3-methoxyphenanthro[4,3-b][1]benzothiophene | 485824-10-0

• 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-methoxyphenanthro[4,3-b][1]benzothiophene
• 英文别名: 18-Methoxy-3-thiapentacyclo[11.8.0.02,10.04,9.016,21]henicosa-1(13),2(10),4,6,8,11,14,16(21),17,19-decaene；18-methoxy-3-thiapentacyclo[11.8.0.02,10.04,9.016,21]henicosa-1(13),2(10),4,6,8,11,14,16(21),17,19-decaene
• CAS: 485824-10-0
• 化学式: C₂₁H₁₄OS
• 分子量: 314.408
• InChiKey: YYROPLPMQLNNJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methoxyphenanthro[4,3-b][1]benzothiophene 在 potassium dihydrogenphosphate 、 potassium nitrososulfonate 、 Adogen-464 、 三溴化硼 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 27.0h， 生成 phenanthro[4,3-b][1]benzothiophene-3,4-dione
  参考文献：
  名称：

  Synthesis of Dihydrodiol Metabolites Implicated in the Mechanism of Carcinogenesis of Phenanthro[4,3-b][1]benzothiophene and Phenanthro[3,4-b][1]benzothiophene, the Polycyclic Sulfur Heterocycles with a “Fjord” Structure

  摘要：

  Dihydrodiols, which are potential proximate carcinogens of phenanthro[4,3-b][1]benzothiophene (3) and phenanthro[3,4-b] [1]benzothiophene (4) and possess a "fjord" structure, were synthesized. The dihydrodiols synthesized were trans-3,4-dihydroxy-3,4-dihydrophenanthro[4,3-b] [1]benzothiophene (5) and trans-3,4-dihydroxy-3,4-dihydrophenanthro [3,4-b] [ 11 benzothiophene (6). The precursors to the dihydrodiols 5 and 6 were 3-methoxyphenanthro[4,3-b][1]benzothiophene (11) and 3-methoxyphenanthro[3,4-b][1]benzothiophene (16). Compound 11 was obtained via Suzuki cross-coupling reaction of easily accessible starting materials. However, this synthetic strategy utilizing Suzuki reaction for the preparation of 16 was comparatively less productive than that described previously due to time-consuming synthesis of the starting material(s), and extremely poor yield associated with cyclization of the epoxide 15 to 16. The methoxy derivatives 11 and 16 were converted to the corresponding dihydrodiols 5 and 6 by a sequence involving demethylation, oxidation, and reduction. The trans-stereochemistry of the dihydrodiols was established by H-1 NMR, which indicated a large coupling constant between vicinal carbinol protons. The UV spectra of the dihydrodiols 5 and 6 are presented.

  DOI：

  10.1021/jo020493l
• 作为产物：
  描述：

  2-溴-5-甲氧基苯甲醛 在 氢氧化钾 、 四(三苯基膦)钯 、 甲烷磺酸 、 cesium fluoride 作用下， 以 乙二醇二甲醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 55.0h， 生成 3-methoxyphenanthro[4,3-b][1]benzothiophene
  参考文献：
  名称：

  Synthesis of Dihydrodiol Metabolites Implicated in the Mechanism of Carcinogenesis of Phenanthro[4,3-b][1]benzothiophene and Phenanthro[3,4-b][1]benzothiophene, the Polycyclic Sulfur Heterocycles with a “Fjord” Structure

  摘要：

  Dihydrodiols, which are potential proximate carcinogens of phenanthro[4,3-b][1]benzothiophene (3) and phenanthro[3,4-b] [1]benzothiophene (4) and possess a "fjord" structure, were synthesized. The dihydrodiols synthesized were trans-3,4-dihydroxy-3,4-dihydrophenanthro[4,3-b] [1]benzothiophene (5) and trans-3,4-dihydroxy-3,4-dihydrophenanthro [3,4-b] [ 11 benzothiophene (6). The precursors to the dihydrodiols 5 and 6 were 3-methoxyphenanthro[4,3-b][1]benzothiophene (11) and 3-methoxyphenanthro[3,4-b][1]benzothiophene (16). Compound 11 was obtained via Suzuki cross-coupling reaction of easily accessible starting materials. However, this synthetic strategy utilizing Suzuki reaction for the preparation of 16 was comparatively less productive than that described previously due to time-consuming synthesis of the starting material(s), and extremely poor yield associated with cyclization of the epoxide 15 to 16. The methoxy derivatives 11 and 16 were converted to the corresponding dihydrodiols 5 and 6 by a sequence involving demethylation, oxidation, and reduction. The trans-stereochemistry of the dihydrodiols was established by H-1 NMR, which indicated a large coupling constant between vicinal carbinol protons. The UV spectra of the dihydrodiols 5 and 6 are presented.

  DOI：

  10.1021/jo020493l

文献信息

• Electrophilic Chemistry of Thia-PAHs:  Stable Carbocations (NMR and DFT), S-Alkylated Onium Salts, Model Electrophilic Substitutions (Nitration and Bromination), and Mutagenicity Assay
  作者：Kenneth K. Laali、Joong-Hyun Chun、Takao Okazaki、Subodh Kumar、Gabriela L. Borosky、Carol Swartz

  DOI：10.1021/jo701502y

  日期：2007.10.1

  from several classes of thia-PAHs with four fused rings, namely, benzo[b]naphtho[2,1-d]thiophene (1) and its 3-methoxy derivative (2), phenanthro[4,3-b]thiophene (3) and its 7-methoxy (4), 10-methoxy (5), and 9-methoxy (6) derivatives, phenanthro[3,4-b]thiophene (7) and its 7-methoxy (8) and 9-methoxy (9) derivatives, and 3-methoxybenzo[b]naphtha[1,2-d]thiophene (11). In several cases, the resulting carbocations

  从具有四个稠环的几类硫杂多环芳烃中报道了稳定碳正离子的第一个例子，即苯并[ b ]萘并[2,1- d ]噻吩 ( 1 ) 及其 3-甲氧基衍生物 ( 2 )，菲 [4 ] ,3- b ]噻吩( 3 )及其7-甲氧基( 4 )、10-甲氧基( 5 )和9-甲氧基( 6 )衍生物、菲[3,4- b ]噻吩( 7 )及其7-甲氧基 ( 8 ) 和 9-甲氧基 ( 9 ) 衍生物，以及 3-甲氧基苯并[ b ] 萘[1,2- d ] 噻吩 ( 11）。在一些情况下，GIAO-DFT 还研究了由此产生的碳正离子。探测了所得碳正离子中的电荷离域模式。一系列S-烷基化的四氟硼酸鎓，即1Me +, 1Et +, 2Et +, 和7Me +（从1、2和7），10Me +和10Et +(来自苯并[ b ]石脑油[1,2- d ]噻吩10 ), 12Me +和12Et +（来自菲 [3,2- b ][1] 苯并噻吩12），13Me