2,2-dimethyl-3-oxobutyl 4-(benzothiazol-2-yl)-3-hydroxybenzenecarboxylate | 1225266-06-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,2-dimethyl-3-oxobutyl 4-(benzothiazol-2-yl)-3-hydroxybenzenecarboxylate
• 英文别名: (2,2-Dimethyl-3-oxobutyl) 4-(1,3-benzothiazol-2-yl)-3-hydroxybenzoate
• CAS: 1225266-06-7
• 化学式: C₂₀H₁₉NO₄S
• 分子量: 369.441
• InChiKey: OWDPEXMPMBHKPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  105
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-[4-(benzothiazol-2-yl)-3-hydroxyphenyl]-4,4,5-trimethyl-2,6,7-trioxabicyclo[3.2.0]heptane 以 氘代对二甲苯-d10 为溶剂， 反应 0.33h， 以99%的产率得到2,2-dimethyl-3-oxobutyl 4-(benzothiazol-2-yl)-3-hydroxybenzenecarboxylate
  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

• 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.