diethyl 2-(2-((tert-butyldimethylsilyl)oxy)-4-(2-hydroxyethoxy)benzylidene)malonate | 1345837-01-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: diethyl 2-(2-((tert-butyldimethylsilyl)oxy)-4-(2-hydroxyethoxy)benzylidene)malonate
• CAS: 1345837-01-5
• 化学式: C₂₂H₃₄O₇Si
• 分子量: 438.593
• InChiKey: CHHLYFAGCLQMDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.95
• 重原子数：
  30.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  91.29
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为产物：
  描述：

  4-hydroxyethoxy-2-methoxybenzaldehyde 在 咪唑 、 四氯化钛 、 对甲苯磺酸 、 lithium chloride 、 magnesium bromide 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 78.0h， 生成 diethyl 2-(2-((tert-butyldimethylsilyl)oxy)-4-(2-hydroxyethoxy)benzylidene)malonate
  参考文献：
  名称：

  Reactive Fluorescence Turn-On Probes for Fluoride Ions in Purely Aqueous Media Fabricated from Functionalized Responsive Block Copolymers

  摘要：

  We report on the fabrication of a novel type of responsive double double hydrophilic block copolymer (DHBC)-based highly selective and sensitive fluorescence "turn on" reactive probes for fluoride ions (F-) working in purely aqueous media by exploiting F--induced cyclization reaction of nonfluorescent moieties to induce the formation of fluorescent coumarin moieties, as inspired by the previous; work of the Swager research group (Angew. Chem. Int. Ed. 2003, 42, 4803). Diblock copolymers bearing F--reactive moieties (SiCouMA) in the thermoresponsive block, PEO-b-P(MEO(2)MA-co-OEGMA-co-SiCouMA), were synthesized at first via reversible addition-fragmentation chain transfer (RAFT) technique followed by postmodification, where PEO, MEO(2)MA, and OEGMA are poly(ethylene glycol), di(ethylene glycol) monomethyl ether methacrylate, and oligo(ethylene glycol) monomethyl ether methacrylate, respectively. As-synthesized diblock copolymers molecularly dissolve in water at room temperature and self-assemble into micellar nanoparticles above the critical micellization temperature (33 degrees C). In the presence of F- ions, deprotection of nonfluorescent SiCouMA moieties followed by spontaneous cyclization reaction. leads to the formation of highly fluorescent coumarin residues (CouMA). Thus, PEO-b-P(MEO(2)MA-co-OEGMA-co-SiCouMA) diblock copolymers can serve as highly efficient and selective fluorescence "turn-on" reaction probes for F ions in aqueous media. In the range of 0-1600 equiv of F- ions, diblock unimers and micellar solutions at 20 and 40 degrees C exhibit similar to 88-fold and similar to 30-fold increase in fluorescence emission intensity (20 mm incubation time), respectively. The detection limits were determined to be 0.065 and 0.05 ppm for diblock unimers and micelles, respectively. Most importantly, in the low F- concentration range, excellent linear correlation between F- concentration and emission intensity was observed (0-15 ppm for unimers at 20 degrees C and 0-8 ppm for micelles at 40 degrees C). Interestingly, upon complete transformation of nonfluorescent SiCouMA moieties into fluorescent CouMA, the emission intensity of diblock copolymer solution decreases linearly with temperatures in the range of 20-60 degrees C, suggesting its further application as fluorometric temperature sensors. To the best of our knowledge, this work represents the first example of F--reactive polymeric probes working in purely aqueous media, which are capable of highly sensitive and selective fluorescent F- sensing in the form of both unimers and micellar nanoparticles.

  DOI：

  10.1021/ma2018588