N-Phenyltetrathiamonoaza-15-crown-5 | 148932-07-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-Phenyltetrathiamonoaza-15-crown-5
• 英文别名: 13-phenyl-1,4,7,10-tetrathia-13-azacyclopentadecane；N-phenyltetrathia-13-aza-15-crown-5；1-phenyl-4,7,10,13-tetrathia-1-azacyclopentadecane
• CAS: 148932-07-4
• 化学式: C₁₆H₂₅NS₄
• 分子量: 359.645
• InChiKey: KLTQAQXUUXMZMD-UHFFFAOYSA-N

物化性质

• 沸点：
  545.7±50.0 °C(predicted)
• 密度：
  1.126±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-Phenyltetrathiamonoaza-15-crown-5 在 溶剂黄146 三氯氧磷 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 13-[4'-(benzothiazol-2"-yl)phenyl]-1,4,7,10-tetrathia-13-azacyclopentadecane
  参考文献：
  名称：

  Ishikawa, Junichi; Sakamoto, Hidefumi; Wada, Hiroko, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1999, # 6, p. 1273 - 1279

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N-二羟乙基苯胺 在 sodium hydroxide 、 caesium carbonate 、 sodium iodide 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 24.0h， 生成 N-Phenyltetrathiamonoaza-15-crown-5
  参考文献：
  名称：

  Silver Ion Selective Extraction with Dithiaza-, Tetrathiaza-, and Tetrathiadiazacrown Ether Derivatives

  摘要：

  合成了二硫氮杂冠醚、四硫氮杂冠醚以及两种四硫二氮杂冠醚衍生物，这些化合物在每一个氮原子外围都带有一个苯基。使用水-1,2-二氯乙烷系统，研究了这些化合物对某些过渡金属离子的萃取。所有这些硫氮杂冠醚化合物都对银离子有选择性，并且形成了银离子：配体：月桂酸离子1:1:1的络合物，作为被萃取到1,2-二氯乙烷溶液中的反离子。银离子的萃取能力（萃取常数，Kex）按以下顺序递减：7,16-二苯基四硫-7,16-二氮杂-18-冠-6（3）（log Kex = 1.18 ± 0.13）> 13-苯基四硫-13-氮杂-15-冠-5（2）（0.75 ± 0.09）> 7-苯基二硫-7-氮杂-9-冠-3（1）（−0.47 ± 0.06）> 13,16-二苯基四硫-13,16-二氮杂-18-冠-6（4）（−0.62 ± 0.16）。

  DOI：

  10.1246/bcsj.68.2831

文献信息

• Hydrazones Derived from Dithiamonoaza and Tetrathiamonoaza Analogs of Polyethers as Silver Ion Selective Ionophores: Syntheses, Proton-Dissociation Behaviors, and Metal Ion Complexing Properties in 1,4-Dioxane–Water Acidic Solution
  作者：Junichi Ishikawa、Hidefumi Sakamoto、Tamao Mizuno、Makoto Otomo

  DOI：10.1246/bcsj.68.3071

  日期：1995.11

  Cyclic and acyclic dithiamonoaza, tetrathiamonoaza, and tetrathiadiaza analogs of polyethers bearing a hydrazone moiety on nitrogen atom(s) were synthesized. Their acidity constants in 1,4-dioxane–water solution and stability constants of hydrazones derived from dithiamonoaza and tetrathiamonoaza analogs of polyethers for some heavy metal ions in same acidic media were measured spectrophotometrically

  合成了在氮原子上带有腙部分的聚醚的环状和非环状二硫单氮杂、四硫单氮杂和四硫二氮杂类似物。它们在 1,4-二氧六环 - 水溶液中的酸度常数和衍生自聚醚的二硫单氮杂和四硫单氮杂类似物的腙在相同酸性介质中对某些重金属离子的稳定性常数进行了分光光度法测量。环状和非环状四硫单氮杂系列的腙具有高度的 Ag+ 选择性络合性。
• Steady-state and time-resolved investigations of a crown thioether conjugated with methylacridinium and its complexes with metal ions
  作者：Tiziana del Giacco、Benedetta Carlotti、Stefano De Solis、Arianna Barbafina、Fausto Elisei

  DOI：10.1039/c0cp01411g

  日期：——

  The crown thioether 9-[4-(4,7,10,13-tetrathia-1-azacyclopentadecyl]phenyl-N-methylacridinium perchlorate (TCMA) was synthesized and characterized with the aim to verify its ability to interact selectively with metal ions and substantiate the possibility to detect easily the presence of heavy metals in fluid samples. The spectroscopic properties of TCMA, alone and in the presence of metal ions, were therefore studied in polar solvents (MeCN and H2O); in particular, steady-state UV-Vis spectrophotometric and fluorimetric techniques were used together with transient absorption spectroscopy with fs time resolution to investigate the spectral and dynamic properties of the lowest excited singlet state of TCMA and of TCMA/metal ion complexes. The absorption in the Vis region is characterized by a charge-transfer nature with the methylacridinium moiety acting as the electron-acceptor and the anilic group as the electron-donor. No emission from the S1 was detected both in MeCN and H2O, while a small S2 → S0 fluorescence emission (λmax = 485 nm and ϕF = 0.0011) was detected in water. Time-resolved measurements with fs resolution of TCMA in MeCN have shown that the relaxed S1 state is reached ∼0.6 ps after the laser pulse, while the S1 → S0 time constant is 3.7 ps. Among the investigated metal ions, only Fe3+ (in MeCN) and Hg2+ (in MeCN and H2O) were able to form stable complexes (association constant, Kass = 1–11 × 104 M−1) with TCMA. The S1 state of the TCMA/Mn+ complexes emits with low quantum yield (ϕF = 0.0023–0.014) and decays with time constants much longer than TCMA itself, at least in the case of TCMA/Hg2+ in MeCN. This study showed that TCMA is a good candidate for colorimetric/fluorimetric sensing of Hg2+ in aqueous media owing to its high selectivity towards metal ions.

  合冠硫醚9-[4-(4,7,10,13-四硫-1-氮杂环戊十五烷)苯基]-N-甲基acridinium高氯酸盐（TCMA）被合成并表征，旨在验证其选择性与金属离子相互作用的能力，并证实在流体样本中轻松检测重金属存在的可能性。因此，TCMA在极性溶剂（MeCN和H2O）中，单独及在金属离子存在下的光谱特性进行了研究；特别是，使用了稳态UV-Vis光谱法和荧光测定技术，并结合飞秒时间分辨率的瞬态吸收光谱法，研究了TCMA及其与金属离子形成的复合物的最低激发单态的光谱和动态特性。可见光区域的吸收具有电荷转移特性，N-甲基acridinium部分作为电子受体，而邻氨基部分作为电子供体。在MeCN和 中都未检测到S1态的发射，但在水中检测到少量的S2 → S0荧光发射（λMAx = 485 nm，ϕF = 0.0011）。在MeCN中对TCMA进行的飞秒分辨率的时间分辨测量表明，松弛的S1态在激光脉冲后约0.6 ps内达到，而S1 → S0的时间常数为3.7 ps。在调查的金属离子中，仅有Fe3+（在MeCN中）和Hg2+（在MeCN和 中）能够与TCMA形成稳定的复合物（结合常数Kass = 1–11 × 10⁴ M⁻¹）。TCMA/Mn+复合物的S1态发射量子产率较低（ϕF = 0.0023–0.014），其衰变的时间常数远长于TCMA自身，至少在TCMA/Hg2+的MeCN情况下如此。这项研究表明，由于其对金属离子的高选择性，TCMA是水介质中Hg2+比色法/荧光法检测的良好候选物。
• Silver Selectivity of Novel Monoazapolythioether Derivatives Bearing a Hydrazone Group in the Solvent Extraction
  作者：Hidefumi Sakamoto、Junichi Ishkawa、Tamao Mizuno、Kunio Doi、Makoto Otomo

  DOI：10.1246/cl.1993.609

  日期：1993.4

  Novel acyclic and cyclic monoazapolythioether derivatives incorporating a substituted hydrazone group were synthesized. The acyclic and the cyclic monoazatetrathioether derivatives exhibited high Ag+ ion selectivity in the extraction with 1,2-dichloroethane. The monoazatetrathioether derivatives gave hypsochromic and bathochromic shifts in the visible absorption spectra when extracted Ag+ ion from the aqueous phase of varying acidities into the organic phase.

  合成了含有取代腙基的新型无环和环状单氮杂环硫醚衍生物。在用 1,2-二氯乙烷萃取时，无环和环状单氮杂环丁硫醚衍生物表现出较高的 Ag+ 离子选择性。将 Ag+ 离子从不同酸度的水相萃取到有机相中时，单氮杂环丁硫醚衍生物在可见吸收光谱中呈现出低色移和浴色移。
• Ishikawa, Junichi; Sakamoto, Hidefumi; Nakamura, Mutsumi, Journal of the Chemical Society, Dalton Transactions, 1999, # 2, p. 191 - 199
  作者：Ishikawa, Junichi、Sakamoto, Hidefumi、Nakamura, Mutsumi、Doi, Kunio、Wada, Hiroko

  DOI：——

  日期：——
• MODIFIED METALLOTHIONEINS AND METHODS FOR SCREENING AND TREATMENT OF DISEASES ASSOCIATED WITH OXIDATIVE STRESS
  申请人：The President and Fellows of Harvard College

  公开号：EP2007786A2

  公开（公告）日：2008-12-31