3-(2-Bromoethoxy)-2-(2-propenyloxy)benzaldehyde | 130642-25-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-(2-Bromoethoxy)-2-(2-propenyloxy)benzaldehyde
• 英文别名: 3-(2-Bromoethoxy)-2-prop-2-enoxybenzaldehyde
• CAS: 130642-25-0
• 化学式: C₁₂H₁₃BrO₃
• 分子量: 285.137
• InChiKey: UFSFLTZJGXJQRD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(2-Bromoethoxy)-2-(2-propenyloxy)benzaldehyde 在 对甲苯磺酸 sodium sulfide 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 40.0h， 生成 2,2'-phenylene>>bis(1,3-dioxolane)
  参考文献：
  名称：

  Macrocyclic trinucleating ligands for the cocomplexation of two "soft" (Cu2+, Ni2+, or Zn2+) metal centers and one "hard" (Ba2+ or Cs+) metal center

  摘要：

  Macrocyclic heterotrinucleating ligands that have one compartment for complexation of alkaline or alkaline earth cations and two compartments for transition-metal cations have been synthesized. The Ba2+-templated (2 + 2) macrocyclization of the dialdehydes 3a and 3b with the diamine 8 yielded the barium complexes (9b, 9e) in high yield. The Cs+-templated (2 + 2) macrocyclization of the dialdehyde 3a and the diamine 8 gave the cesium complex 9c. The mononuclear complexes were converted into the heterotrinuclear complexes 10a-h by reaction with 2 equiv of copper, nickel, or zinc acetate. The barium complex 9b, the dicopper/barium complex 10a, and the dinickel/barium complex 10b have been analyzed by X-ray crystallography. In all three crystal structures the O10 cavity is folded around the barium cation. The copper-copper distance in the dicopper/barium complex 10a is 3.50 angstrom and the nickel-nickel distance in the dinickel/barium complex 10b is 3.42 angstrom. The electrochemistry of the copper-containing heterotrinuclear complexes 10a, 10d, and 10g and the nickel-containing heterotrinuclear complexes 10b, 10e, and 10h has been studied by polarography, cyclic voltammetry, and coulometry in DMSO. The dinickel/barium complex 10b was also studied by Kalousek polarography. The dicopper/metal complexes 10a, 10d, and 10g all show a copper-copper interaction, which is the strongest for the dicopper/barium complex 10a. Coulometry revealed that the complexes 10a, 10d, and 10g undergo a reduction with two electrons, and cyclic voltammetry showed that the reduction/oxidation processes of 10a, 10d, and 10g are chemically reversible. The reduction/oxidation processes of the nickel-containing heterotrinuclear complexes 10b, 10e, and 10h are complicated by adsorption phenomena. Frozen EPR spectra of 10a and 10g exhibit typical triplet spectra with a zero-field splitting of about 0.04 cm-1. This behavior is typical for Cu(II) dimers and confirms that both Cu(II) cations are also exchange coupled in solution. A Cu-Cu distance in solution of 3.6 angstrom agrees best with the spectra. Attempts to add exogenous bridging ligands like F- and imidazolate were unsuccessful.

  DOI：

  10.1021/jo00001a043
• 作为产物：
  描述：

  2-allyloxy-3-hydroxybenzaldehyde 、 1,2-二溴乙烷 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以98%的产率得到3-(2-Bromoethoxy)-2-(2-propenyloxy)benzaldehyde
  参考文献：
  名称：

  Macrocyclic trinucleating ligands for the cocomplexation of two "soft" (Cu2+, Ni2+, or Zn2+) metal centers and one "hard" (Ba2+ or Cs+) metal center

  摘要：

  Macrocyclic heterotrinucleating ligands that have one compartment for complexation of alkaline or alkaline earth cations and two compartments for transition-metal cations have been synthesized. The Ba2+-templated (2 + 2) macrocyclization of the dialdehydes 3a and 3b with the diamine 8 yielded the barium complexes (9b, 9e) in high yield. The Cs+-templated (2 + 2) macrocyclization of the dialdehyde 3a and the diamine 8 gave the cesium complex 9c. The mononuclear complexes were converted into the heterotrinuclear complexes 10a-h by reaction with 2 equiv of copper, nickel, or zinc acetate. The barium complex 9b, the dicopper/barium complex 10a, and the dinickel/barium complex 10b have been analyzed by X-ray crystallography. In all three crystal structures the O10 cavity is folded around the barium cation. The copper-copper distance in the dicopper/barium complex 10a is 3.50 angstrom and the nickel-nickel distance in the dinickel/barium complex 10b is 3.42 angstrom. The electrochemistry of the copper-containing heterotrinuclear complexes 10a, 10d, and 10g and the nickel-containing heterotrinuclear complexes 10b, 10e, and 10h has been studied by polarography, cyclic voltammetry, and coulometry in DMSO. The dinickel/barium complex 10b was also studied by Kalousek polarography. The dicopper/metal complexes 10a, 10d, and 10g all show a copper-copper interaction, which is the strongest for the dicopper/barium complex 10a. Coulometry revealed that the complexes 10a, 10d, and 10g undergo a reduction with two electrons, and cyclic voltammetry showed that the reduction/oxidation processes of 10a, 10d, and 10g are chemically reversible. The reduction/oxidation processes of the nickel-containing heterotrinuclear complexes 10b, 10e, and 10h are complicated by adsorption phenomena. Frozen EPR spectra of 10a and 10g exhibit typical triplet spectra with a zero-field splitting of about 0.04 cm-1. This behavior is typical for Cu(II) dimers and confirms that both Cu(II) cations are also exchange coupled in solution. A Cu-Cu distance in solution of 3.6 angstrom agrees best with the spectra. Attempts to add exogenous bridging ligands like F- and imidazolate were unsuccessful.

  DOI：

  10.1021/jo00001a043

文献信息

• Synthesis and Characterization of a Novel Heteroditopic Macrocyclic System – Monometallic Nickel( <scp>II</scp> ) and Uranyl Complexes and Their Corresponding Heterobimetallic Carbonylrhodium( <scp>I</scp> ) Complexes
  作者：Mauro Bassetti、Andrea Calenne、Lucilla Mastrofrancesco、Michela Salamone、Gabriele Bocelli、Andrea Cantoni、Amos Musatti

  DOI：10.1002/ejic.200500703

  日期：2006.3

  ligand system for selective coordination of two different transition metal ions has been obtained in the form of monometallic salen complexes of NiII (LNi, 1) and uranyl (LUO2, 2). The system is characterized by the presence of a dianionic, tetradentate salen donor system (N2O2) derived from cis-1,2-diaminocyclohexane and of a neutral, tridentate 2,6-bis(alkylthiomethyl)pyridine group (NS2). The two binding

  以 NiIII (LNi, 1) 和铀酰 (LUO2, 2) 的单金属 salen 配合物的形式获得了一种用于选择性配位两种不同过渡金属离子的新型异双位大环配体系统。该系统的特征在于存在衍生自顺-1,2-二氨基环己烷的双阴离子四齿salen供体系统(N2O2)和中性三齿2,6-双(烷硫基甲基)吡啶基团(NS2)。两个结合位点由两条氧乙基链连接。合成过程包括将 2,6-双（巯基甲基）吡啶的二钠盐与两当量的 3-（2-溴乙氧基）-2-（2-丙烯氧基）苯甲醛偶联。通过钯催化从反应产物 (I) 中去除保护性烯丙基，得到配体合成子 2,6-双[2-(3-甲酰基-2-羟基苯基)氧基乙基]硫甲基吡啶 (II)。单金属大环配合物 1 和 2，分别由顺式 1,2-二氨基环己烷、ligson II 和相应的 NiII 或醋酸铀酰盐在双（三氟乙酸）钡存在下通过金属模板合成得到。通过溶液中的光谱技术和固态下的 X