，并且是无痕迹的，不会在连接的肽产品中留下残留原子。

  公开号：

  US08410247B2

文献信息

• Selective Synthesis of Bisdimethylamine Derivatives from Diols and an Aqueous Solution of Dimethylamine through Iridium‐Catalyzed Borrowing Hydrogen Pathway
  作者：Jaeyoung Jeong、Ken‐ichi Fujita

  DOI：10.1002/cctc.202101499

  日期：2022.2.8

  A new system for the selective synthesis of bisdimethylamine derivatives using diols and aqueous dimethylamine as the starting materials was developed. An iridium complex bearing an N-heterocyclic carbene ligand was used as the catalyst, and the reaction proceeded based on the borrowing hydrogen strategy in an aqueous medium under mild conditions. Various bisdimethylamine derivatives were obtained

  开发了一种以二醇和二甲胺水溶液为原料选择性合成二甲胺衍生物的新系统。以带有N-杂环卡宾配体的铱配合物为催化剂，反应在温和条件下在水介质中基于借氢策略进行。以良好至极好的收率获得了各种双二甲胺衍生物。
• Synthesis and Properties ofpara-Substituted NCN-Pincer Palladium and Platinum Complexes
  作者：Martijn Q. Slagt、Gema Rodríguez、Michiel M. P. Grutters、Robertus J. M. Klein Gebbink、Wim Klopper、Leonardus W. Jenneskens、Martin Lutz、Anthony L. Spek、Gerard van Koten

  DOI：10.1002/chem.200305336

  日期：2004.3.19

  NCN-pincer palladium(II) and platinum(II) complexes [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)) were synthesised by routes involving substitution reactions, either prior to or, notably, after metalation of the ligand. The solubility of the pincer complexes is dominated by the

  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
• Synthesis and Characterization of the Bis-Cyclometalating Ligand 3,3‘,5,5‘-Tetrakis[(dimethylamino)methyl]biphenyl and Its Use in the Preparation of Bimetallic M(II), M(IV) (M = Pt, Pd), and Mixed-Valence Pt(II)−Pt(IV) Complexes <i>via</i> a Dilithio-Derivative. Crystal Structure of the Pd Dimer [ClPd{2,6-(Me₂NCH₂)₂C₆H₂}]₂
  作者：María-Cristina Lagunas、Robert A. Gossage、Anthony L. Spek、Gerard van Koten

  DOI：10.1021/om970650k

  日期：1998.2.1

  PtII dimer with 2 equiv of Cl2IPh. 1H NMR spectroscopic studies show that mixtures of the PtII and PtIV dimers in acetonitrile solution are in equilibrium with a mixed-valence (PtII,PtIV) species [(MeCN)PtII2,6-(Me2NCH2)2C6H2−C6H2(CH2NMe2)-2,6}PtIVCl2(NCMe)](CF3SO3)2, which, however, could not be isolated in pure form. The reaction of the PtII dimer with ≤1 equiv of Cl2IPh also gave a PtIV dimer, along

  一锅合成由3,5-（Me 2 NCH 2）2 C 6 H 3 Br制备了潜在的双环金属化配体3,3'，5,5'-四[（二甲基氨基）甲基]联苯涉及锂-卤素交换，过渡金属化和还原消除反应。该配体在联苯基的4和4'位置经历选择性二氢脱氢形成[Li 2 2,6-（Me 2 NCH 2）2 C 6 H 2 } 2 ] n，它是双金属配合物的多用途前体。通过双重金属转移反应。新型同双核Pt（II）和Pd（II）化合物[（MeCN）Pt 2,6-（Me 2 NCH 2）2 C 6 H 2 }-] 2（CF 3 SO 3）的合成与表征2和[CLPD 2,6-（ME 2 NCH 2）2 c ^ 6 ħ 2 } - ] 2，据报道，除了一个新的合成路线复杂[CLPT 2,6-（ME 2 NCH 2）2 C 6 H 2 } −] 2。通过单晶X射线衍射确定Pd二聚体的固态结构。将Cl 2氧化添加到后一种
• Metal ion detection by luminescent 1,3-bis(dimethylaminomethyl) phenyl receptor-modified chromophores and cruciforms
  作者：Anshuman Mangalum、Robert J. Gilliard Jr.、Jessica M. Hanley、Austa Marie Parker、Rhett C. Smith

  DOI：10.1039/c0ob00156b

  日期：——

  Chromophores ranging from simple small molecule π-conjugated systems comprised of phenylene ethynylene or fluorenylethynyl units to cross-conjugated Bunz-type cruciforms have been derivatized to include 1,3-bis(dimethylaminomethyl)phenyl moieties. The photophysical responsiveness of these diamino-substituted chromophores to metal ions has been examined. Both emission enhancement (turn-on) and ratiometric fluorescence detection of Cu2+ and Zn2+ ions have been achieved in THF.

  从简单的小分子π-共轭体系（由苯乙炔或芴乙炔单元构成）到交叉共轭的Bunz型十字形化合物，这些色素已被衍生化以包含1,3-双（N,N-二甲基氨基甲基）苯基基团。这些二氨基取代色素对金属离子的光物理响应性已被研究。在THF中，已实现对Cu2+和Zn2+离子的发射增强（开关）和比率荧光检测。
• Coulombic effects on the traceless Staudinger ligation in water
  作者：Annie Tam、Ronald T. Raines

  DOI：10.1016/j.bmc.2008.02.047

  日期：2009.2

  The traceless Staudinger ligation can be mediated by phosphinothiols under physiological conditions. Proximal positive charges are necessary to achieve that transformation, presumably because those charges discourage protonation of the key iminophosphorane intermediate. Here, a series of cationic phosphinothiols is used to probe Coulombic effects on the traceless Staudinger ligation in aqueous buffers

  无痕施陶丁格结扎可以在生理条件下由膦硫醇介导。近端正电荷是实现这种转化所必需的，大概是因为这些电荷会阻碍关键亚氨基膦中间体的质子化。在这里，一系列阳离子膦硫醇用于探测水性缓冲液中无痕施陶丁格结扎的库仑效应。试剂双（米- Ñ，Ñ -dimethylaminomethylphenyl）phosphinomethanethiol（3）被发现是优于其他，无论在它的介导无痕施陶丁格连接在水和其合成的效率的能力。