2-bromo-4-(3',5'-di-tert-butyl-4'-acetoxyphenyl)styrene | 159767-68-7

• 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: 2-bromo-4-(3',5'-di-tert-butyl-4'-acetoxyphenyl)styrene
• 英文别名: [4-(3-Bromo-4-ethenylphenyl)-2,6-ditert-butylphenyl] acetate
• CAS: 159767-68-7
• 化学式: C₂₄H₂₉BrO₂
• 分子量: 429.397
• InChiKey: NUOLWWAIVGRBDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-bromo-4-(3',5'-di-tert-butyl-4'-acetoxyphenyl)styrene 在 氢氧化钾 、 乙基溴化镁 、 溴 作用下， 以 氯仿 、 水 、 二甲基亚砜 、 乙腈 为溶剂， 反应 25.33h， 生成 1-[2-bromo-4-[3',5'-di-tert-butyl-4'-(trimethylsilyloxy)phenyl]phenyl]-2-(trimethylsilyl)acetylene
  参考文献：
  名称：

  高自旋氧苯基苯并环化脱氢[12]环烯

  摘要：

  合成了基态四重分子2,8,14-三氧苯基三苯并三脱氢[12]环烯；脱氢环烯作为悬垂自旋的有效铁磁耦合器。

  DOI：

  10.1246/cl.1999.161
• 作为产物：
  描述：

  在 sodium hydroxide 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 2-bromo-4-(3',5'-di-tert-butyl-4'-acetoxyphenyl)styrene
  参考文献：
  名称：

  Poly(phenylenevinylene)-Attached Phenoxyl Radicals:  Ferromagnetic Interaction through Planarized and π-Conjugated Skeletons

  摘要：

  Chemically stable poly[2-(3,5-di-tert-butyl-4-oxyphenyl)-1,4(p)-phenylenevinylene], poly[4-(3,5-di-tert-butyl-4-oxyphenyl)-1,3(m)-phenylenevinylene], and poly[4-(3,5-di-tert-butyl-4-oxyphenyl)-1,2(o)-phenylenevinylene] were synthesized via the polymerization of 4-bromo-2-(3,5-di-tert-butyl-4-acetoxyphenyl)styrene, 5-bromo-2-(3,5-di-tert-butyl-4-acetoxyphenyl) styrene, and 2-bromo-4-(3,5-di-tert-butyl-4-acetoxyphenyl) styrene, respectively, using a palladium catalyst. The o- and p-polyradicals, even with their spin concentration of 0.6 spin/unit, displayed S values of 4/2 to 5/2 (S = 5/2 for the o-polyradical with a degree of polymerization of 17 and a spin concentration of 0.68), while the m-polyradical has a singlet ground state. A long-range intramolecular through-bond ferromagnetic exchange interaction was realized between the pendant unpaired electrons for the o- and p-polyradicals, in accordance with theoretical predictions based on the molecular connectivity. The average value of the exchange coupling constant for the o-polyradical, 2 (J) over bar = 48 +/- 6 cm(-1), was larger than 2 (J) over bar = 32 +/- 2 cm(-1) for the p-polyradical, while they were almost coincident with or much larger than the exchange coupling constants for the corresponding diradical model compounds. Both force field calculations and spectroscopic results indicated a less hindered steric structure with a planarized pi-conjugated skeleton for the o-polyradical.

  DOI：

  10.1021/ja961721u

文献信息

• A Nanometer-Sized High-Spin Polyradical:  Poly(4-phenoxyl-1,2-phenylenevinylene) Planarily Extended in a Non-Kekulé Fashion and Its Magnetic Force Microscopic Images
  作者：Hiroyuki Nishide、Takahiro Ozawa、Makoto Miyasaka、Eishun Tsuchida

  DOI：10.1021/ja002944u

  日期：2001.6.1

  non-Kekulé- and nondisjoint-type poly(1,2-phenylenevinylene) network bearing 4-substituted di-tert-butylphenoxyls was synthesized through a one-pot polycondensation of the star-shaped subpart and the subsequent oxidation, which was persistent even at room temperature. The polyphenoxyl radical with a spin concentration of 0.4 displayed an average S of 10/2. The polyradical with the molecular weight of 3

  通过星形子部分的一锅缩聚反应和随后的氧化，合成了带有 4-取代二叔丁基苯氧基的 pi 共轭但非 Kekulé 型和非分离型聚（1,2-亚苯基亚乙烯基）网络，即使在室温下也能持续存在。自旋浓度为 0.4 的聚苯氧基自由基的平均 S 为 10/2。分子量为 3.2 x 10(4) 的多自由基给出了大约的圆盘状图像。35 x 0.6 nm 具有原子力显微镜和磁力显微镜：分子图像被检查为纳米级和基于单分子的磁点。
• Optical nonlinearity of an open-shell and degenerate π-conjugated polymer: poly(4-oxyphenyl-1,2-phenylenevinylene) radical
  作者：Masahiro Takahashi、Eishun Tsuchida、Hiroyuki Nishide、Masahiro Takahashi、Shinji Yamada、Hiro Matsuda、Hachiro Nakanishi

  DOI：10.1039/a705028c

  日期：——

  Third-order nonlinear optical susceptibility is enhanced by three orders of magnitude for the degenerate and high-spin ground state conjugated polymer, poly(4-oxyphenyl-1,2-phenylenevinylene), as compared with a precursor conjugated polymer with a closed-shell configuration, in a z-scan measurement.

  在 Z 扫描测量中，与具有闭壳构型的前体共轭聚合物相比，变性和高自旋基态共轭聚合物聚（4-氧苯基-1,2-苯基乙烯）的三阶非线性光学感度增强了三个数量级。
• Acyclic and Cyclic Di- and Tri(4-oxyphenyl-1,2-phenyleneethynylene)s:  Their Synthesis and Ferromagnetic Spin Interaction
  作者：Hiroyuki Nishide、Masahiro Takahashi、Junichi Takashima、Yong-Jin Pu、Eishun Tsuchida

  DOI：10.1021/jo990575i

  日期：1999.10.1

  A new set of pi-conjugated and alternant but non-Kekule-type di- and tri(1,2-phenyleneethynylene)s pendantly substituted with phenoxyl radicals at the 4 positions (1a, 2a, and 3a) was synthesized. The synthesis of these acyclic and cyclic compounds was achieved through the head-to-tail coupling of a-bromo(or -iodo)-4-[3',5'-di-tert-butyl-4'-trimethylsiloxyl(or-hydroxy)phenyl]-1-ethynylbenzenes. The di- and triphenoxyl compounds (1a, and 2a and 3a) were triplet and quartet at the ground state, respectively, which was ascribed to a ferromagnetic coupling effect of the diphenyl ethynylene bridge for the pendant phenoxyls' spins. The cyclic pi-conjugation in 3a exhibited a stronger effect on the spin alignment.
• Poly(phenylenevinylene)-Attached Phenoxyl Radicals:  Ferromagnetic Interaction through Planarized and π-Conjugated Skeletons
  作者：Hiroyuki Nishide、Takashi Kaneko、Takeshi Nii、Kohya Katoh、Eishun Tsuchida、Paul M. Lahti

  DOI：10.1021/ja961721u

  日期：1996.1.1

  Chemically stable poly[2-(3,5-di-tert-butyl-4-oxyphenyl)-1,4(p)-phenylenevinylene], poly[4-(3,5-di-tert-butyl-4-oxyphenyl)-1,3(m)-phenylenevinylene], and poly[4-(3,5-di-tert-butyl-4-oxyphenyl)-1,2(o)-phenylenevinylene] were synthesized via the polymerization of 4-bromo-2-(3,5-di-tert-butyl-4-acetoxyphenyl)styrene, 5-bromo-2-(3,5-di-tert-butyl-4-acetoxyphenyl) styrene, and 2-bromo-4-(3,5-di-tert-butyl-4-acetoxyphenyl) styrene, respectively, using a palladium catalyst. The o- and p-polyradicals, even with their spin concentration of 0.6 spin/unit, displayed S values of 4/2 to 5/2 (S = 5/2 for the o-polyradical with a degree of polymerization of 17 and a spin concentration of 0.68), while the m-polyradical has a singlet ground state. A long-range intramolecular through-bond ferromagnetic exchange interaction was realized between the pendant unpaired electrons for the o- and p-polyradicals, in accordance with theoretical predictions based on the molecular connectivity. The average value of the exchange coupling constant for the o-polyradical, 2 (J) over bar = 48 +/- 6 cm(-1), was larger than 2 (J) over bar = 32 +/- 2 cm(-1) for the p-polyradical, while they were almost coincident with or much larger than the exchange coupling constants for the corresponding diradical model compounds. Both force field calculations and spectroscopic results indicated a less hindered steric structure with a planarized pi-conjugated skeleton for the o-polyradical.
• High-Spin Oxyphenylbenzo-Annelated Dehydro[12]annulene
  作者：Yong-Jin Pu、Masahiro Takahashi、Eishun Tsuchida、Hiroyuki Nishide

  DOI：10.1246/cl.1999.161

  日期：1999.2

  A ground state quartet molecule, 2,8,14-trisoxyphenyltribenzotrisdehydro[12]annulene, was synthesized; the dehydroannulene acted as an effective ferromagnetic coupler for the pendant spins.

  合成了基态四重分子2,8,14-三氧苯基三苯并三脱氢[12]环烯；脱氢环烯作为悬垂自旋的有效铁磁耦合器。