4,4',4''-((4-(2-(2-bromoethoxy)ethoxy)phenyl)methanetriyl)-tris(tert-butylbenzene) | 253600-70-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4,4',4''-((4-(2-(2-bromoethoxy)ethoxy)phenyl)methanetriyl)-tris(tert-butylbenzene)
• 英文别名: 1-[2-(2-Bromoethoxy)ethoxy]-4-[tris(4-tert-butylphenyl)methyl]benzene；1-[2-(2-bromoethoxy)ethoxy]-4-[tris(4-tert-butylphenyl)methyl]benzene
• CAS: 253600-70-3
• 化学式: C₄₁H₅₁BrO₂
• 分子量: 655.759
• InChiKey: CPWBMMQLIVGGBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.6
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 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：

  4,4',4''-((4-(2-(2-bromoethoxy)ethoxy)phenyl)methanetriyl)-tris(tert-butylbenzene) 在 三苯基膦 bis-triphenylphosphine-palladium(II) chloride 、 cesium hydroxide 、 copper(l) iodide 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 丙酮 、 甲苯 为溶剂， 反应 108.0h， 生成 5-[4-[2-[5-[2-[2-[2,6-Di(propan-2-yl)phenoxy]ethoxy]ethoxy]naphthalen-1-yl]ethynyl]phenyl]-2-[4-[2-[2-[4-[tris(4-tert-butylphenyl)methyl]phenoxy]ethoxy]ethylsulfanyl]-1,3-dithiol-2-ylidene]-[1,3]dithiolo[4,5-c]pyrrole
  参考文献：
  名称：

  功能刚性双稳态 [2] 轮烷

  摘要：

  已合成并表征了简并萘 (NP) 穿梭和非简并单吡咯并四硫富瓦烯 (MPTTF)/NP 氧化还原可控开关形状的两站 [2] 轮烷。它们的哑铃形组分由沿其长度中断的聚醚链组成，由 (i) 两个富电子站 - 两个 NP 部分或一个 MPTTF 单元和一个 NP 部分 - 与 (ii) 刚性芳乙炔基或丁二炔基间隔物位于两个站，并由（iii）在哑铃的每一端灵活系绳的疏水塞终止。研究这种修饰是为了简化之前在相关双稳态 [2] 轮烷中观察到的分子结构和转换功能，在它们的站之间具有柔性间隔物并结合环双（百草枯-对亚苯基）（CBPQT4+）环。非简并 MPTTF-NP 开关被分离为接近无异构体的双稳态 [2] 轮烷。MPTTF 的使用消除了表征四硫富瓦烯 (TTF) 母体核心结构的顺/反异构化。此外，仅观察到一种平移异构体（> 95 < 5），令人惊讶的是在很宽的温度范围内（198-323 K），这意味着 CBPQT4+

  DOI：

  10.1021/ja0663529
• 作为产物：
  描述：

  mono-p-phenyl ether of di(ethylene glycol) 在 三乙胺 、 lithium bromide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 6.0h， 生成 4,4',4''-((4-(2-(2-bromoethoxy)ethoxy)phenyl)methanetriyl)-tris(tert-butylbenzene)
  参考文献：
  名称：

  A Transition Metal Containing Rotaxane in Motion: Electrochemically Induced Pirouetting of the Ring on the Threaded Dumbbell

  摘要：

  In this work we describe a rotaxane in which a new type of motion, pirouetting of the wheel around its axle, can be electrochemically triggered. The rotaxane was synthesized by using the three-dimensional effect of copper(I). It incorporates both a hetero-biscoordinating ring (containing both 2,9-diphenyl-1,10-phenanthroline and 2,2':6',2"-terpyridine units) and a molecular string which contains only one 2,9-diphenyl-1,10-phenanthroline. Both ends of the string are functionnalized by a bulky stopper ( tris(p-tert-butylphenyl) (4-hydroxypbenyl)methane). Large molecular motions have been induced electrochemically in this molecule and were detected by using cyclic voltammetry. The driving force of the two rearrangement processes observed is the high stability of two markedly different coordination environments for copper(I) and copper(II) ions. In the copper(I) state, two phenanthroline units tone of the ring, one of the string) interact with the metal in a tetrahedral geometry (Cu-(4)(I)), whereas in the copper(II) state the five-coordinate geometry (Cu-(5)(II)) is due to the phenanthroline of the string and to the terpyridine of the ring. The kinetic rate constants of the two molecular motion processes (from Cu-(5)(I)) to Cu-(4)(II)) and fom Cu-(4)(II)) to Cu-(5)(II))) have been determined and both rates are much faster than the ones in previously studied analoguous systems. In addition, the rate of the pirouetting motion depends greatly on the copper oxidation state. The divalent four-coordinate copper complex (Cu-(4)(II))) rearranges in tens of seconds, whereas the monovalent five-coordinate copper system leads to the four-coordinate complex in the millisecond time scale.

  DOI：

  10.1002/(sici)1521-3765(19991105)5:11<3310::aid-chem3310>3.0.co;2-r

文献信息

• Rotaxanes and Biofunctionalized Pseudorotaxanes via Thiol-Maleimide Click Chemistry
  作者：Umesh Choudhary、Brian H. Northrop

  DOI：10.1021/ol300614z

  日期：2012.4.20

  Base-catalyzed thiol-maleimide click chemistry has been applied to the synthesis of neutral donor–acceptor [2]rotaxanes in good yield. This method is extended further to the synthesis of a glutathione-functionalized [2]pseudorotaxane, a precursor to integrated conjugates of interlocked molecules with proteins and enzymes.

  碱催化的巯基-马来酰亚胺点击化学已以良好的产率用于合成中性供体-受体[2]轮烷。该方法进一步扩展到谷胱甘肽功能化的[2]假轮烷的合成，这是互锁分子与蛋白质和酶的整合结合物的前体。
• Functionally Rigid Bistable [2]Rotaxanes
  作者：Sune Nygaard、Ken C.-F. Leung、Ivan Aprahamian、Taichi Ikeda、Sourav Saha、Bo W. Laursen、Soo-Young Kim、Stinne W. Hansen、Paul C. Stein、Amar H. Flood、J. Fraser Stoddart、Jan O. Jeppesen

  DOI：10.1021/ja0663529

  日期：2007.1.1

  hydrophobic stoppers at each end of the dumbbells. This modification was investigated as a means to simplify both molecular structure and switching function previously observed in related bistable [2]rotaxanes with flexible spacers between their stations and incorporating a cyclobis(paraquat-p-phenylene) (CBPQT4+) ring. The nondegenerate MPTTF-NP switch was isolated as near isomer-free bistable [2]rotaxane

  已合成并表征了简并萘 (NP) 穿梭和非简并单吡咯并四硫富瓦烯 (MPTTF)/NP 氧化还原可控开关形状的两站 [2] 轮烷。它们的哑铃形组分由沿其长度中断的聚醚链组成，由 (i) 两个富电子站 - 两个 NP 部分或一个 MPTTF 单元和一个 NP 部分 - 与 (ii) 刚性芳乙炔基或丁二炔基间隔物位于两个站，并由（iii）在哑铃的每一端灵活系绳的疏水塞终止。研究这种修饰是为了简化之前在相关双稳态 [2] 轮烷中观察到的分子结构和转换功能，在它们的站之间具有柔性间隔物并结合环双（百草枯-对亚苯基）（CBPQT4+）环。非简并 MPTTF-NP 开关被分离为接近无异构体的双稳态 [2] 轮烷。MPTTF 的使用消除了表征四硫富瓦烯 (TTF) 母体核心结构的顺/反异构化。此外，仅观察到一种平移异构体（> 95 < 5），令人惊讶的是在很宽的温度范围内（198-323 K），这意味着 CBPQT4+
• A Transition Metal Containing Rotaxane in Motion: Electrochemically Induced Pirouetting of the Ring on the Threaded Dumbbell
  作者：Laurence Raehm、Jean-Marc Kern、Jean-Pierre Sauvage

  DOI：10.1002/(sici)1521-3765(19991105)5:11<3310::aid-chem3310>3.0.co;2-r

  日期：1999.11.5

  In this work we describe a rotaxane in which a new type of motion, pirouetting of the wheel around its axle, can be electrochemically triggered. The rotaxane was synthesized by using the three-dimensional effect of copper(I). It incorporates both a hetero-biscoordinating ring (containing both 2,9-diphenyl-1,10-phenanthroline and 2,2':6',2"-terpyridine units) and a molecular string which contains only one 2,9-diphenyl-1,10-phenanthroline. Both ends of the string are functionnalized by a bulky stopper ( tris(p-tert-butylphenyl) (4-hydroxypbenyl)methane). Large molecular motions have been induced electrochemically in this molecule and were detected by using cyclic voltammetry. The driving force of the two rearrangement processes observed is the high stability of two markedly different coordination environments for copper(I) and copper(II) ions. In the copper(I) state, two phenanthroline units tone of the ring, one of the string) interact with the metal in a tetrahedral geometry (Cu-(4)(I)), whereas in the copper(II) state the five-coordinate geometry (Cu-(5)(II)) is due to the phenanthroline of the string and to the terpyridine of the ring. The kinetic rate constants of the two molecular motion processes (from Cu-(5)(I)) to Cu-(4)(II)) and fom Cu-(4)(II)) to Cu-(5)(II))) have been determined and both rates are much faster than the ones in previously studied analoguous systems. In addition, the rate of the pirouetting motion depends greatly on the copper oxidation state. The divalent four-coordinate copper complex (Cu-(4)(II))) rearranges in tens of seconds, whereas the monovalent five-coordinate copper system leads to the four-coordinate complex in the millisecond time scale.