4-bromo-1,2-bis(octyloxy)benzene | 291753-67-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-bromo-1,2-bis(octyloxy)benzene
• 英文别名: 4-bromo-1,2-dioctoxybenzene
• CAS: 291753-67-8
• 化学式: C₂₂H₃₇BrO₂
• 分子量: 413.439
• InChiKey: NCPOKNBUYXLCFU-UHFFFAOYSA-N

物化性质

• 熔点：
  33-34 °C
• 沸点：
  452.1±25.0 °C(Predicted)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  25
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  4-bromo-1,2-bis(octyloxy)benzene 在 palladium diacetate 、 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 potassium carbonate 、 三(邻甲基苯基)磷 作用下， 以 四氢呋喃 、 甲醚 、 水 为溶剂， 反应 5.0h， 生成 2-bromo-4,5,3',4'-tetrakis-octyloxy-biphenyl
  参考文献：
  名称：

  Synthesis and Properties of Poly(10-Octylphenothiazine-CO-2′,3′,6′,7′-Tertrakis-Octyloxy-9-Spirobifluorene) for OLEDs

  摘要：

  Many attempts have been focused on polymer light-emitting diodes ( PLEDs) for large area display application. We report synthesis and properties of new phenothiazyl polymer derivatives, Poly(10-octyl-10H-phenothiazine-3,7-diyl) ( POP), Poly( 20,30,60,70-tertrakis-octyloxy-9-spirobifluorene-2,7-diyl) ( PTOSF), and their random copolymers, Poly( 10-octylphenothiazine-co-20,30,60,70- tertrakis-octyloxy-9-spirobifluorene) ( POTOSF), which were polymerized by Yamamoto reaction. The obtained compound was identified by H-1- NMR, UV- Visible spectroscopy and GPC data. Weight average molecular number ( Mn) of the polymers ranged from 17,000 to 300,000 g= mol with polydispersity indices of 1.6 similar to 6.5. Maximum UV-Visible absorption of the polymers was distributed from 285 to 403 nm. PL emission of POP, PTOSF and POTOSF copolymer were found to be 480, 434 and 484 nm, respectively. EL emission peak of double- layer EL device of POTOSF was at 494nm ( bluish green).

  DOI：

  10.1080/15421400601013429
• 作为产物：
  描述：

  1,2-二(辛氧基)苯 在 copper(ll) bromide 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以64%的产率得到4-bromo-1,2-bis(octyloxy)benzene
  参考文献：
  名称：

  溴化铜 (II)：一种用于富电子芳香族化合物的简单且选择性的单溴化试剂

  摘要：

  摘要 溴化铜 (II) 被发现是一种在室温下单溴化富电子芳香化合物的简单有效的试剂。与苯酚、芳烷基醚和芳香胺的反应顺利进行，以中等至良好的收率选择性地提供相应的单溴化产物。

  DOI：

  10.1080/00908320701230026

文献信息

• Copper(II) Bromide: A Simple and Selective Monobromination Reagent for Electron‐Rich Aromatic Compounds
  作者：Suchitra Bhatt、Sandip K. Nayak

  DOI：10.1080/00908320701230026

  日期：2007.4.1

  Abstract Copper(II) bromide was found to be a simple and efficient reagent for monobromination of electron‐rich aromatic compounds at room temperature. The reaction proceeded smoothly with phenols, aryl alkyl ethers, and aromatic amines to afford the corresponding monobrominated product selectively in moderate to good yields.

  摘要 溴化铜 (II) 被发现是一种在室温下单溴化富电子芳香化合物的简单有效的试剂。与苯酚、芳烷基醚和芳香胺的反应顺利进行，以中等至良好的收率选择性地提供相应的单溴化产物。
• Synthesis of oleophilic electron-rich phenylhydrazines
  作者：Aleksandra Jankowiak、Piotr Kaszyński

  DOI：10.3762/bjoc.8.29

  日期：——

  Phenylhydrazines 1 substituted with two or three long-chain alkyl, alkoxy or alkylsulfanyl groups were successfully prepared by acid-induced removal of the Boc group in hydrazides 2. The reaction is carried out with 5 equivalents of TfOH in CF₃CH₂OH/CH₂Cl₂ at −40 °C for 1.5 min. Under these conditions, the deprotected hydrazine 1 is fully protonated, which increases its stability in the reaction medium. The hydrazines were isolated in 60–86% yields and purities >90%. The hydrazides 2 were obtained in 43–71% yields from aryl bromides 5, which were lithiated with t-BuLi and subsequently reacted with di-tert-butyl azodicarboxylate (DTBAD).

  苯基肼1通过酸诱导去除肼酰胺2中的Boc基团，成功地取代了两个或三个长链烷基、烷氧基或烷基硫基团。反应在CF₃CH₂OH/CH₂Cl_{2>中以5当量的TfOH在-40°C下进行1.5分钟。在这些条件下，去保护的肼1被完全质子化，增加了其在反应介质中的稳定性。肼类产物以60-86%的产率和纯度>90%的纯度分离。肼酰胺2以43-71%的产率从芳基溴化物5中获得，该溴化物通过与t-BuLi锂化，然后与双tert-丁基叠氮二羧酸酯（DTBAD）反应得到。}
• Liquid crystalline behavior of tetraaryl derivatives of benzo[c]cinnoline, tetraazapyrene, phenanthrene, and pyrene: the effect of heteroatom and substitution pattern on phase stability
  作者：Monika J. Sienkowska、John M. Farrar、Fan Zhang、Sharat Kusuma、Paul A. Heiney、Piotr Kaszynski

  DOI：10.1039/b615545f

  日期：——

  A series of closely related tetrasubstituted derivatives of benzo[c]cinnoline (1), tetraazapyrene (2), phenanthrene (3), and pyrene (4) were investigated for their mesogenic properties using thermal, optical, spectroscopic, and powder XRD analyses. Only three 3,4-dioctyloxyphenyl derivatives exhibited mesogenic properties. Substitution of N for CH (3 → 1 and 4 → 2 pairs) and also increase of the core element size (1 → 2 and 3 → 4 pairs) significantly increases the mesophase stability. The findings and observed trends were rationalized by analysis of conformational properties which included calculation of the planarization energy, and modeling of aliphatic chain density and fill fractions. MO calculations showed that the tetraaza derivative 2c is significantly electron deficient and suitable for electron conductive materials.

  一系列密切相关的四取代苯并[c]吡咯啉（1）、四烯氮（2）、菲（3）和芘（4）衍生物的介质性质通过热学、光学、光谱及粉末XRD分析进行了研究。只有三种3,4-二辛氧基苯衍生物表现出了介质特性。将N替换为CH（3→1和4→2对）以及核心元素尺寸的增加（1→2和3→4对）显著提高了相位稳定性。研究结果及观察到的趋势通过对构象特性的分析进行了合理化，包括平面化能量的计算，以及脂肪链密度和填充分数的建模。分子轨道计算显示，四氮衍生物2c显著缺电子，适合用于电子导电材料。
• Thermotropic MIDA Boronates as a Case Study for the Role of Dipolar Interactions in Liquid Crystalline Self-Assembly
  作者：Tobias Wöhrle、Rafet Gündemir、Wolfgang Frey、Friederike Knecht、Andreas Köhn、Sabine Laschat

  DOI：10.1002/chem.201605648

  日期：2017.3.23

  decoupled from the MIDA head group. These theoretical findings were supported by IR and Raman spectra as well as by asingle crystal structure analysis of 4‐ethoxyphenyl MIDA boronate. Calculations of the electrostatic potential of the MIDA boronate reveal a special polarity pattern that can support the formation of a two‐dimensional network and is likely to explain the liquid crystalline self‐assembly. The

  合成了一系列带有4-烷氧基，3,4-双烷氧基或3,4,5-三烷氧基苯基取代基的MIDA（N-甲基亚氨基二乙酸）硼酸酯，并通过差示扫描量热法（DSC），偏光光学显微镜对它们的介晶性质进行了表征。 （POM）和X射线衍射（XRD）技术，例如小角度和广角X射线散射（分别为SAXS和WAXS）。大多数衍生物是液晶的。对于单或双烷氧基取代的衍生物，尽管MIDA头基庞大，但C 6链已经诱导了近晶A（SmA）中间相。随着链长的增加，圆柱状六角形（Col h）相取代了双取代系列中的SmA相。对一系列MIDA硼酸盐的量子化学计算表明，B-N键是一个在硼原子上带正电荷而在氮和氧原子上带负电荷的双键。此外，未发现芳基部分和B-N键之间存在π相互作用，因此介晶单元与MIDA头基电子分离。IR和拉曼光谱以及4-乙氧基苯基MIDA硼酸酯的单晶体结构分析为这些理论发现提供了支持。MIDA硼酸酯的静电势的计算揭示了一种特
• Self-assembly of columnar mesophases from diaminotriazines
  作者：Kenneth E. Maly、Caroline Dauphin、James D. Wuest

  DOI：10.1039/b610666h

  日期：——

  Diaminotriazines are known to self-associate in solution, in the solid state, and on surfaces via characteristic hydrogen bonding motifs. Although complementary hydrogen bonding between diaminotriazine derivatives and carboxylic acids has been shown to induce mesomorphic properties, the hydrogen-bonded self-association of diaminotriazines to form liquid crystalline phases has not been reported. Here, we describe the synthesis and mesophase characterization of biphenyldiaminotriazines bearing one alkoxy side-chain (compound 3) or two alkoxy side-chains (compound 2). Although compound 3 does not show any mesomorphism, derivatives of compound 2 exhibit thermotropic columnar mesophases as shown by polarized optical microscopy, differential scanning calorimetry, and variable-temperature X-ray powder diffraction. The results are consistent with self-assembly of a hexameric hydrogen-bonded rosette that can stack to form columnar mesophases, suggesting that the association of diaminotriazines by hydrogen bonding can play an important role in directing molecular organization in liquid crystalline phases.

  已知二氨基三嗪通过特征性氢键结构在溶液、固态和表面上能够自组装。虽然二氨基三嗪衍生物和羧酸之间的互补氢键已被证实可以诱导介晶性质,但二氨基三嗪通过氢键自组装形成液晶相尚未见报道。本文描述了带有一个烷氧基侧链(化合物3)或两个烷氧基侧链(化合物2)的联苯二氨基三嗪的合成和介晶相表征。虽然化合物3不显示任何介晶性,但化合物2的衍生物表现出热致柱状介晶相,这通过偏光显微镜、差示扫描量热法和可变温X射线粉末衍射得到证实。结果表明,六聚体氢键玫瑰环可以堆积形成柱状介晶相,说明二氨基三嗪通过氢键结合在液晶相分子组织中起重要作用。