2,3-二氮杂双环[2.2.2]辛-2-烯-1-基甲醇 | 143471-24-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 2,3-二氮杂双环[2.2.2]辛-2-烯-1-基甲醇
• 英文名称: 1-(hydroxymethyl)-2,3-diazabicyclo<2.2.2>oct-2-ene
• 英文别名: 1-(hydroxymethyl)-2,3-diazabicyclo[2.2.2]oct-2-ene；1-hydroxymethyl-2,3-diazabicyclo[2.2.2]-oct-2-ene；1-hydroxymethyl-2,3-diazabicyclo[2.2.2]oct-2-ene；(2,3-Diazabicyclo[2.2.2]oct-2-en-1-yl)methanol；2,3-diazabicyclo[2.2.2]oct-2-en-1-ylmethanol
• CAS: 143471-24-3
• 化学式: C₇H₁₂N₂O
• mdl: MFCD18811872
• 分子量: 140.185
• InChiKey: BLPFRIWLENNLFA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  45
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,3-二氮杂双环[2.2.2]辛-2-烯-1-基甲醇 在 六甲基磷酰三胺 、 lithium aluminium tetrahydride 、 sodium azide 、 三甲胺盐酸盐 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 38.0h， 生成 1-(2,3-二氮杂双环[2.2.2]辛-2-烯-1-基)甲胺
  参考文献：
  名称：

  基于荧光的直接测量生物聚合物中亚微秒分子内接触形成的方法：对多肽的探索性研究

  摘要：

  已经合成了一种荧光氨基酸衍生物 (Fmoc-DBO)，其中包含 2,3-二氮杂双环 [2.2.2]oct-2-ene (DBO) 作为一种具有极长荧光寿命（325 ns in H2O 和空气中 D2O 中的 505 ns）。含有 DBO 残基和高效荧光猝灭剂的多肽允许测量分子内端到端接触形成的速率常数。双分子淬灭实验表明，Trp、Cys、Met 和 Tyr 是 DBO 的有效淬灭剂（k(q) = 20、5.1、4.5 和 3.6 x 10(8) M(-1) xs(-1) 在 D2O 中） ，而其他氨基酸效率低下。被选为内在猝灭剂的 Trp 的猝灭被认为涉及激基复合物诱导的失活。灵活的无结构多肽，Trp-(Gly-Ser)n-DBO-NH2，通过标准固相合成制备，并通过时间相关单光子计数、激光闪光光解和稳态荧光法通过 Trp 对 DBO 的分子内荧光猝灭来测量接触形成率。对于 n = 0、1、2、4、6

  DOI：

  10.1021/ja010493n
• 作为产物：
  描述：

  1,3-环己二烯-1-甲醇 在 palladium on activated charcoal 氢氧化钾 、 氢气 作用下， 以 乙醇 、 异丙醇 为溶剂， 生成 2,3-二氮杂双环[2.2.2]辛-2-烯-1-基甲醇
  参考文献：
  名称：

  Exploiting Long-Lived Molecular Fluorescence

  摘要：

  基于偶氮基团2,3-二氮杂双环[2.2.2]辛-2-烯的荧光团被称为荧光偶氮基团（fluorazophores），显示出极长的荧光寿命。除了在时间分辨筛选分析中的应用，其中长寿命荧光可以进行时间分隔，从而提高信号与背景比，荧光偶氮基团的另一个明显应用领域是生物聚合物动力学。为此，一端标记有荧光偶氮基团，另一端标记有高效荧光猝灭剂。然后，探针/猝灭剂标记的肽的荧光寿命反映了分子内端对端碰撞的动力学。描述了对多肽的应用以及建立熄灭机制性质的对照实验，这些实验表明这是一个需要亲密的探针/猝灭剂接触的扩散过程。

  DOI：

  10.2533/000942903777679424

文献信息

• A long-lived amphiphilic fluorescent probe studied in POPC air–water monolayer and solution bilayer systems
  作者：Gabriela Gramlich、Jiayun Zhang、Mathias Winterhalter、Werner M Nau

  DOI：10.1016/s0009-3084(01)00133-5

  日期：2001.11

  partitioning into a lipid membrane model was quantified at the air-water interface by spreading 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) monolayers. Measurements with different molar fractions of Fluorazophore-L revealed a small but significant reduction of the mean area in the mixed monolayer. The excess free energy of mixing (-0.5+/-0.1 kT) indicated a weakly attractive interaction slightly

  合成并表征了一种新型的两亲性荧光探针（Fluorazophore-L），该探针以强偶极非离子偶氮烷为头基，棕榈酰尾巴为特征。发现纯的氟唑啉酮-L具有足够的两亲性，可以形成稳定的空气-水单层。表面压力对面积的分析表明，在29 mN m（-1）时，每个分子的面积约为34 +/- 2 A（2）。通过散布1-棕榈酰基-2-油酰基-sn-甘油-3-磷酸胆碱（POPC）单层在空气-水界面处定量划分为脂质膜模型。用氟唑啉酮-L的不同摩尔分数进行的测量表明，混合单层的平均面积有小幅但显着的减少。多余的混合自由能（-0.5 +/- 0.1 kT）表明相互作用力较热能稍弱，这表明荧光探针在脂质单层内具有良好的可混溶性，而没有重大的结构修饰。光谱测量证实了将氟偶氮磷-L掺入POPC囊泡中。荧光寿命非常长（在空气中为125 +/- 5 ns），具有单指数荧光衰减。
• A Fluorescence-Based Method for Direct Measurement of Submicrosecond Intramolecular Contact Formation in Biopolymers:  An Exploratory Study with Polypeptides
  作者：Robert R. Hudgins、Fang Huang、Gabriela Gramlich、Werner M. Nau

  DOI：10.1021/ja010493n

  日期：2002.1.1

  steady-state fluorometry. Rate constants of 4.1, 6.8, 4.9, 3.1, 2.0, and 1.1 x 10(7) s(-1) for n = 0, 1, 2, 4, 6, and 10 were obtained. Noteworthy was the relatively slow quenching for the shortest peptide (n = 0). The kinetic data are in agreement with recent transient absorption studies of triplet probes for related peptides, but the rate constants are significantly larger. In contrast to the flexible structureless

  已经合成了一种荧光氨基酸衍生物 (Fmoc-DBO)，其中包含 2,3-二氮杂双环 [2.2.2]oct-2-ene (DBO) 作为一种具有极长荧光寿命（325 ns in H2O 和空气中 D2O 中的 505 ns）。含有 DBO 残基和高效荧光猝灭剂的多肽允许测量分子内端到端接触形成的速率常数。双分子淬灭实验表明，Trp、Cys、Met 和 Tyr 是 DBO 的有效淬灭剂（k(q) = 20、5.1、4.5 和 3.6 x 10(8) M(-1) xs(-1) 在 D2O 中） ，而其他氨基酸效率低下。被选为内在猝灭剂的 Trp 的猝灭被认为涉及激基复合物诱导的失活。灵活的无结构多肽，Trp-(Gly-Ser)n-DBO-NH2，通过标准固相合成制备，并通过时间相关单光子计数、激光闪光光解和稳态荧光法通过 Trp 对 DBO 的分子内荧光猝灭来测量接触形成率。对于 n = 0、1、2、4、6
• Intramolecular triplet energy transfer in ester-linked bichromophoric azoalkanes and naphthalenes
  作者：Paul S. Engel、Douglas W. Horsey、John N. Scholz、Takashi Karatsu、Akihide Kitamura

  DOI：10.1021/j100198a011

  日期：1992.9

  The photophysics of a series of compounds has been studied wherein a triplet sensitizer such as benzophenone (BB) or thioxanthone (TH) is linked via an ester group to an azoalkane such as 3,3,5,5-tetramethyl-1-pyrazoline (PY) or 2,3-diazabicyclo-[2.2.2]oct-2-ene (DBO). The observation of phosphorescence from the sensitizer moiety in a frozen glass and triplet lifetime measurements in solution show that intramolecular triplet energy transfer (ET) can be remarkably slow. Model compounds in which naphthalene replaces the azo group behave normally, exhibiting complete and rapid intramolecular ET. Despite the small size of the azo group, its critical radius, R0, for intermolecular ET in a frozen glass is comparable to that of naphthalene. When the donor and azo chromophores are closely linked by alkyl groups, ET is very rapid. No phosphorescence or T-T absorption of the azo group could be detected, but quenching experiments show that the triplet lifetime of cyclic azoalkanes is much shorter than their singlet lifetime.
• Kinetics of End-to-End Collision in Short Single-Stranded Nucleic Acids
  作者：Xiaojuan Wang、Werner M. Nau

  DOI：10.1021/ja038263r

  日期：2004.1.28

  A novel fluorescence-based method, which entails contact quenching of the long-lived fluorescent state of 2,3-diazabicyclo[2.2.2]-oct-2-ene (DBO), was employed to measure the kinetics of end-to-end collision in short single-stranded oligodeoxyribonucleotides of the type 5'-DBO-(X)(n)-dG with X = dA, dC, dT, or dU and n = 2 or 4. The fluorophore was covalently attached to the 5' end and dG was introduced as an efficient intrinsic quencher at the 3' terminus. The end-to-end collision rates, which can be directly related to the efficiency of intramolecular fluorescence quenching, ranged from 0.1 to 9.0 x 10(6) s(-1). They were strongly dependent on the strand length, the base sequence, as well as the temperature. Oligonucleotides containing dA in the backbone displayed much slower collision rates and significantly higher positive activation energies than strands composed of pyrimidine bases, suggesting a higher intrinsic rigidity of oligoadenylate. Comparison of the measured collision rates in short single-stranded oligodeoxy-ribonucleotides with the previously reported kinetics of hairpin formation indicates that the intramolecular collision is significantly faster than the nucleation step of hairpin closing. This is consistent with the configurational diffusion model suggested by Ansari et al.
• A Joint Structural, Kinetic, and Thermodynamic Investigation of Substituent Effects on Host−Guest Complexation of Bicyclic Azoalkanes by β-Cyclodextrin
  作者：Xiangyang Zhang、Gabriela Gramlich、Xiaojuan Wang、Werner M. Nau

  DOI：10.1021/ja011866n

  日期：2002.1.1

  Derivatives of the azoalkane 2,3-diazabicyclo[2,2,2]oct-2-ene (1a) with bridgehead 1,4-dialkyl (1b), 1,4-dichloro (1c), 1-hydroxymethyl (1d), 1-aminomethyl (1e), and 1-ammoniummethyl (1f) substituents form host-guest inclusion complexes with beta-cyclodextrin. They were employed as probes to assess substituent effects on the kinetics and thermodynamics of this complexation by using time-resolved and steady-state fluorimetry, UV spectrophotometry, induced circular dichroism (ICD) measurements, and H-1 NMR spectroscopy. The kinetic analysis based on quenching of the long-lived fluorescence of the azoalkanes by addition of host provided excited-state association rate constants between 2.6 x 10(8) and 7.0 x 10(8) M-1 s(-1). The binding constants for 1a (1100 M-1), 1b (900 M-1), 1c (1900 M-1), 1d (180 M-1), 1e (250 M-1), and 1f (ca. 20 M-1) were obtained by UV, NMR, and ICD titrations. A positive ICD signal of the azo absorption around 370 nm was observed for the beta-cyclodextrin complexes of 1a, 1d, and 1f with the intensity order 1a much greater than 1d approximate to 1f, and a negative signal was measured for those of 1b, 1c, and 1e with the intensity order 1c < 1b approximate to 1e. The ICD was employed for the assignment of the solution structures of the complexes, in particular the relative orientation of the guest in the host (co-conformation).