1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6-dioxabicyclo[3.1.0]hexane | 1037296-41-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻唑类
• 英文名称: 1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6-dioxabicyclo[3.1.0]hexane
• CAS: 1037296-41-5
• 化学式: C₂₃H₂₅NO₃S
• 分子量: 395.522
• InChiKey: KPLORSJYXAWHJP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.69
• 重原子数：
  28.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  54.88
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane 在 三苯基膦 作用下， 以 氯仿 为溶剂， 反应 1.5h， 以98.5%的产率得到1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6-dioxabicyclo[3.1.0]hexane
  参考文献：
  名称：

  Intramolecular Charge-Transfer-Induced Decomposition Promoted by an Aprotic Polar Solvent for Bicyclic Dioxetanes Bearing a 4-(Benzothiazol-2-yl)-3-hydroxyphenyl Moiety

  摘要：

  Bicyclic dioxetanes 3a-d bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl group decomposed to give the corresponding keto esters 4a-d accompanied by the emission of bright light when simply dissolved in an aprotic polar solvent such as N-methylpyrrolidone (NMP) or DMF at 50-100 degrees C. This solvent-promoted decomposition (SPD) was effectively a chemiluminescence process caused by the hydrogen bonding of a phenolic OH with a solvent molecule(s). The characteristics of the chemiluminescence in SPD resembled those in base-induced decomposition (BID), which occurs through an oxidoaryl-substituted dioxetane 5 by an intramolecular charge-transfer-induced decomposition (CTID) mechanism. Both free energies of activation, Delta G*(SPD) and Delta G*(BID), increased in the order 3a < 3b < 3c < 3d, and were linearly correlated with each other. However, SPD showed features different from those of BID in terms of enthalpy of activation and entropy of activation. SPD had large negative values for Delta S* (ca. -71 J mol(-1) K-1) regardless of the substituent Rat the 5-position for 3a-d, while the Delta S* values for BID changed from 0.5 to -22 J mol(-1) K-1 as R became smaller. The enthalpy of activation Delta H* for SPD was 14-21 kJ mol(-1) smaller than that for BID.

  DOI：

  10.1021/jo1021822

文献信息

• Solvent-promoted chemiluminescent decomposition of a bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety
  作者：Masakatsu Matsumoto、Masatoshi Tanimura、Taichi Akimoto、Nobuko Watanabe、Hisako K. Ijuin

  DOI：10.1016/j.tetlet.2008.04.110

  日期：2008.6

  An aprotic polar solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic polar solvent. SPD caused intramolecular CT-induced chemiluminescence similar

  非质子极性溶剂，例如N-甲基吡咯烷酮（NMP），在不添加任何碱的情况下促进了带有4-（苯并噻唑-2-基）-3-羟基苯基部分1的双环二氧杂环丁烷的热分解。在非质子极性溶剂中，这种溶剂促进的分解（SPD）产生的光与碱诱导的分解（BID）一样有效。SPD引起分子内CT诱导的化学发光，与BID相似，但与BID相比，SPD通过具有较大负熵激活的途径进行。还显示了由于在对二甲苯中加热时激发态的分子内质子转移（ESIPT），二氧环乙烷1会发光。