o-methoxybenzyl allenyl ketone | 219660-45-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: o-methoxybenzyl allenyl ketone
• 英文别名: 1-(2-methoxyphenyl)penta-3,4-dien-2-one
• CAS: 219660-45-4
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: YTCHIAOBPREZDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  o-methoxybenzyl allenyl ketone 在 silver nitrate 作用下， 以 乙腈 为溶剂， 以88%的产率得到2-(2-methoxybenzyl)furan
  参考文献：
  名称：

  Mercury(II)-Catalyzed Synthesis of Spiro[4.5]decatrienediones from Allenyl Ketones and Comparison with Silver(I)-, Palladium(II)- and Brønsted Acid-Catalyzed Reactions

  摘要：

  The allenyl p-methoxybenzyl ketone 3a and allenyl p-siloxybenzyl ketones 6b selectively delivered three different products with three different transition metal-catalysts. With Hg(II)-catalysts a spiro[4.5]decene 9, with Ag(I)-catalysts a 2-substituted furan (10/11) and with Pd(II)-catalysts a 2,4-disubstituted furan (8/12) was formed. Only with perchloric acid the intermolecular addition of water to the allene, leading to 1,3-dicarbonyl compounds 7, was observed. While with the corresponding allenyl o-methoxybenzyl ketone 3b the Ag(I)- and Pd(II)-catalysts provided the expected products, the mercury-catalyst led to a new and interesting side-product rac-17 which combined both the furan moiety and the spiro[4.5]decene moiety. Efforts to prepare allenyl hydroxybenzyl ketones failed, in one case a small amount of a 5H-benzo[b]oxepin-4-one 21 was isolated. It also was not possible to extend the spirocyclization to allenyl p-siloxyphenyl ketone 6a or allenyl 2-(p-siloxyphenyl)ethyl ketone 6c.

  DOI：

  10.1002/(sici)1521-3897(200001)342:1<40::aid-prac40>3.0.co;2-v
• 作为产物：
  描述：

  2-甲氧基苯乙酸甲酯 、 allenylmagnesium bromide 以 乙醚 为溶剂， 反应 0.25h， 以57%的产率得到o-methoxybenzyl allenyl ketone
  参考文献：
  名称：

  Mercury(II)-Catalyzed Synthesis of Spiro[4.5]decatrienediones from Allenyl Ketones and Comparison with Silver(I)-, Palladium(II)- and Brønsted Acid-Catalyzed Reactions

  摘要：

  The allenyl p-methoxybenzyl ketone 3a and allenyl p-siloxybenzyl ketones 6b selectively delivered three different products with three different transition metal-catalysts. With Hg(II)-catalysts a spiro[4.5]decene 9, with Ag(I)-catalysts a 2-substituted furan (10/11) and with Pd(II)-catalysts a 2,4-disubstituted furan (8/12) was formed. Only with perchloric acid the intermolecular addition of water to the allene, leading to 1,3-dicarbonyl compounds 7, was observed. While with the corresponding allenyl o-methoxybenzyl ketone 3b the Ag(I)- and Pd(II)-catalysts provided the expected products, the mercury-catalyst led to a new and interesting side-product rac-17 which combined both the furan moiety and the spiro[4.5]decene moiety. Efforts to prepare allenyl hydroxybenzyl ketones failed, in one case a small amount of a 5H-benzo[b]oxepin-4-one 21 was isolated. It also was not possible to extend the spirocyclization to allenyl p-siloxyphenyl ketone 6a or allenyl 2-(p-siloxyphenyl)ethyl ketone 6c.

  DOI：

  10.1002/(sici)1521-3897(200001)342:1<40::aid-prac40>3.0.co;2-v

文献信息

• Studies on the Himbert Intramolecular Arene/Allene Diels–Alder Cycloaddition. Mechanistic Studies and Expansion of Scope to All-Carbon Tethers
  作者：Yvonne Schmidt、Jonathan K. Lam、Hung V. Pham、K. N. Houk、Christopher D. Vanderwal

  DOI：10.1021/ja4025963

  日期：2013.5.15

  The unusual intramolecular arene/allene cycloaddition described 30 years ago by Himbert permits rapid access to strained polycyclic compounds that offer great potential for the synthesis of complex scaffolds. To more fully understand the mechanism of this cycloaddition reaction, and to guide efforts to extend its scope to new substrates, quantum mechanical computational methods were employed in concert

  30 年前由 Himbert 描述的不寻常的分子内芳烃/丙二烯环加成允许快速获得紧张的多环化合物，这些化合物为复杂支架的合成提供了巨大的潜力。为了更全面地了解这种环加成反应的机制，并指导将其范围扩展到新底物的努力，量子力学计算方法与实验室实验相结合。这些研究表明环加成很可能通过协同过程进行；在所研究的案例中，逐步双自由基机制显示出更高的能量。原始的 Himbert 环加成化学也从杂环系统扩展到碳环系统，并使用计算指导来预测热力学有利的情况。
• Mercury(II)-catalyzed synthesis of spiro[4.5]decatrienediones in the presence of water
  作者：A.Stephen K. Hashmi、Lothar Schwarz、Michael Bolte

  DOI：10.1016/s0040-4039(98)02057-7

  日期：1998.12

  Treatment of the easily available p-methoxybenzyl allenyl ketone 2 or the (p-tert-butyldimethylsiloxybenzyl) allenyl ketone 9 with 1% Hg(ClO4)(2) in acetonitrile/water provided good yields of the spiro[4.5]deca-3,5,9-triene-2,8-dione 6c. The Hg(II)-catalyzed addition of water to the allene was much slower, the 1,3-diketone 7 was only a minor side-product. The isomeric a-methoxybenzyl allenyl ketone 12 formed some spiro[4.5]deca-3,7,9-triene-2,6-dione 13, the side-reactions were the addition of water and a new spirocyclization/dimerization leading to 15. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Mercury(II)-Catalyzed Synthesis of Spiro[4.5]decatrienediones from Allenyl Ketones and Comparison with Silver(I)-, Palladium(II)- and Brønsted Acid-Catalyzed Reactions
  作者：A. Stephen K. Hashmi、Lothar Schwarz、J. W. Bats

  DOI：10.1002/(sici)1521-3897(200001)342:1<40::aid-prac40>3.0.co;2-v

  日期：2000.1

  The allenyl p-methoxybenzyl ketone 3a and allenyl p-siloxybenzyl ketones 6b selectively delivered three different products with three different transition metal-catalysts. With Hg(II)-catalysts a spiro[4.5]decene 9, with Ag(I)-catalysts a 2-substituted furan (10/11) and with Pd(II)-catalysts a 2,4-disubstituted furan (8/12) was formed. Only with perchloric acid the intermolecular addition of water to the allene, leading to 1,3-dicarbonyl compounds 7, was observed. While with the corresponding allenyl o-methoxybenzyl ketone 3b the Ag(I)- and Pd(II)-catalysts provided the expected products, the mercury-catalyst led to a new and interesting side-product rac-17 which combined both the furan moiety and the spiro[4.5]decene moiety. Efforts to prepare allenyl hydroxybenzyl ketones failed, in one case a small amount of a 5H-benzo[b]oxepin-4-one 21 was isolated. It also was not possible to extend the spirocyclization to allenyl p-siloxyphenyl ketone 6a or allenyl 2-(p-siloxyphenyl)ethyl ketone 6c.