6-methyl-6H-dibenzopyran | 120211-92-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 6-methyl-6H-dibenzopyran
• 英文别名: 6-methyl-6H-benzo[c]chromene
• CAS: 120211-92-9
• 化学式: C₁₄H₁₂O
• 分子量: 196.249
• InChiKey: WLWJMTOELYMTRM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-methyl-6H-dibenzopyran 在 亚碘酰苯 、 C₇₂H₅₂MnN₂O₂⁽¹⁺⁾*F₆P^(1-) 作用下， 以 二氯甲烷 为溶剂， 以47%的产率得到(S)-6-methyl-6H-benzo[c]chromene
  参考文献：
  名称：

  环状苯甲醚的氧化动力学拆分

  摘要：

  据报道，锰通过不对称的C（sp 3）-H氧化反应催化了环苄醚的氧化动力学拆分。实际的方法适用于范围广泛的1,3-二氢异苯并呋喃，其在α位置带有多种官能团和取代基，并具有非常有效的对映歧化作用。该策略的普遍性通过另一种五元环状苄基醚，2,3-二氢苯并呋喃和六元6H-苯并[c]苯二酚的有效氧化动力学拆分得到了进一步证明。进一步探索了否则难以获得的生物活性分子的直接后期氧化动力学拆分。

  DOI：

  10.1002/anie.202009594
• 作为产物：
  描述：

  苯并[c]苯并吡喃-6-酮 在 二氢吡啶 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 6-methyl-6H-dibenzopyran
  参考文献：
  名称：

  环状苯甲醚的氧化动力学拆分

  摘要：

  据报道，锰通过不对称的C（sp 3）-H氧化反应催化了环苄醚的氧化动力学拆分。实际的方法适用于范围广泛的1,3-二氢异苯并呋喃，其在α位置带有多种官能团和取代基，并具有非常有效的对映歧化作用。该策略的普遍性通过另一种五元环状苄基醚，2,3-二氢苯并呋喃和六元6H-苯并[c]苯二酚的有效氧化动力学拆分得到了进一步证明。进一步探索了否则难以获得的生物活性分子的直接后期氧化动力学拆分。

  DOI：

  10.1002/anie.202009594

文献信息

• An Efficient Preparation of Chroman Derivatives from 3-Aryl-1-propanols and Related Compounds with 1,3-Diiodo-5,5-dimethylhydantoin under Irradiation Conditions
  作者：Hideo Togo、Shusuke Furuyama

  DOI：10.1055/s-0030-1258017

  日期：2010.9

  under irradiation with a tungsten lamp gave the corresponding chroman derivatives in good to moderate yields. The present reaction proceeds via the initial formation of an alkoxyl radical and the radical cyclization onto the aromatic ring, followed by the oxidation of the formed radical intermediate with DIH to provide the chroman derivative. The same treatment of o-biphenyldimethylcarbinol, o-phenylbenzoic

  在钨灯照射下，在乙酸乙酯或 1,2-二氯乙烷中用 1,3-二碘-5,5-二甲基乙内酰脲 (DIH) 处理各种 3-芳基-1-丙醇，得到相应的色满衍生物，产率良好至中等. 本反应通过烷氧基的初始形成和芳环上的自由基环化进行，然后用DIH氧化形成的自由基中间体以提供色满衍生物。用 DIH 对邻联苯基二甲基甲醇、邻苯基苯甲酸和邻烷基苯甲酸进行相同处理，分别以良好的收率提供相应的色满衍生物和内酯衍生物。
• One-Pot Synthesis of O-Heterocycles or Aryl Ketones Using an InCl₃/Et₃SiH System by Switching the Solvent
  作者：Wenqiang Jia、Qiumu Xi、Tianqi Liu、Minjian Yang、Yonghui Chen、Dali Yin、Xiaojian Wang

  DOI：10.1021/acs.joc.9b00140

  日期：2019.5.3

  An efficient one-pot synthesis of O-heterocycles or aryl ketones has been achieved using Et3SiH in the presence of InCl3 via a sequential ionic hydrogenation reaction by switching the solvent. This methodology can be used to construct C–O bonds and to prepare conjugate reduction products, including chromans, tetrahydrofurans, tetrahydropyrans, dihydroisobenzofurans, dihydrochalcones, and 1,4-diones

  使用Int 3 SiH的Et 3 SiH通过转换溶剂进行顺序离子氢化反应，可以在InCl 3存在下实现O-杂环或芳基酮的有效一锅合成。该方法可用于轻松构建C–O键并制备共轭物还原产物，包括苯并二氢吡喃，四氢呋喃，四氢吡喃，二氢异苯并呋喃，二氢查耳酮和1,4-二酮。另外，通过实验研究证实了涉及共轭物还原和串联还原性环化的新型合理机制。
• Photocyclization of o-phenoxybenzyl alcohols in aqueous solution. A simple synthesis of 6H-dibenzo[b,d]pyrans
  作者：Peter Wan、Cai-Gu Huang

  DOI：10.1039/c39880001193

  日期：——

  A new photochemical cyclization reaction of o-phenoxybenzyl alcohols is reported, which is observed only in aqueous solution, giving rise to 6H-dibenzo[b,d]pyrans in good yields.

  据报道，仅在水溶液中观察到一种新的邻苯氧基苄醇的光化学环化反应，以良好的产率产生了6 H-二苯并[ b，d ]吡喃。
• Mechanism of photoisomerization of xanthene to 6H-dibenzo[b,d]pyran in aqueous solution
  作者：C. G. Huang、Deepak Shukla、Peter Wan

  DOI：10.1021/jo00018a044

  日期：1991.8

  A new photoreaction, the photoisomerization of xanthene (1) to 6H-dibenzo[b,d]pyran (2) (almost-equal-to 70%) (PHI = 0.0035 in 7:3 H2O-CH3CN) in aqueous CH3CN solution is reported. In addition to 2, 2-benzylphenol (3) (PHI almost-equal-to 0.001), 9,9'-bixanthyl (4) (PHI < 0.001), and 2-(2'-hydroxyphenyl)benzyl alcohol (5) (PHI < 0.001) are also observed as minor products. 9-Methylxanthene (9) also photoisomerizes to the corresponding pyran derivative 10, although in this case much lower yields are observed due to secondary photochemistry of 10. The photoisomerization of 1 is most efficient in aqueous solution: PHI increased with increasing water content in a H2O-CH3CN solvent mixture. A mechanism of photoisomerization is proposed that involves initial Ar-O bond homolysis from S1, to generate a singlet biradical. Trivial recombination gives back unreacted 1. Hydrogen abstraction from solvent leads to the photoreduction product 3. However, recombination of the biradical at the ipso benzylic position (ortho to phenol) gives a cyclohexadienone intermediate 17. Subsequent transformation of this species to 2 occurs via an o-quinone methide intermediate 18, which itself can be trapped with MeOH or H2O, to give the corresponding methyl ether derivative 8 or alcohol 5.
• Photochemistry of phenoxybenzyl alcohols in aqueous solution: photosolvolysis vs. photorearrangement to 6H-dibenzo[b,d]pyrans
  作者：C. G. Huang、Peter Wan

  DOI：10.1021/jo00016a009

  日期：1991.8

  The photochemistry of three phenoxybenzyl alcohols (1-3) has been studied in MeOH, CH3CN, and in aqueous solution. It was found that both of the ortho-substituted phenoxybenzyl alcohols 1 and 2 gave the corresponding 6H-dibenzo[b,d]pyrans 6 and 10, via a mechanism believed to involve initial aryl C-O bond homolysis followed by rearrangement to give a 2-(2'-hydroxyphenyl)benzyl alcohol (biphenyl) derivative, which subsequently undergoes a photocyclization reaction to the corresponding 6H-dibenzo[b,d]pyran. The quantum yield for formation of 6 (from 1) was 0.0073 in neutral 6:4 H2O-CH3CN. Lower quantum yields for formation of 6 were observed on photolysis in pure organic solvents (PHI = 0.0015 in 100% CH3CN). The meta-substituted isomer 3 did not give any reaction via a similar photocyclization process: its photochemistry involves initial aryl C-O bond homolysis followed by simple radical recoupling to give isomeric hydroxybiphenyls, as well as products derived from radical escape. In aqueous sulfuric acid solution (pH < 2), a competing acid-catalyzed photosolvolysis reaction was observed for all of these compounds (i.e., C-OH bond heterolysis with assistance of hydronium ion); it was the only observed reaction in moderately concentrated sulfuric acid solution.