3-Hydroperoxy-2-methylene-butyric acid methyl ester | 102710-69-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-Hydroperoxy-2-methylene-butyric acid methyl ester
• 英文别名: Methyl 2-(1-hydroperoxyethyl)acrylate；methyl 3-hydroperoxy-2-methylidenebutanoate
• CAS: 102710-69-0
• 化学式: C₆H₁₀O₄
• 分子量: 146.143
• InChiKey: WOQGMQKTAJFJKP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-Hydroperoxy-2-methylene-butyric acid methyl ester 在 bis(acetylacetonate)oxovanadium 氧气 、 tetraphenylporphyrin 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以73%的产率得到3-羟基-2-亚甲基丁酸甲酯
  参考文献：
  名称：

  Photooxygenation of olefins in the presence of titanium(IV) catalyst. A convienient "one-pot" synthesis of epoxy alcohols.

  摘要：

  DOI：

  10.1021/ja00183a032
• 作为产物：
  描述：

  惕各酸甲酯 在 氧气 、 tetraphenylporphyrin 作用下， 以 四氯化碳 为溶剂， 反应 26.0h， 以81%的产率得到3-Hydroperoxy-2-methylene-butyric acid methyl ester
  参考文献：
  名称：

  Regioselective Synthesis of 2-Hydroperoxy-2-methylenebutanoic Acid Derivatives via Photooxygenation of Tiglic Acid Derivatives

  摘要：

  在四苯基卟啉催化剂存在下，将(E)-2-甲基-2-丁烯酸衍生物（虎尾草酸衍生物）在四氯化碳中进行光氧化反应，通常可以高产率地得到3-羟基过氧-2-亚甲基丁酸衍生物。通过酸催化的环脱水反应，所获得的3-羟基过氧-2-亚甲基丁酸容易生成5-甲基-4-亚甲基-3-氧代-1,2-二氧杂环戊烷（一种过氧内酯），产率为61%。类似地，通过将(E)-2-甲基-2-丁烯醛就地氧化生成的3-羟基过氧-2-亚甲基丁醛进行环脱水反应，则生成3-羟基-5-甲基-4-亚甲基-1,2-二氧杂环戊烷。

  DOI：

  10.1055/s-1986-31871

文献信息

• Regioselective Synthesis of 2-Hydroperoxy-2-methylenebutanoic Acid Derivatives via Photooxygenation of Tiglic Acid Derivatives
  作者：Waldemar Adam、Axel Griesbeck

  DOI：10.1055/s-1986-31871

  日期：——

  Photooxygenation of (E)-2-methyl-2-butenoic acid derivatives (tiglic acid derivatives) in tetrachloromethane in the presence of catalytic amounts of tetraphenylporphine affords 3-hydroperoxy-2-methylenebutanoic derivatives in generally high yields. Acid-catalyzed cyclodehydration of the 3-hydroperoxy-2-methylenebutanoic acid thus obtained readily gives 5-methyl-4-methylene-3-oxo-1,2-dioxolane, a peroxylactone, in 61% yield. The analogous cyclodehydration of 3-hydroperoxy-2-methylenebutanal [generated in situ by oxygenation of (E)-2-methyl-2-butenal] leads to the formation of 3-hydroxy-5-methyl-4-methylene-1, 2-dioxolane.

  在四苯基卟啉催化剂存在下，将(E)-2-甲基-2-丁烯酸衍生物（虎尾草酸衍生物）在四氯化碳中进行光氧化反应，通常可以高产率地得到3-羟基过氧-2-亚甲基丁酸衍生物。通过酸催化的环脱水反应，所获得的3-羟基过氧-2-亚甲基丁酸容易生成5-甲基-4-亚甲基-3-氧代-1,2-二氧杂环戊烷（一种过氧内酯），产率为61%。类似地，通过将(E)-2-甲基-2-丁烯醛就地氧化生成的3-羟基过氧-2-亚甲基丁醛进行环脱水反应，则生成3-羟基-5-甲基-4-亚甲基-1,2-二氧杂环戊烷。
• Regioselective reaction of singlet oxygen with α,β-unsaturated esters
  作者：Michael Orfanopoulos、Christopher S. Foote

  DOI：10.1016/s0040-4039(00)98279-0

  日期：1985.1

  The reaction of singlet oxygen with α,β-unsaturated esters shows a general preference for hydrogen abstraction on the alkyl group geminal to the ester.

  单线态氧与α，β-不饱和酯的反应显示出一般优先选择与该酯成对的烷基上的氢。
• A New Experimental Protocol for Intrazeolite Photooxidations. The First Product-Based Estimate of an Upper Limit for the Intrazeolite Singlet Oxygen Lifetime
  作者：Andrea Pace、Edward L. Clennan

  DOI：10.1021/ja027053w

  日期：2002.9.1

  interior of the zeolite was documented. The nearly identical reaction rates in the two slurry solvents are attributed to a leveling of the singlet oxygen lifetime by the zeolite framework. A consideration of the rates of the various intrazeolite processes was used to estimate an upper limit for the intrazeolite lifetime of singlet oxygen.

  已经在己烷和全氟己烷浆液中检测了几种烯烃的沸石内光氧化。全氟己烷增加烯烃对沸石内部的亲合力的能力被记录在案。两种浆液溶剂中几乎相同的反应速率归因于沸石骨架使单线态氧寿命变平。考虑各种内部沸石过程的速率被用来估计单线态氧的内部沸石寿命的上限。
• Enzymatic preparation of optically active α-methylene β-lactones by lipase-catalyzed kinetic resolution through asymmetric transesterification
  作者：Waldemar Adam、Peter Groer、Chantu R. Saha-Möller

  DOI：10.1016/s0957-4166(97)00054-2

  日期：1997.3

  The lipase-catalyzed asymmetric transesterification of racemic α-methylene β-lactones 1 with benzyl alcohol in organic media afforded the optically active β-lactones and the corresponding β-hydroxy esters 2 in excellent enantiomeric excess (ee 95–99%).

  在有机介质中，脂肪酶催化的外消旋α-亚甲基β-内酯1与苯甲醇的不对称酯交换反应提供了旋光性β-内酯和相应的β-羟基酯2，其对映体过量极多（ee 95-99％）。
• Photooxidations of Alkenes in Fluorinated Constrained Media:  Fluoro-organically Modified NaY as Improved Reactors for Singlet Oxygen “Ene” Reactions
  作者：Andrea Pace、Paola Pierro、Silvestre Buscemi、Nicolò Vivona、Edward L. Clennan

  DOI：10.1021/jo0625047

  日期：2007.3.1

  Creating a stationary fluorinated environment inside the zeolite cavity can increase the reactivity observed for intrazeolite photooxidation of alkenes. Exchanging the zeolite with fluorinated organic cations is a much more effective strategy than simply using a fluorinated solvent for slurry irradiations. Use of cations containing C-F bonds is also more efficient than use of deuterated cations for creation of a singlet oxygen friendly environment where the quenching processes are slowed down. Doping the zeolite with fluoro-organic cation 4 resulted in an increase in the singlet oxygen lifetime to 12 mu s.