2'-(6-Ethynylpyridin-2-yl)spiro[3-oxa-9,23-diazaheptacyclo[17.7.1.15,9.02,17.04,15.023,27.013,28]octacosa-1(27),2(17),4(15),5(28),13,18-hexaene-16,3'-isoindole]-1'-one | 1398592-38-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2'-(6-Ethynylpyridin-2-yl)spiro[3-oxa-9,23-diazaheptacyclo[17.7.1.15,9.02,17.04,15.023,27.013,28]octacosa-1(27),2(17),4(15),5(28),13,18-hexaene-16,3'-isoindole]-1'-one
• 英文别名: 2'-(6-ethynylpyridin-2-yl)spiro[3-oxa-9,23-diazaheptacyclo[17.7.1.15,9.02,17.04,15.023,27.013,28]octacosa-1(27),2(17),4(15),5(28),13,18-hexaene-16,3'-isoindole]-1'-one
• CAS: 1398592-38-5
• 化学式: C₃₉H₃₄N₄O₂
• 分子量: 590.725
• InChiKey: SOZOWHUDRFQHRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  45
• 可旋转键数：
  2
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  48.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2'-(6-Ethynylpyridin-2-yl)spiro[3-oxa-9,23-diazaheptacyclo[17.7.1.15,9.02,17.04,15.023,27.013,28]octacosa-1(27),2(17),4(15),5(28),13,18-hexaene-16,3'-isoindole]-1'-one 、 叠氮三甘醇单甲醚 在 copper(II) acetate monohydrate 、 sodium ascorbate 、 三[(1-苄基-1H-1,2,3-三唑-4-基)甲基]胺 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 12.0h， 以59%的产率得到2'-[6-[1-[2-[2-(2-Methoxyethoxy)ethoxy]ethyl]triazol-4-yl]pyridin-2-yl]spiro[3-oxa-9,23-diazaheptacyclo[17.7.1.15,9.02,17.04,15.023,27.013,28]octacosa-1(27),2(17),4(15),5(28),13,18-hexaene-16,3'-isoindole]-1'-one
  参考文献：
  名称：

  Tricolor Emission of a Fluorescent Heteroditopic Ligand over a Concentration Gradient of Zinc(II) Ions

  摘要：

  The internal charge transfer (ICT) type fluoroionophore arylvinyl-bipy (bipy = 2,2'-bipyridyl) is covalently tethered to the spirolactam form of rhodamine to afford fluorescent heteroditopic ligand 4. Compound 4 can be excited in the visible region, the emission of which undergoes sequential bathochromic shifts over an increasing concentration gradient of Zn(ClO4)(2) in acetonitrile. Coordination of Zn2+ stabilizes the ICT excited state of the arylvinyl-bipy component of 4, leading to the first emission color shift from blue to green. At sufficiently high concentrations of Zn(ClO4)(2), the nonfluorescent spirolactam component of 4 is transformed to the fluorescent rhodamine, which turns the emission color from green to orange via intramolecular fluorescence resonance energy transfer (FRET) from the Zn2+-bound arylvinyl-bipy fluorophore to rhodamine. While this work offers a new design of ratiometric chemosensors, in which sequential analyte-induced emission band shifts result in the sampling of multiple colors at different concentration ranges (i.e., from blue to green to orange as [Zn2+] increases in the current case), it also reveals the nuances of rhodamine spirolactam chemistry that have not been sufficiently addressed in the published literature. These issues include the ability of rhodamine spirolactam as a fluorescence quencher via electron transfer, and the slow kinetics of spirolactam ring-opening effected by Zn2+ coordination under pH neutral aqueous conditions.

  DOI：

  10.1021/jo3016659
• 作为产物：
  描述：

  2-氨基-6-溴吡啶 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 、 potassium hydroxide 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 反应 14.08h， 生成 2'-(6-Ethynylpyridin-2-yl)spiro[3-oxa-9,23-diazaheptacyclo[17.7.1.15,9.02,17.04,15.023,27.013,28]octacosa-1(27),2(17),4(15),5(28),13,18-hexaene-16,3'-isoindole]-1'-one
  参考文献：
  名称：

  Tricolor Emission of a Fluorescent Heteroditopic Ligand over a Concentration Gradient of Zinc(II) Ions

  摘要：

  The internal charge transfer (ICT) type fluoroionophore arylvinyl-bipy (bipy = 2,2'-bipyridyl) is covalently tethered to the spirolactam form of rhodamine to afford fluorescent heteroditopic ligand 4. Compound 4 can be excited in the visible region, the emission of which undergoes sequential bathochromic shifts over an increasing concentration gradient of Zn(ClO4)(2) in acetonitrile. Coordination of Zn2+ stabilizes the ICT excited state of the arylvinyl-bipy component of 4, leading to the first emission color shift from blue to green. At sufficiently high concentrations of Zn(ClO4)(2), the nonfluorescent spirolactam component of 4 is transformed to the fluorescent rhodamine, which turns the emission color from green to orange via intramolecular fluorescence resonance energy transfer (FRET) from the Zn2+-bound arylvinyl-bipy fluorophore to rhodamine. While this work offers a new design of ratiometric chemosensors, in which sequential analyte-induced emission band shifts result in the sampling of multiple colors at different concentration ranges (i.e., from blue to green to orange as [Zn2+] increases in the current case), it also reveals the nuances of rhodamine spirolactam chemistry that have not been sufficiently addressed in the published literature. These issues include the ability of rhodamine spirolactam as a fluorescence quencher via electron transfer, and the slow kinetics of spirolactam ring-opening effected by Zn2+ coordination under pH neutral aqueous conditions.

  DOI：

  10.1021/jo3016659

文献信息

• Tricolor Emission of a Fluorescent Heteroditopic Ligand over a Concentration Gradient of Zinc(II) Ions
  作者：Kesavapillai Sreenath、Ronald J. Clark、Lei Zhu

  DOI：10.1021/jo3016659

  日期：2012.9.21

  The internal charge transfer (ICT) type fluoroionophore arylvinyl-bipy (bipy = 2,2'-bipyridyl) is covalently tethered to the spirolactam form of rhodamine to afford fluorescent heteroditopic ligand 4. Compound 4 can be excited in the visible region, the emission of which undergoes sequential bathochromic shifts over an increasing concentration gradient of Zn(ClO4)(2) in acetonitrile. Coordination of Zn2+ stabilizes the ICT excited state of the arylvinyl-bipy component of 4, leading to the first emission color shift from blue to green. At sufficiently high concentrations of Zn(ClO4)(2), the nonfluorescent spirolactam component of 4 is transformed to the fluorescent rhodamine, which turns the emission color from green to orange via intramolecular fluorescence resonance energy transfer (FRET) from the Zn2+-bound arylvinyl-bipy fluorophore to rhodamine. While this work offers a new design of ratiometric chemosensors, in which sequential analyte-induced emission band shifts result in the sampling of multiple colors at different concentration ranges (i.e., from blue to green to orange as [Zn2+] increases in the current case), it also reveals the nuances of rhodamine spirolactam chemistry that have not been sufficiently addressed in the published literature. These issues include the ability of rhodamine spirolactam as a fluorescence quencher via electron transfer, and the slow kinetics of spirolactam ring-opening effected by Zn2+ coordination under pH neutral aqueous conditions.