1:2-epoxy-1,2-dihydroacridine | 155007-31-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 1:2-epoxy-1,2-dihydroacridine
• 英文别名: Acridine 1,2-oxide；1a,9b-Dihydrooxireno[2,3-a]acridine
• CAS: 155007-31-1
• 化学式: C₁₃H₉NO
• 分子量: 195.221
• InChiKey: FJRTWUDZFLUIHA-UHFFFAOYSA-N

物化性质

• 沸点：
  392.7±30.0 °C(Predicted)
• 密度：
  1.330±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  25.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1:2-epoxy-1,2-dihydroacridine 在 氢氧化钾 作用下， 以 叔丁醇 为溶剂， 反应 72.0h， 以55%的产率得到trans-1,2-Dihydroxy-1,2-dihydroacridine
  参考文献：
  名称：

  Synthesis and Solvolysis of Acridine 1,2- and 3,4-Oxides: Crystal Structure of Acridine 1,2-Oxide

  摘要：

  Acridine 1,2- and 3,4-oxides were synthesized from 3,4- and 1,2-dihydroacridine, respectively, via intermediate bromohydrin acetates. Crystals of acridine 1,2-oxide were sufficiently stable to allow the first determination of X-ray crystallographic structural features of a non-K-region arene oxide. Aqueous alkaline hydrolysis of the acridine 1,2- and 3,4-oxides produced trans-1,2-dihydrorxy-1,2-dihydroacridine and trans-3,4-dihydroxy-3,4-dihydroacridine, respectively. The former dihydrodiol was also obtained by a six-step synthesis from 3,4-dihydroacridine. Acid-catalyzed hydrolysis of acridine 1,2-oxide yielded the corresponding cis- and trans-1,2-dihydrodiols (20%) in addition to 1-hydroxy- (12%) and 2-hydroxyacridine (68%). By contrast, solvolysis of acridine 3,4-oxide under acid conditions gave 4-hydroxyacridine as the exclusive product. pH-rate profiles for hydrolysis of the acridine oxides in 1:9 dioxane-water at 25 degrees C were compared with those for anthracene 1,2-oxide, naphthalene 1,2-oxide, and quinoline 5,6- and 7,8-oxides. Second-order rate constants for the hydronium ion-catalyzed ring opening of anthracene 1,2-, acridine 3,4-, and acridine 1,2-oxide are 585, 7.81, and 0.45 M(-1) s(-2), respectively, and are 3-5 times larger than the rate constants for the corresponding naphthalene 1,2-, quinoline 7,8-, and quinoline 5,6-oxides. Rate constants for uncatalyzed ring opening of anthracene 1,2- and acridine 3,4-oxides (117 x 10(-5) s(-1) and 2.4 X 10(-5) s(-1), respectively) are about two to three times larger than the corresponding rate constants for naphthalene 1,2- and quinoline 7,8-oxides, whereas the rate of nucleophilic ring opening by hydroxide ion to give the trans-dihydrodiols is accelerated by less than a factor of 2 for the acridine oxides as compared with their quinoline analogs. The pH-rate profiles for solvolysis of the acridine oxides, like those of the quinoline oxides, exhibit a pH-independent region at pH values below the pK(a) of the ring nitrogen that is attributed to formation of an unreactive N-protonated species.

  DOI：

  10.1021/jo00084a013
• 作为产物：
  描述：

  2-氨基苯甲醛 在 偶氮二异丁腈 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 PPA 、 sodium methylate 、 N-溴代乙酰胺 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.0h， 生成 1:2-epoxy-1,2-dihydroacridine
  参考文献：
  名称：

  Synthesis and Solvolysis of Acridine 1,2- and 3,4-Oxides: Crystal Structure of Acridine 1,2-Oxide

  摘要：

  Acridine 1,2- and 3,4-oxides were synthesized from 3,4- and 1,2-dihydroacridine, respectively, via intermediate bromohydrin acetates. Crystals of acridine 1,2-oxide were sufficiently stable to allow the first determination of X-ray crystallographic structural features of a non-K-region arene oxide. Aqueous alkaline hydrolysis of the acridine 1,2- and 3,4-oxides produced trans-1,2-dihydrorxy-1,2-dihydroacridine and trans-3,4-dihydroxy-3,4-dihydroacridine, respectively. The former dihydrodiol was also obtained by a six-step synthesis from 3,4-dihydroacridine. Acid-catalyzed hydrolysis of acridine 1,2-oxide yielded the corresponding cis- and trans-1,2-dihydrodiols (20%) in addition to 1-hydroxy- (12%) and 2-hydroxyacridine (68%). By contrast, solvolysis of acridine 3,4-oxide under acid conditions gave 4-hydroxyacridine as the exclusive product. pH-rate profiles for hydrolysis of the acridine oxides in 1:9 dioxane-water at 25 degrees C were compared with those for anthracene 1,2-oxide, naphthalene 1,2-oxide, and quinoline 5,6- and 7,8-oxides. Second-order rate constants for the hydronium ion-catalyzed ring opening of anthracene 1,2-, acridine 3,4-, and acridine 1,2-oxide are 585, 7.81, and 0.45 M(-1) s(-2), respectively, and are 3-5 times larger than the rate constants for the corresponding naphthalene 1,2-, quinoline 7,8-, and quinoline 5,6-oxides. Rate constants for uncatalyzed ring opening of anthracene 1,2- and acridine 3,4-oxides (117 x 10(-5) s(-1) and 2.4 X 10(-5) s(-1), respectively) are about two to three times larger than the corresponding rate constants for naphthalene 1,2- and quinoline 7,8-oxides, whereas the rate of nucleophilic ring opening by hydroxide ion to give the trans-dihydrodiols is accelerated by less than a factor of 2 for the acridine oxides as compared with their quinoline analogs. The pH-rate profiles for solvolysis of the acridine oxides, like those of the quinoline oxides, exhibit a pH-independent region at pH values below the pK(a) of the ring nitrogen that is attributed to formation of an unreactive N-protonated species.

  DOI：

  10.1021/jo00084a013

文献信息

• Biomimetic One-Pot Route to Acridine Epoxides
  作者：Margarida Linhares、Susana L. H. Rebelo、Krzysztof Biernacki、Alexandre L. Magalhães、Cristina Freire

  DOI：10.1021/jo5023525

  日期：2015.1.2

  The first direct epoxidation of acridine on the edge positions is reported. The reaction proceeds under mild conditions using a biomimetic catalytic system based on a Mn(III) porphyrin. The successive oxyfunctionalization to mono-, di-, and tetraepoxy derivatives is accomplished using hydrogen peroxide as a green oxidant at room temperature. Computed optimized geometries showed only slight shifts to

  据报道，a啶在边缘位置上首次直接环氧化。该反应在温和条件下使用基于锰（III）卟啉的仿生催化系统进行。在室温下，使用过氧化氢作为绿色氧化剂，可以完成连续的羟基官能化为单，二和四环氧衍生物。通过环氧化作用脱芳香化后，计算出的最佳几何形状仅显示基本平整度的变化，这是DNA嵌入和生物活性的重要特征。核磁共振研究和理论值的比较允许分配反和反异构体的立体化学。-二环氧和-四环氧衍生物以及由环氧化物开环产生的化合物，例如环氧二醇。以约4的抗：顺式比例形成二环氧化物，并通过微波过程与乙腈回流10分钟，选择性地并完全转化亲核试剂的攻击，例如乙基苯胺。最后，对静电势的研究使得4-羟基ac啶的形成机理和二环氧oxy啶与亲核试剂的区域选择性反应得以合理化。
• Green Aromatic Epoxidation with an Iron Porphyrin Catalyst for One-Pot Functionalization of Renewable Xylene, Quinoline, and Acridine
  作者：Gabriela A. Corrêa、Susana L. H. Rebelo、Baltazar de Castro

  DOI：10.3390/molecules28093940

  日期：——

  ethanol as a green solvent in the presence of a highly electron withdrawing iron porphyrin catalyst. The results show unusual initial epoxidation of the aromatic ring by the green catalytic system. The epoxides were isolated or evolved through rearrangement, ring opening by nucleophiles, and oxidation. Acridine was oxidized to mono- and di-oxides in the peripheral ring: 1:2-epoxy-1,2-dihydroacridine and

  可再生芳烃的可持续功能化是满足我们目前对特种化学品需求和追求向循环、无化石经济过渡的关键步骤。在目前的工作中，三种典型稳定的芳香族化合物，代表可从生物质或回收过程中大量获得的产品，在室温下使用 H2O2 作为绿色氧化剂和乙醇作为绿色溶剂在室温下进行一锅氧化反应进行功能化高吸电子铁卟啉催化剂。结果显示绿色催化系统对芳环的初始环氧化反应异常。环氧化物通过重排、亲核试剂开环和氧化分离或进化。吖啶在外围环中被氧化成单氧化物和二氧化物：1:2-epoxy-1,2-dihydroacridine 和 anti-1:2,3：
• Synthesis and Solvolysis of Acridine 1,2- and 3,4-Oxides: Crystal Structure of Acridine 1,2-Oxide
  作者：Derek R. Boyd、R. Jeremy H. Davies、Lynne Hamilton、John J. McCullough、John F. Malone、H. Patricia Porter、Allison Smith、John M. Carl、Jane M. Sayer、Donald M. Jerina

  DOI：10.1021/jo00084a013

  日期：1994.3

  Acridine 1,2- and 3,4-oxides were synthesized from 3,4- and 1,2-dihydroacridine, respectively, via intermediate bromohydrin acetates. Crystals of acridine 1,2-oxide were sufficiently stable to allow the first determination of X-ray crystallographic structural features of a non-K-region arene oxide. Aqueous alkaline hydrolysis of the acridine 1,2- and 3,4-oxides produced trans-1,2-dihydrorxy-1,2-dihydroacridine and trans-3,4-dihydroxy-3,4-dihydroacridine, respectively. The former dihydrodiol was also obtained by a six-step synthesis from 3,4-dihydroacridine. Acid-catalyzed hydrolysis of acridine 1,2-oxide yielded the corresponding cis- and trans-1,2-dihydrodiols (20%) in addition to 1-hydroxy- (12%) and 2-hydroxyacridine (68%). By contrast, solvolysis of acridine 3,4-oxide under acid conditions gave 4-hydroxyacridine as the exclusive product. pH-rate profiles for hydrolysis of the acridine oxides in 1:9 dioxane-water at 25 degrees C were compared with those for anthracene 1,2-oxide, naphthalene 1,2-oxide, and quinoline 5,6- and 7,8-oxides. Second-order rate constants for the hydronium ion-catalyzed ring opening of anthracene 1,2-, acridine 3,4-, and acridine 1,2-oxide are 585, 7.81, and 0.45 M(-1) s(-2), respectively, and are 3-5 times larger than the rate constants for the corresponding naphthalene 1,2-, quinoline 7,8-, and quinoline 5,6-oxides. Rate constants for uncatalyzed ring opening of anthracene 1,2- and acridine 3,4-oxides (117 x 10(-5) s(-1) and 2.4 X 10(-5) s(-1), respectively) are about two to three times larger than the corresponding rate constants for naphthalene 1,2- and quinoline 7,8-oxides, whereas the rate of nucleophilic ring opening by hydroxide ion to give the trans-dihydrodiols is accelerated by less than a factor of 2 for the acridine oxides as compared with their quinoline analogs. The pH-rate profiles for solvolysis of the acridine oxides, like those of the quinoline oxides, exhibit a pH-independent region at pH values below the pK(a) of the ring nitrogen that is attributed to formation of an unreactive N-protonated species.