rac-(1R,2S)-bis(2-hydroxyethyl) 1,2-dicyanocyclobutane-1,2-dicarboxylate | 1219094-47-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: rac-(1R,2S)-bis(2-hydroxyethyl) 1,2-dicyanocyclobutane-1,2-dicarboxylate
• 英文别名: (1R,2S)-bis(2-hydroxyethyl) 1,2-dicyanocyclobutane-1,2-dicarboxylate
• CAS: 1219094-47-9
• 化学式: C₁₂H₁₄N₂O₆
• 分子量: 282.253
• InChiKey: WJAIMGAJERAMIW-TXEJJXNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.13
• 重原子数：
  20.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  140.64
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  2-溴-2-甲基丙酰溴 、 rac-(1R,2S)-bis(2-hydroxyethyl) 1,2-dicyanocyclobutane-1,2-dicarboxylate 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以67%的产率得到rac-(1R,2S)-bis(2-(2-bromo-2-methylpropanoyloxy)ethyl) 1,2-dicyanocyclobutane-1,2-dicarboxylate
  参考文献：
  名称：

  Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores

  摘要：

  Ultrasound activation of mechanophores embedded in polymer backbones has been extensively studied of late as a method for realizing chemical reactions using force. To date, however, there have been few attempts at systematically investigating the effects of mechanophore structure upon rates of activation by an acoustic field. Herein, we develop a method for comparing the relative reactivities of various cyclobutane mechanophores. Through the synthesis and ultrasonic irradiation of a molecular weight series of poly(methyl acrylate) polymers in which each macromolecule has a single chain-centered mechanophore, we find measurable and statistically significant shifts in molecular weight thresholds for mechanochemical activation that depend on the structure of the mechanophore. We also show that calculations based on the constrained geometries simulate external force method reliably predict the trends in mechanophore reactivity. These straightforward calculations and the experimental methods described herein may be useful in guiding the design and the development of new mechanophores for targeted applications.

  DOI：

  10.1021/ja2086728
• 作为产物：
  描述：

  dimethyl 2,5-dicyano-2,5-di(pent-2-en-3-yl)hexanedioate 在 硫酸 、 溴 、 对甲苯磺酸 、 臭氧 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 rac-(1R,2S)-bis(2-hydroxyethyl) 1,2-dicyanocyclobutane-1,2-dicarboxylate
  参考文献：
  名称：

  Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores

  摘要：

  Ultrasound activation of mechanophores embedded in polymer backbones has been extensively studied of late as a method for realizing chemical reactions using force. To date, however, there have been few attempts at systematically investigating the effects of mechanophore structure upon rates of activation by an acoustic field. Herein, we develop a method for comparing the relative reactivities of various cyclobutane mechanophores. Through the synthesis and ultrasonic irradiation of a molecular weight series of poly(methyl acrylate) polymers in which each macromolecule has a single chain-centered mechanophore, we find measurable and statistically significant shifts in molecular weight thresholds for mechanochemical activation that depend on the structure of the mechanophore. We also show that calculations based on the constrained geometries simulate external force method reliably predict the trends in mechanophore reactivity. These straightforward calculations and the experimental methods described herein may be useful in guiding the design and the development of new mechanophores for targeted applications.

  DOI：

  10.1021/ja2086728

文献信息

• Masked Cyanoacrylates Unveiled by Mechanical Force
  作者：Matthew J. Kryger、Mitchell T. Ong、Susan A. Odom、Nancy R. Sottos、Scott R. White、Todd J. Martinez、Jeffrey S. Moore

  DOI：10.1021/ja1008932

  日期：2010.4.7

  Mechanical damage of polymers is often a destructive and irreversible process. However, desirable outcomes may be achieved by controlling the location of chain cleavage events through careful design and incorporation of mechanically active chemical moieties known as mechanophores. It is possible that mechanophores can be used to generate reactive intermediates that can autopolymerize or cross-link, thus healing mechanically induced damage. Herein we report the generation of reactive cyanoacrylate units from a dicyanocyclobutane mechanophore located near the center of a polymer chain. Because cyanoacrylates (which are used as monomers in the preparation of superglue) autopolymerize, the generated cyanoacrylate-terminated polymers may be useful in self-heating polymers. Sonication studies of polymers with the mechanophore incorporated into the chain center have shown that selective cleavage of the mechanophore occurs. Trapping experiments with an amine-based chromophore support cyanoacrylate formation. Additionally, computational studies of small-molecule models predict that force-induced bond cleavage should occur with greater selectivity for the dicyanocyclobutane mechanophore than for a control molecule.