Benz[a]anthracen-6-ol, 5,6-dihydro-5-methoxy-4-methyl-, cis- | 120014-47-3

• 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: Benz[a]anthracen-6-ol, 5,6-dihydro-5-methoxy-4-methyl-, cis-
• 英文别名: Benz[a]anthracen-6-ol, 5,6-dihydro-5-methoxy-4-methyl-, trans-
• CAS: 120014-47-3；133867-80-8；133867-91-1；146683-95-6；146684-13-1
• 化学式: C₂₀H₁₈O₂
• 分子量: 290.362
• InChiKey: CJFABQJXQXTEOA-PMACEKPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.55
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  Benz[a]anthracen-6-ol, 5,6-dihydro-5-methoxy-4-methyl-, cis- 在 三氟化硼乙醚 作用下， 以 乙醚 为溶剂， 反应 6.0h， 生成 4-methylbenzo[a]anthracen-6-ol 、 6-methoxy-4-methylbenzo[a]anthracene 、 5-methoxy-4-methylbenzo[a]anthracene
  参考文献：
  名称：

  Sterically induced methoxyl migration on acid-catalyzed dehydration of K-region trans-dihydrodiol monomethyl ethers

  摘要：

  The regioisomers of the trans-dihydrodiol monomethyl ethers (DME) at the K-regions of 4- and 7-methyl- and 7,12-dimethylbenz[a] anthracene, which possess a ring methyl substituent peri to the methoxyl group, react with BF3.etherate to form a single phenol and two regioisomeric phenol methyl ethers, one of which arises by migration of the methoxyl group. In contrast, for DME of benz[a]-anthracene and its 1-, 4-, 7-, 11- and 12-methyl- and 7,12-dimethyl-substituted derivatives where there is no peri methyl group, methoxyl migration does not occur, and thus only the phenol methyl ether resulting from loss of water is formed. These results are consistent with a mechanism in which the initially formed carbocation with a pseudoaxial methoxyl group must undergo either conformational change to align the bond of the leaving proton with the empty p-orbital prior to proton loss or migration of the methoxyl group to the adjacent carbocation via a cyclic oxonium ion. In the absence of a ring substituent peri to the methoxyl group, conformational change is faster than formation of the cyclic oxonium ion, and therefore migration of the methoxyl group does not occur. A methyl substituent peri to the methoxyl group raises the activation energy barrier for conformational isomerization due to adverse steric interaction between the two groups. Consequently, formation of the cyclic oxonium ion becomes competitive with conformational change. The resulting oxonium ion opens to the regioisomeric carbocation resulting in rearrangement. Formation of the cyclic oxonium ion in these reactions is analogous to the rapid internal return of the hydroxy carbocation intermediate to protonated epoxide that is thought to occur in the reactions of peri-methyl-substituted K-region arene oxides.

  DOI：

  10.1021/jo00075a030
• 作为产物：
  描述：

  sodium methylate 、 4-methylbenzanthracene 5,6-oxide 以 甲醇 、 乙腈 为溶剂， 生成 Benz[a]anthracen-6-ol, 5,6-dihydro-5-methoxy-4-methyl-, cis- 、 Benz[a]anthracen-5-ol, 5,6-dihydro-6-methoxy-4-methyl-, cis-
  参考文献：
  名称：

  K 区芳烃氧化物的甲醇分解：酸催化和甲醇离子加成反应的比较

  摘要：

  摘要：苯并 [a] 蒽 (BA-0) 及其 1- (1-MBA-0)、4- (CMBA-0)、7- (7-MBA-0) 的 K 区芳烃氧化物的反应， 11-(1 1-MBA-0)、12-甲基-(I2-MBA-O)、7,12-二甲基-(DMBA-O)和7-溴-(7-BrBA-0)取代的衍生物，苯并[a]芘(BaP-0)、苯并[c]菲(BcP-0)、苯并[e]芘(BeP-0)、苯并[g]芘(BgC-0)、芘(Chr-0) 、二苯并 [a,h] 蒽 (DBA-0)、菲 (Phe-0)、3-溴菲 (3-BrPhe-0) 和芘 (Pyr-0) 与甲醇中的酸和甲醇离子进行了比较。对于酸催化反应，产物由顺式和反式甲醇加合物和酚类组成。当用氘代替迁移的氢时，对苯酚与由 Phe-0 或 BcP-0 产生的溶剂加合物的比率没有同位素影响。该观察结果与酸中产物分布由溶剂捕获和碳正离子中间体的构象反转的相对速率决

  DOI：

  10.1021/ja00058a015

文献信息

• Solvolysis of K-region arene oxides: substituent effects on reactions of benz[a]anthracene 5,6-oxide
  作者：Nashaat T. Nashed、Suresh K. Balani、Richard J. Loncharich、Jane M. Sayer、David Y. Shipley、Ram S. Mohan、Dale L. Whalen、Donald M. Jerina

  DOI：10.1021/ja00010a036

  日期：1991.5

  dioxane-water and in methanol at 25 o C are reported. These substitutions result in >150-fold differences in their rates of acid-catalyzed solvolysis and cause marked changes in the distribution of solvent adducts and phenols resulting from isomerization. Optically pure BA-O, 7-MBA-O, 12-MBA-O, and 7,12-DMBA-O as well as their optically pure trans dihydrodiols were utilized to determine the point of attack by

  苯并 [a] 蒽 5,6-氧化物 (BA-O) 在取代 1 (1-MBA-O)、4 (4-MBA-O)、7 ( 7-MBA-O)、11 (11-MBA-O) 和 12 (12-MBA-O)、7,12-二甲基取代 (7,12-DMBA-O) 和 7-溴取代1:9 二恶烷-水和甲醇在 25 o C 报告。这些取代导致其酸催化溶剂分解的速率差异 > 150 倍，并导致异构化导致的溶剂加合物和酚类的分布发生显着变化。利用光学纯的 BA-O、7-MBA-O、12-MBA-O 和 7,12-DMBA-O 以及它们的光学纯反式二氢二醇来确定水解反应中水的攻击点
• Methanolysis of K-region arene oxides: comparison between acid-catalyzed and methoxide ion addition reactions
  作者：Nashaat T. Nashed、Ad Bax、Richard J. Loncharich、Jane M. Sayer、Donald M. Jerina

  DOI：10.1021/ja00058a015

  日期：1993.3

  kH/kH-) + b, where kMd and kH are the second-order rate constants of the methoxide ion addition and acid-catalyzed reaction, respectively, and kM~Phc-o and kHPbe-O are the corresponding rate constants for the reference compound phenanthrene oxide. A plot of log kMso/kMsoM vs log kH/kHPhbO for the reaction of l-MBA-O,12-MBA-O, DMBA-0, BcP-0, and BgC-0, which have either a methyl substituent in the bay

  摘要：苯并 [a] 蒽 (BA-0) 及其 1- (1-MBA-0)、4- (CMBA-0)、7- (7-MBA-0) 的 K 区芳烃氧化物的反应， 11-(1 1-MBA-0)、12-甲基-(I2-MBA-O)、7,12-二甲基-(DMBA-O)和7-溴-(7-BrBA-0)取代的衍生物，苯并[a]芘(BaP-0)、苯并[c]菲(BcP-0)、苯并[e]芘(BeP-0)、苯并[g]芘(BgC-0)、芘(Chr-0) 、二苯并 [a,h] 蒽 (DBA-0)、菲 (Phe-0)、3-溴菲 (3-BrPhe-0) 和芘 (Pyr-0) 与甲醇中的酸和甲醇离子进行了比较。对于酸催化反应，产物由顺式和反式甲醇加合物和酚类组成。当用氘代替迁移的氢时，对苯酚与由 Phe-0 或 BcP-0 产生的溶剂加合物的比率没有同位素影响。该观察结果与酸中产物分布由溶剂捕获和碳正离子中间体的构象反转的相对速率决
• Sterically induced methoxyl migration on acid-catalyzed dehydration of K-region trans-dihydrodiol monomethyl ethers
  作者：Nashaat T. Nashed、Tata Venkata S. Rao、Donald M. Jerina

  DOI：10.1021/jo00075a030

  日期：1993.11

  The regioisomers of the trans-dihydrodiol monomethyl ethers (DME) at the K-regions of 4- and 7-methyl- and 7,12-dimethylbenz[a] anthracene, which possess a ring methyl substituent peri to the methoxyl group, react with BF3.etherate to form a single phenol and two regioisomeric phenol methyl ethers, one of which arises by migration of the methoxyl group. In contrast, for DME of benz[a]-anthracene and its 1-, 4-, 7-, 11- and 12-methyl- and 7,12-dimethyl-substituted derivatives where there is no peri methyl group, methoxyl migration does not occur, and thus only the phenol methyl ether resulting from loss of water is formed. These results are consistent with a mechanism in which the initially formed carbocation with a pseudoaxial methoxyl group must undergo either conformational change to align the bond of the leaving proton with the empty p-orbital prior to proton loss or migration of the methoxyl group to the adjacent carbocation via a cyclic oxonium ion. In the absence of a ring substituent peri to the methoxyl group, conformational change is faster than formation of the cyclic oxonium ion, and therefore migration of the methoxyl group does not occur. A methyl substituent peri to the methoxyl group raises the activation energy barrier for conformational isomerization due to adverse steric interaction between the two groups. Consequently, formation of the cyclic oxonium ion becomes competitive with conformational change. The resulting oxonium ion opens to the regioisomeric carbocation resulting in rearrangement. Formation of the cyclic oxonium ion in these reactions is analogous to the rapid internal return of the hydroxy carbocation intermediate to protonated epoxide that is thought to occur in the reactions of peri-methyl-substituted K-region arene oxides.