(spiro[5-dihydro-2,3-dioxobenzocycloheptane-4,2'-(3',6'-dihydro)benzotetrahydropyran]-1-yl)acetic acid ethyl ester | 854307-26-9

• 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: (spiro[5-dihydro-2,3-dioxobenzocycloheptane-4,2'-(3',6'-dihydro)benzotetrahydropyran]-1-yl)acetic acid ethyl ester
• 英文别名: Ethyl 2-spiro[1,4-dihydroisochromene-3,4'-1,5-dihydro-2,3-benzodioxepine]-1'-ylacetate
• CAS: 854307-26-9
• 化学式: C₂₁H₂₂O₅
• 分子量: 354.403
• InChiKey: ZRTXUALEPMTYGJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (spiro[5-dihydro-2,3-dioxobenzocycloheptane-4,2'-(3',6'-dihydro)benzotetrahydropyran]-1-yl)acetic acid ethyl ester 在 锂硼氢 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以94%的产率得到2-(spiro[5-dihydro-2,3-dioxobenzocycloheptane-4,2'-(3',6'-dihydro)benzotetrahydropyran]-1-yl)ethanol
  参考文献：
  名称：

  On the Susceptibility of Organic Peroxy Bonds to Hydride Reduction

  摘要：

  Reduction of organic molecules that contain a peroxy bond is broadly considered as a "risky" and uncertain operation when cleavage of the peroxy linkage is not desired. For this reason, such reduction steps are normally avoided at the planning stage of the synthesis when possible. As a natural consequence, the information in the literature about the susceptibility of organic peroxy bonds to reducing species is scant. In this work the tolerance of organic peroxy bonds to some common hydride reductants was examined systematically for the first time. Using reduction of ester group to alcohol as a probe, LiAlH4, LiAlH((OBU)-B-t)(3), LiBHEt3, and LiBH4 were found to be significantly better than other reductants examined when taking into consideration both the completeness of the reduction of ester groups and the peroxy bond survival rate. LiBH4 appeared to be the most suitable reductant for the reduction under discussion, not only because of the high reduction yields/excellent compatibility with peroxy bonds, but also because of the advantages in practical aspects. The results disclosed herein may (hopefully) provide a handy reference for dealing with reduction of other peroxy bond-containing molecules in the future.

  DOI：

  10.1021/jo050139y
• 作为产物：
  描述：

  1-溴-2-((甲氧基甲氧基)甲基)苯 在 palladium dichloride 盐酸 、 正丁基锂 、 草酰氯 、 air 、 2,2,2-三氟乙醇 、 三氟化硼乙醚 、 水 、 sodium hydride 、 二甲基亚砜 、 二乙胺 、 三乙胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 287.5h， 生成 (spiro[5-dihydro-2,3-dioxobenzocycloheptane-4,2'-(3',6'-dihydro)benzotetrahydropyran]-1-yl)acetic acid ethyl ester
  参考文献：
  名称：

  螺过氧化物的设计，合成及体外抗疟活性

  摘要：

  设计和合成了几种螺过氧抗疟疾化合物，使用过氧化氢在UHP中（脲-H 2 O 2络合物）作为过氧键的来源。掺入H 2 O 2在当前情况下，由于在酮羰基上存在羟基γ或δ，形成五元或六元环状半缩酮的可能性极大地促进了通过缩酮交换反应进入有机分子骨架。当迈克尔受体中的吸电子基团是硝基时，在水氧化条件下，过氧环的闭合很容易发生。与过氧环稠合的苯环的存在有效地降低了闭环步骤过渡态的自由度，并使原本非常困难的七元1,2-二氧戊环很容易通过分子内迈克尔加成而形成。

  DOI：

  10.1016/j.tet.2006.05.065

文献信息

• Synthesis of benzene-fused 1,7,8-trioxa-spiro[5.6]dodecanes
  作者：Hong-Xia Jin、Yikang Wu

  DOI：10.1016/j.tetlet.2005.08.031

  日期：2005.10

  Two novel organic peroxides with one or two benzene rings fused to a 1,7,8-trioxaspiro[5.6]dodecan framework were synthesized, which provided the first examples of employing Kobayashi ' s methodology in the synthesis of seven-membered peroxy rings. CSA was found to be a potent catalyst for introduction of the hydroperoxyl group, making a useful complement to Kobayashi ' s methodology in constructing spiroperoxides. (c) 2005 Elsevier Ltd. All rights reserved.
• On the Susceptibility of Organic Peroxy Bonds to Hydride Reduction
  作者：Hong-Xia Jin、He-Hua Liu、Qi Zhang、Yikang Wu

  DOI：10.1021/jo050139y

  日期：2005.5.1

  Reduction of organic molecules that contain a peroxy bond is broadly considered as a "risky" and uncertain operation when cleavage of the peroxy linkage is not desired. For this reason, such reduction steps are normally avoided at the planning stage of the synthesis when possible. As a natural consequence, the information in the literature about the susceptibility of organic peroxy bonds to reducing species is scant. In this work the tolerance of organic peroxy bonds to some common hydride reductants was examined systematically for the first time. Using reduction of ester group to alcohol as a probe, LiAlH4, LiAlH((OBU)-B-t)(3), LiBHEt3, and LiBH4 were found to be significantly better than other reductants examined when taking into consideration both the completeness of the reduction of ester groups and the peroxy bond survival rate. LiBH4 appeared to be the most suitable reductant for the reduction under discussion, not only because of the high reduction yields/excellent compatibility with peroxy bonds, but also because of the advantages in practical aspects. The results disclosed herein may (hopefully) provide a handy reference for dealing with reduction of other peroxy bond-containing molecules in the future.
• Design, synthesis and in vitro antimalarial activity of spiroperoxides
  作者：Hong-Xia Jin、Qi Zhang、Hye-Sook Kim、Yusuke Wataya、He-Hua Liu、Yikang Wu

  DOI：10.1016/j.tet.2006.05.065

  日期：2006.8

  group. When the electron-withdrawing group in the Michael acceptor was a nitro group, the closure of the peroxy ring occurred readily under the hydroxidation conditions. Presence of a benzene ring fused to the peroxy ring effectively reduced the degrees of freedom in the transition state for the ring-closure step and made the otherwise very difficult seven-membered 1,2-dioxepane rather easy to form

  设计和合成了几种螺过氧抗疟疾化合物，使用过氧化氢在UHP中（脲-H 2 O 2络合物）作为过氧键的来源。掺入H 2 O 2在当前情况下，由于在酮羰基上存在羟基γ或δ，形成五元或六元环状半缩酮的可能性极大地促进了通过缩酮交换反应进入有机分子骨架。当迈克尔受体中的吸电子基团是硝基时，在水氧化条件下，过氧环的闭合很容易发生。与过氧环稠合的苯环的存在有效地降低了闭环步骤过渡态的自由度，并使原本非常困难的七元1,2-二氧戊环很容易通过分子内迈克尔加成而形成。