1,3-bis(6-bromohexyloxy)benzene | 194854-06-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,3-bis(6-bromohexyloxy)benzene
• 英文别名: Benzene, 1,3-bis[(6-bromohexyl)oxy]-；1,3-bis(6-bromohexoxy)benzene
• CAS: 194854-06-3
• 化学式: C₁₈H₂₈Br₂O₂
• 分子量: 436.227
• InChiKey: WSAWZXVUQLCWLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  22
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-bis(6-bromohexyloxy)benzene 在 silver(I) acetate 、 碘 作用下， 以 氯仿 为溶剂， 反应 1.58h， 以84%的产率得到2,4-bis((6-bromohexyl)oxy)-1-iodobenzene
  参考文献：
  名称：

  机械手性平面手性rac- [2]轮烷的合成是通过分配非手性的[2]轮烷来实现的。

  摘要：

  通过将大体积的吡咯部分引入非手性[2]轮烷的轴成分中，合成了机械平面的手性[2]轮烷。通过手性HPLC分离对映体。在高温下两个隔室之间的环组分的穿梭引起了机械平面手性[2]轮烷的立体反转。定量研究了立体反转的速率，并确定了动力学参数。

  DOI：

  10.1021/acs.orglett.7b02043
• 作为产物：
  描述：

  1,6-二溴己烷 、 间苯二酚 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 以47%的产率得到1,3-bis(6-bromohexyloxy)benzene
  参考文献：
  名称：

  涉及2,9-双（4-羟苯基）-1,10-菲咯啉，α，ω-二溴化物和间苯二酚或2,7-二羟基萘的威廉姆森醚合成的大环化合物的合成，结构研究和碘化铜配合物

  摘要：

  制备了1,3-双（6-溴己氧基）苯，2,7-双（6-溴己氧基）萘，1,3-双（4-溴甲基苄氧基）苯和1,3-双（3-溴甲基苄氧基）苯通过间苯二酚或2,7-二羟基萘和1,6-二溴己烷，1,4-双（溴甲基）苯或1,3-双（溴甲基）苯进行的Williamson醚合成（产率21-47％）。在K 2 CO 3存在下，将这些二溴化物与2,9-双（4-羟苯基）-1,10-菲咯啉缩合，得到相应的31至35元大环化合物（3a – d，22–63％收率）。当3a - d用CuI处理时，形成单核1：1的配合物，其中CuI螯合到菲咯啉部分的氮供体原子上（4a – d，40–80％的产量）。使用密度泛函理论计算并在轮烷烷的情况下确定并分析了3a – c和4a – c的晶体结构，轮烷可以通过用末端炔烃处理4a – d来形成（例如大环尺寸，空隙体积）。4a - c中的铜和碘原子显着从菲咯啉部分的最小二乘平面突出（0.46-0

  DOI：

  10.1071/ch16587

文献信息

• Syntheses, X-ray structures and conformational studies of tetraoxa[n.n]metacyclophanes
  作者：Takuji Ogawa、Tomoaki Kishimoto、Keijiro Kobayashi、Noboru Ono

  DOI：10.1039/a705995g

  日期：——

  New types of macrocyclic ligands with tetraoxa[n.n]metacyclophane molecular skeletons have been synthesized. The structures of 14,28-dibromo-1,8,15,22-tetraoxa[8.8]metacyclophane 2a, 16,32-dibromo-1,10,17,26-tetraoxa[10.10]metacyclophane 2b, 14,28-dibromo-2,7,16,21-tetraoxa[8.8]metacyclophane 3a, 16,32-dibromo-2,9,18,25-tetraoxa[10.10]metacyclophane 3c, 18,36-dibromo-2,11,20,29-tetraoxa[12.12]metacyclophane 3d, 20,40-dibromo-2,13,22,33-tetraoxa[14.14]metacyclophane 3e and 14,28-diiodo- 2,7,16,21-tetraoxa[8.8]metacyclophane 9a have been determined by single-crystal X-ray structure analyses. In compounds 2a and 2b, two bromide atoms face each other within the macrocyclic ring while in compounds 3c, 3d and 3e the bromine atoms face in opposite directions, outwards from the macrocyclic ring. In the smaller ring compounds 3a and 9a the structure was intermediate between these two types.Substitution of the bromine atoms via lithiation has been achieved smoothly with iodine and methyl iodide as the electrophiles to afford disubstituted compounds in good yields, while with trimethylsilyl chloride as the electrophile the mono-substituted compound has been obtained.

  新型的具有四氧杂[n.n]甲桥并苯分子骨架的大环配体已被合成。通过单晶X射线结构分析确定了14,28-二溴-1,8,15,22-四氧杂[8.8]甲桥并苯2a、16,32-二溴-1,10,17,26-四氧杂[10.10]甲桥并苯2b、14,28-二溴-2,7,16,21-四氧杂[8.8]甲桥并苯3a、16,32-二溴-2,9,18,25-四氧杂[10.10]甲桥并苯3c、18,36-二溴-2,11,20,29-四氧杂[12.12]甲桥并苯3d、20,40-二溴-2,13,22,33-四氧杂[14.14]甲桥并苯3e和14,28-二碘-2,7,16,21-四氧杂[8.8]甲桥并苯9a的结构。在化合物2a和2b中，两个溴原子相对地位于大环内部，而在化合物3c、3d和3e中，溴原子则相对地向大环外部。在较小环的化合物3a和9a中，结构介于这两种类型之间。通过锂化反应，利用碘和甲基碘作为亲电试剂，顺利地实现了溴原子的取代，得到了产率良好的二取代化合物，而使用三甲基氯硅烷作为亲电试剂时，则得到了单取代的化合物。
• Template Synthesis of [2]Rotaxanes with Large Ring Components and Tris(biphenyl)methyl Group as the Blocking Group. The Relationship between the Ring Size and the Stability of the Rotaxanes
  作者：Shinichi Saito、Kazuko Nakazono、Eiko Takahashi

  DOI：10.1021/jo060829h

  日期：2006.9.1

  phenanthrolines 3a−e and a tris(biphenyl)methyl derivative 4. [2]Rotaxanes with large ring components (10a,b) were synthesized by the template method, and the stability of the rotaxanes was examined. The study revealed that the tris(biphenyl)methyl group is an effective blocking group for the rotaxanes with up to a 33-membered ring. Even a rotaxane with a 37-membered macrocyclic phenanthroline (10b) could

  我们合成了一系列大环菲咯啉3a - e和三（联苯）甲基衍生物4。[2]采用模板法合成了具有大环组分（10a，b）的轮烷，并考察了轮烷的稳定性。该研究表明，三（联苯）甲基是具有多达33元环的轮烷的有效保护基团。甚至可以分离出具有37元大环菲咯啉（10b）的轮烷。10b的解离发生在60°C。
• Syntheses, Structural Studies, and Copper Iodide Complexes of Macrocycles Derived from Williamson Ether Syntheses Involving 2,9-Bis(4-hydroxyphenyl)-1,10-phenanthroline, α,ω-Dibromides, and Resorcinol or 2,7-Dihydroxynaphthalene
  作者：Zuzana Baranová、Hashem Amini、Madhav Neupane、Sydney C. Garrett、Andreas Ehnbom、Nattamai Bhuvanesh、Joseph H. Reibenspies、John A. Gladysz

  DOI：10.1071/ch16587

  日期：——

  9-bis(4-hydroxyphenyl)-1,10-phenanthroline in the presence of K2CO3 to give the corresponding 31- to 35-membered macrocycles (3a–d, 22–63 % yield). When 3a–d were treated with CuI, mononuclear 1 : 1 complexes formed, in which the CuI chelates to the nitrogen donor atoms of the phenanthroline moiety (4a–d, 40–80 % yield). The crystal structures of 3a–c and 4a–c were determined and analyzed using density

  制备了1,3-双（6-溴己氧基）苯，2,7-双（6-溴己氧基）萘，1,3-双（4-溴甲基苄氧基）苯和1,3-双（3-溴甲基苄氧基）苯通过间苯二酚或2,7-二羟基萘和1,6-二溴己烷，1,4-双（溴甲基）苯或1,3-双（溴甲基）苯进行的Williamson醚合成（产率21-47％）。在K 2 CO 3存在下，将这些二溴化物与2,9-双（4-羟苯基）-1,10-菲咯啉缩合，得到相应的31至35元大环化合物（3a – d，22–63％收率）。当3a - d用CuI处理时，形成单核1：1的配合物，其中CuI螯合到菲咯啉部分的氮供体原子上（4a – d，40–80％的产量）。使用密度泛函理论计算并在轮烷烷的情况下确定并分析了3a – c和4a – c的晶体结构，轮烷可以通过用末端炔烃处理4a – d来形成（例如大环尺寸，空隙体积）。4a - c中的铜和碘原子显着从菲咯啉部分的最小二乘平面突出（0.46-0
• Synthesis, Structure and Catalytic Activity of Macrocyclic NHC Pd Pincer Complexes
  作者：Shinichi Saito、Isao Azumaya、Noriaki Watarai、Hiroyasu Kawasaki、Ryu Yamasaki

  DOI：10.3987/com-08-s(d)13

  日期：——

  We synthesized a series of new N-heterocyclic carbene (NHC) macrocyclic Pd pincer complexes (17-22) by the reaction of Pd(OAC)(2) or Pd-2(dba)(3) with the corresponding macrocycles, which were prepared by the coupling reaction of dibromides with bisimidazoles. The complex adopted twisted conformation, and the activation energy of the conformational interconversion of the macrocycle was determined by VT-NMR. We also examined the catalytic activity of these Pd complexes in Mizoroki-Heck and oxidative alkynyl-alkynyl homocoupling reactions.
• A Metal-Capped Conjugated Polyyne Threaded through a Phenanthroline-Based Macrocycle. Probing beyond the Mechanical Bond to Interactions in Interlocked Molecular Architectures
  作者：Hiba Sahnoune、Zuzana Baranová、Nattamai Bhuvanesh、John A. Gladysz、Jean-François Halet

  DOI：10.1021/om400709q

  日期：2013.11.11

  DFT calculations with long-range dispersion corrections have been used to analyze the structures and binding energies of rotaxanes featuring dimetal polyynediyl Pt2Cn dumbbells threaded through a 1,10-phenanthroline-based macrocycle. Results indicate that (i) the threading of the organometallic wire hardly affects its geometric and electronic properties and (ii) the noncovalent binding energies between the axle and macrocycle not only arise from mechanical bonding enforced weak interactions derived from the close proximity of the sp carbon chain to the macrocycle atoms, but also include hydrogen-bonding contacts involving hydrogen atoms of the metal bound phosphine ligands of the former and the nitrogen and oxygen atoms of the latter. The optimized geometries of the rotaxane and macrocycle are compared to the corresponding crystal structures where available.