(E)-3-(4-Methoxy-naphthalen-1-yl)-1-[4-(2-phenyl-[1,3]dioxolan-2-yl)-phenyl]-propenone | 148788-22-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (E)-3-(4-Methoxy-naphthalen-1-yl)-1-[4-(2-phenyl-[1,3]dioxolan-2-yl)-phenyl]-propenone
• CAS: 148788-22-1
• 化学式: C₂₉H₂₄O₄
• 分子量: 436.507
• InChiKey: YAFDMDOHKOAJAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.99
• 重原子数：
  33.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (E)-3-(4-Methoxy-naphthalen-1-yl)-1-[4-(2-phenyl-[1,3]dioxolan-2-yl)-phenyl]-propenone 在 palladium on activated charcoal 盐酸 、 sodium hydroxide 、 氢气 、 potassium carbonate 、 一水合肼 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 丙酮 、 二乙二醇 为溶剂， 反应 63.0h， 生成 4-(3-(4-Methoxynaphthyl)propyl)benzophenone
  参考文献：
  名称：

  激光闪光光解法研究[（羟基萘基）丙基]二苯甲酮的分子内氢原子转移和[（甲氧基萘基丙基）]二苯甲酮通过三重态激基复合物的分子内质子诱导的电子转移

  摘要：

  Laser photolysis studies at 355 nm have been carried out on the intramolecular hydrogen atom transfer (intra-HT) reaction of [(hydroxynaphthyl)propyl]benzophenone, BP-(CH2)3-ROH, and the proton-induced intramolecular ionization (intra-p-ion) reaction of [(methoxynaphthyl)propyl]benzophenone, BP-(CH2)3-ROMe, in acetonitrile-water (4:1 v/v) at 295 K. After 355-nm laser pulsing to BP-(CH2)3-ROH and BP-(CH2)3-ROMe, the intramolecular triplet energy transfer (intra-ET) reactions from the triplet moiety (3BP*) to the naphthol (ROH) and methoxynaphthalene (ROMe) moieties occur to yield BP-(CH2)3-3ROH* and BP-(CH2)3-3ROMe* on a nanosecond time scale. The former triplet molecule (BP-(CH2)3-3ROH*) undergoes intramolecular hydrogen atom transfer (intra-HT) with an efficiency (phi(HT)) of unity to yield a biradical molecule with benzophenone ketyl radical (>COH-) and naphthoxy radical (RO') moieties (>COH-(CH2)3-RO.). The rate constant (k(HT)) for intra-HT was determined to be 9.8 x 105 s-1 and independent of [BP-(CH2)3-ROH]. The deuterium isotope effect on intra-HT was examined by using BP-(CH2)3-ROD. The rate constant (k(DT)) for intra-DT was determined to be 5.1 X 10(5) S-1. In the presence of protons, the rate constant of intra-HT is enhanced proportional to the acid concentration though the value of phi(HT) (= 1.0) is independent of the acid concentration. The triplet molecule (BP-(CH2)3-3ROMe*) undergoes ionization only in the presence of protons (intra-p-ion) to yield a biradical molecule with >COH- and methoxynaphthalene cation radical (-ROMe.+) moieties (>COH-(CH2)3-ROMe.+) with efficiencies (phi(el)) of 0.3 for [H2SO4] = 0.005 M and 1.0 for [H2SO4] = 0.5 M in acetonitrile-water (4:1 v/v) at 295 K. The rate constant for intra-p-ion increases with an increase of the acid concentration. The mechanisms for intra-HT and intra-p-ion were interpreted by considering the intramolecular triplet exciplexes, 3(>CO-(CH2)3-ROH)* and 3(>CO-(CH2)3-ROMe)*, and the intramolecular protonated triplet exciplexes, 3(>+COH-(CH2)3-ROH)* and 3(>+COH-(CH2)3-ROMe)*, respectively. On the basis of the mechanism for intra-HT and intra-p-ion of the two chromophores linked with a propyrene chain, the structures of the triplet exciplex and protonated triplet exciplex are suggested to be sandwichlike with weak charge-transfer character.

  DOI：

  10.1021/j100129a015
• 作为产物：
  描述：

  4-甲氧基-1-萘甲醛 、 4-乙酰基二苯甲酮乙烯缩醛 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 18.0h， 以77%的产率得到(E)-3-(4-Methoxy-naphthalen-1-yl)-1-[4-(2-phenyl-[1,3]dioxolan-2-yl)-phenyl]-propenone
  参考文献：
  名称：

  激光闪光光解法研究[（羟基萘基）丙基]二苯甲酮的分子内氢原子转移和[（甲氧基萘基丙基）]二苯甲酮通过三重态激基复合物的分子内质子诱导的电子转移

  摘要：

  Laser photolysis studies at 355 nm have been carried out on the intramolecular hydrogen atom transfer (intra-HT) reaction of [(hydroxynaphthyl)propyl]benzophenone, BP-(CH2)3-ROH, and the proton-induced intramolecular ionization (intra-p-ion) reaction of [(methoxynaphthyl)propyl]benzophenone, BP-(CH2)3-ROMe, in acetonitrile-water (4:1 v/v) at 295 K. After 355-nm laser pulsing to BP-(CH2)3-ROH and BP-(CH2)3-ROMe, the intramolecular triplet energy transfer (intra-ET) reactions from the triplet moiety (3BP*) to the naphthol (ROH) and methoxynaphthalene (ROMe) moieties occur to yield BP-(CH2)3-3ROH* and BP-(CH2)3-3ROMe* on a nanosecond time scale. The former triplet molecule (BP-(CH2)3-3ROH*) undergoes intramolecular hydrogen atom transfer (intra-HT) with an efficiency (phi(HT)) of unity to yield a biradical molecule with benzophenone ketyl radical (>COH-) and naphthoxy radical (RO') moieties (>COH-(CH2)3-RO.). The rate constant (k(HT)) for intra-HT was determined to be 9.8 x 105 s-1 and independent of [BP-(CH2)3-ROH]. The deuterium isotope effect on intra-HT was examined by using BP-(CH2)3-ROD. The rate constant (k(DT)) for intra-DT was determined to be 5.1 X 10(5) S-1. In the presence of protons, the rate constant of intra-HT is enhanced proportional to the acid concentration though the value of phi(HT) (= 1.0) is independent of the acid concentration. The triplet molecule (BP-(CH2)3-3ROMe*) undergoes ionization only in the presence of protons (intra-p-ion) to yield a biradical molecule with >COH- and methoxynaphthalene cation radical (-ROMe.+) moieties (>COH-(CH2)3-ROMe.+) with efficiencies (phi(el)) of 0.3 for [H2SO4] = 0.005 M and 1.0 for [H2SO4] = 0.5 M in acetonitrile-water (4:1 v/v) at 295 K. The rate constant for intra-p-ion increases with an increase of the acid concentration. The mechanisms for intra-HT and intra-p-ion were interpreted by considering the intramolecular triplet exciplexes, 3(>CO-(CH2)3-ROH)* and 3(>CO-(CH2)3-ROMe)*, and the intramolecular protonated triplet exciplexes, 3(>+COH-(CH2)3-ROH)* and 3(>+COH-(CH2)3-ROMe)*, respectively. On the basis of the mechanism for intra-HT and intra-p-ion of the two chromophores linked with a propyrene chain, the structures of the triplet exciplex and protonated triplet exciplex are suggested to be sandwichlike with weak charge-transfer character.

  DOI：

  10.1021/j100129a015