3,4,11-trihydroxydibenz[a,j]anthracene | 216657-02-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 3,4,11-trihydroxydibenz[a,j]anthracene
• 英文别名: Pentacyclo[12.8.0.03,12.04,9.017,22]docosa-1,3(12),4(9),5,7,10,13,15,17(22),18,20-undecaene-7,8,19-triol
• CAS: 216657-02-2
• 化学式: C₂₂H₁₄O₃
• 分子量: 326.351
• InChiKey: MLJRSNKXRVAXAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,4,11-trihydroxydibenz[a,j]anthracene 在 吡啶 、 sodium tetrahydroborate 、 氧气 作用下， 以 乙醇 为溶剂， 反应 72.0h， 生成 trans-3,4-dihydroxy-3,4-dihydro-11-hydroxydibenz[a,j]anthracene
  参考文献：
  名称：

  Synthesis of Higher Oxidized Metabolites of Dibenz[a,j]anthracene Implicated in the Mechanism of Carcinogenesis

  摘要：

  Higher oxidized metabolites are implicated as active carcinogenic forms of polycyclic aromatic hydrocarbons which have two or more bay or fjord molecular regions, such as dibenz[a,j]anthracene. These include the bis(dihydrodiols) and phenolic dihydrodiols which may potentially undergo further metabolism to the corresponding diol epoxides. The latter react with DNA resulting in mutations that lead to tumorigenesis. Prior characterization of these metabolites has been based largely on HPLC and spectroscopic evidence. This paper reports efficient syntheses of the trans-trans-3,4,8,9-dihydrodiol (1) and the 10- and Il-phenolic trans-3,4-dihydrodiols of dibenz[a,j]anthracene (3a,b). The synthetic route to 1 entails as the key steps asymmetric dihydroxylation of an appropriately substituted stilbene precursor employing a Sharpless catalyst followed by intramolecular cyclodehydrobromination catalyzed by Pd(PPh3)(2)Cl-2. The syntheses of 3a,b proceed via sequences involving a Wittig reaction of anisaldehyde with a phosphonium salt of 2-chloro-3-methylbenzyl bromide to give a stilbene compound and then photocyclization, conversion of the product to a phosphonium salt, a second Wittig reaction and photocyclization, reductive dechlorination, and conversion of the resulting trimethoxydibenz[a,j] anthracenes to the phenolic dihydro diols. A key feature of these syntheses is the effective use of chloro substituents to block photocyclization in an undesired direction. These methods are potentially applicable to the synthesis of analogous higher oxidized metabolites of other polycyclic aromatic carcinogens.

  DOI：

  10.1021/jo980416j
• 作为产物：
  描述：

  7-chloro-3,4,11-trimethoxydibenz[a,j]anthracene 在 lithium aluminium tetrahydride 、 三溴化硼 、 nickel dichloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.5h， 生成 3,4,11-trihydroxydibenz[a,j]anthracene
  参考文献：
  名称：

  Synthesis of Higher Oxidized Metabolites of Dibenz[a,j]anthracene Implicated in the Mechanism of Carcinogenesis

  摘要：

  Higher oxidized metabolites are implicated as active carcinogenic forms of polycyclic aromatic hydrocarbons which have two or more bay or fjord molecular regions, such as dibenz[a,j]anthracene. These include the bis(dihydrodiols) and phenolic dihydrodiols which may potentially undergo further metabolism to the corresponding diol epoxides. The latter react with DNA resulting in mutations that lead to tumorigenesis. Prior characterization of these metabolites has been based largely on HPLC and spectroscopic evidence. This paper reports efficient syntheses of the trans-trans-3,4,8,9-dihydrodiol (1) and the 10- and Il-phenolic trans-3,4-dihydrodiols of dibenz[a,j]anthracene (3a,b). The synthetic route to 1 entails as the key steps asymmetric dihydroxylation of an appropriately substituted stilbene precursor employing a Sharpless catalyst followed by intramolecular cyclodehydrobromination catalyzed by Pd(PPh3)(2)Cl-2. The syntheses of 3a,b proceed via sequences involving a Wittig reaction of anisaldehyde with a phosphonium salt of 2-chloro-3-methylbenzyl bromide to give a stilbene compound and then photocyclization, conversion of the product to a phosphonium salt, a second Wittig reaction and photocyclization, reductive dechlorination, and conversion of the resulting trimethoxydibenz[a,j] anthracenes to the phenolic dihydro diols. A key feature of these syntheses is the effective use of chloro substituents to block photocyclization in an undesired direction. These methods are potentially applicable to the synthesis of analogous higher oxidized metabolites of other polycyclic aromatic carcinogens.

  DOI：

  10.1021/jo980416j

文献信息

• Synthesis of Higher Oxidized Metabolites of Dibenz[<i>a</i>,<i>j</i>]anthracene Implicated in the Mechanism of Carcinogenesis
  作者：Jin-Tao Zhang、Wei Dai、Ronald G. Harvey

  DOI：10.1021/jo980416j

  日期：1998.11.1

  Higher oxidized metabolites are implicated as active carcinogenic forms of polycyclic aromatic hydrocarbons which have two or more bay or fjord molecular regions, such as dibenz[a,j]anthracene. These include the bis(dihydrodiols) and phenolic dihydrodiols which may potentially undergo further metabolism to the corresponding diol epoxides. The latter react with DNA resulting in mutations that lead to tumorigenesis. Prior characterization of these metabolites has been based largely on HPLC and spectroscopic evidence. This paper reports efficient syntheses of the trans-trans-3,4,8,9-dihydrodiol (1) and the 10- and Il-phenolic trans-3,4-dihydrodiols of dibenz[a,j]anthracene (3a,b). The synthetic route to 1 entails as the key steps asymmetric dihydroxylation of an appropriately substituted stilbene precursor employing a Sharpless catalyst followed by intramolecular cyclodehydrobromination catalyzed by Pd(PPh3)(2)Cl-2. The syntheses of 3a,b proceed via sequences involving a Wittig reaction of anisaldehyde with a phosphonium salt of 2-chloro-3-methylbenzyl bromide to give a stilbene compound and then photocyclization, conversion of the product to a phosphonium salt, a second Wittig reaction and photocyclization, reductive dechlorination, and conversion of the resulting trimethoxydibenz[a,j] anthracenes to the phenolic dihydro diols. A key feature of these syntheses is the effective use of chloro substituents to block photocyclization in an undesired direction. These methods are potentially applicable to the synthesis of analogous higher oxidized metabolites of other polycyclic aromatic carcinogens.