1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane | 862211-64-1

• 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-2,6,7-trioxabicyclo[3.2.0]heptane
• 英文别名: 2-(1,3-Benzothiazol-2-yl)-5-(5-tert-butyl-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptan-1-yl)phenol
• CAS: 862211-64-1
• 化学式: C₂₃H₂₅NO₄S
• 分子量: 411.522
• InChiKey: HILRHKTVCDUFMO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  89
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane 以 N-甲基吡咯烷酮 为溶剂， 生成 4-Benzothiazol-2-yl-3-hydroxy-benzoic acid 2,2,4,4-tetramethyl-3-oxo-pentyl ester
  参考文献：
  名称：

  溶剂促进的带有4-（苯并噻唑-2-基）-3-羟苯基部分的双环二氧杂环丁烷的化学发光分解

  摘要：

  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。

  DOI：

  10.1016/j.tetlet.2008.04.110
• 作为产物：
  描述：

  5-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-4-tert-butyl-3,3-dimethyl-2,3-dihydrofuran 在 氧气 、 亚甲兰 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以100%的产率得到1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-5-tert-butyl-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane
  参考文献：
  名称：

  具有4-（苯并噻唑-2-基）-3-羟苯基部分的双环二氧杂环丁烷的热分解和电荷转移诱导的化学发光分解的热力学方面。

  摘要：

  研究了二氧环乙烷的未催化热分解（TD）和电荷转移诱导的分解（CTID），以确定它们的热力学特性。所检查的二恶丁环是一系列1- [4-（苯并噻唑-2-基）-3-羟苯基] -4,4-二甲基-2,6,7-三恶双环[3.2.0]庚烷，1a - d，带有在5位上有一个烷基取代基R，例如甲基，乙基，异丙基或叔丁基，和一个母体二氧杂环丁烷1e，R ＝ H。对1a - d进行X射线单晶分析。激活的两个自由能，Δ ģ ⧧ TD和Δ ģ ⧧ CTID，在为了增加图1A ≤图1b < 1C < 1D。的自由能差ΔΔ ģ ⧧ =Δ ģ ⧧ TD - Δ ģ ⧧ CTID是约 27 kJ mol -1而不考虑取代基R。但是，使用塔夫脱（Taft）双取代参数表明CTID对取代基R的极性比TD更敏感。熵术语用于CTID，Δ小号⧧ CTID，从零的顺序降低至较大的负值叔丁基，异丙基，乙基和甲基，而Δ小号⧧ TD未显示出同样的倾向。

  DOI：

  10.1021/jo100449m

文献信息

• Base-Induced Chemiluminescent Decomposition of Bicyclic Dioxetanes Bearing a (Benzothiazol-2-yl)-3-hydroxyphenyl Group: A Radiationless Pathway Leading to Marked Decline of Chemiluminescence Efficiency
  作者：Masatoshi, Tanimura、Nobuko Watanabe、Hisako K. Ijuin、Masakatsu Matsumoto

  DOI：10.1021/jo300417e

  日期：2012.5.18

  Charge-transfer-induced decomposition (CTID) of bicyclic dioxetanes 1b–d bearing a 3-hydroxylphenyl moiety substituted with a benzothiazol-2-yl group at the 2-, 6-, or 5-position was investigated, and their chemiluminescence properties were compared to each other, based on those for a 4-benzothiazolyl analogue 1a. Dioxetanes 1c and 1d underwent CTID to give the corresponding oxido anions of keto esters

  研究了在2-，6-或5-位上带有被苯并噻唑-2-基取代的3-羟基苯基部分的双环二氧杂环丁烷1b - d的电荷转移诱导分解（CTID），其化学发光性质为根据4-苯并噻唑基类似物1a的结果进行比较。与1a的情况类似，对二氧环乙烷1c和1d进行CTID生成单线激发态的酮酸酯8c或8d的相应氧化阴离子。另一方面，尽管1b仅产生酮酸酯，但其化学发光效率很低。2b。1b化学发光效率的显着下降归因于1b主要通过无辐射途径分解为8b，其中苯并噻唑基中氮的分子内亲核攻击二氧杂环丁烷O-O产生环状中间体cis - 11。
• Thermochemiluminescence of bicyclic dioxetanes bearing a 4-(benzazol-2-yl)-3-hydroxyphenyl moiety in solution and in the solid state
  作者：Nobuko Watanabe、Ayumu Matsumoto、Kai Takanashi、Hisako K. Ijuin、Yoshio Kabe、Masakatsu Matsumoto

  DOI：10.1016/j.tet.2023.133332

  日期：2023.4

  Uncatalyzed thermal decomposition of four bicyclic dioxetanes bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl and their 4-(benzimidazol-2-yl) analogs effectively caused thermochemiluminescence (TCL) due to ESIPT (excited state intramolecular proton transfer) both in solution and in the solid state. The efficiency of TCL (ΦTCL) was ∼15 times higher in the solid state than in solution. This high ΦTCL

  带有 4-(benzothiazol-2-yl)-3-hydroxyphenyl 及其 4-(benzimidazol-2-yl) 类似物的四种双环二氧杂环丁烷的未催化热分解有效地引起了由于 ESIPT（激发态分子内质子转移）引起的热化学发光 (TCL)无论是在溶液中还是在固态中。TCL 的效率 (Φ TCL ) 在固态比在溶液中高约 15 倍。这种固态的高 Φ TCL 被认为是 TCL 几乎没有经历任何聚集引起的淬火的结果，因为基于发射体的 ESIPT 的大斯托克斯位移，并且因为 TCL 通过温度淬火减少很少，与解决方案中的案例。单线态化学激发效率 (Φ S) 似乎增加，达到峰值，然后随着反应温度的升高而降低。
• Bicyclic dioxetanes bearing a 4-(benzoazol-2-yl)-3-hydroxyphenyl moiety: chemiluminescence profile for base-induced decomposition in aprotic medium and in aqueous medium
  作者：Masakatsu Matsumoto、Taichi Akimoto、Yuki Matsumoto、Nobuko Watanabe

  DOI：10.1016/j.tetlet.2005.07.008

  日期：2005.9

  Four bicyclic dioxetanes bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl or 4-(benzoxazol-2-yl)-3-hydroxyphenyl group were synthesized. These dioxetanes underwent base-induced decomposition with accompanying emission of light with high efficiency in NaOH/H2O as well as in tetrabutyl ammonium fluoride (TBAF)/acetonitrile. Among them, benzothiazol-analogs decomposed faster in the aqueous solution than in acetonitrile. (c) 2005 Published by Elsevier Ltd.
• Intramolecular Charge-Transfer-Induced Decomposition Promoted by an Aprotic Polar Solvent for Bicyclic Dioxetanes Bearing a 4-(Benzothiazol-2-yl)-3-hydroxyphenyl Moiety
  作者：Masatoshi Tanimura、Nobuko Watanabe、Hisako K. Ijuin、Masakatsu Matsumoto

  DOI：10.1021/jo1021822

  日期：2011.2.4

  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.