2,2,3-trimethylbenzothiazoline | 2786-37-0

• 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: 2,2,3-trimethylbenzothiazoline
• 英文别名: 2,2,3-Trimethyl-benzthiazolin；2,2,3-Trimethylbenzothiazolin；Benzothiazole, 2,3-dihydro-2,2,3-trimethyl-；2,2,3-trimethyl-1,3-benzothiazole
• CAS: 2786-37-0
• 化学式: C₁₀H₁₃NS
• 分子量: 179.286
• InChiKey: ODZISWCHQQOYGL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  28.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,3-trimethylbenzothiazoline 在 氘代甲醇-d 、 4,4'-di(tert-butyl)-[1,1-biphenyl]yllithium 作用下， 生成 N-methyl-N-(1-d-1-methylethyl)-o-aminobenzenethiol
  参考文献：
  名称：

  Florio, Saverio; Capriati, Vito; Gallo, Antonio, Gazzetta Chimica Italiana, 1996, vol. 126, # 6, p. 351 - 358

  摘要：

  DOI：
• 作为产物：
  描述：

  2,2-dimethyl-2,3-dihydro-benzothiazole 生成 2,2,3-trimethylbenzothiazoline
  参考文献：
  名称：

  Metzger,J. et al., Bulletin de la Societe Chimique de France, 1964, p. 2868 - 2878

  摘要：

  DOI：

文献信息

• Controlling parameters for radical cation fragmentation reactions: Origin of the intrinsic barrier
  作者：Deepak Shukla、Guanghua Liu、Joseph P Dinnocenzo、Samir Farid

  DOI：10.1139/v03-078

  日期：2003.6.1

  C—C bond cleavages of radical cations of 2-substituted benzothiazoline derivatives were investigated to determine the parameters controlling the fragmentation rate constants. In spite of the low oxidation potentials of the compounds, fragmentation rate constants greater than 1 × 10⁶ s^–1 could be achieved through weakening of the fragmenting bond by substituents that stabilize the radical fragment and exert steric crowding. A quantitative assessment of the relative roles of radical stabilization vs. steric effects to weaken the fragmenting C—C bond was achieved through DFT calculations. The calculated activation enthalpies matched reasonably well with the experimentally determined values. A thermokinetic analysis revealed that the fragmentations of benzothiazoline radical cations have relatively large intrinsic kinetic barriers, ascribed to the delocalized nature of the product radical and cation fragments. Interestingly, the same factors that lead to the large intrinsic barriers led, simultaneously, to large thermodynamic driving forces for the fragmentations, which should lead to lower activation barriers. These effects oppose each other kinetically and provide important insight into the design of fast radical ion fragmentation reactions.Key words: benzothiazoline, radical cation, fragmentation, steric effects, DFT.

  2-取代苯并噻唑啉衍生物的自由基阳离子的C-C键裂解进行了研究，以确定控制裂解速率常数的参数。尽管化合物的氧化电位较低，但通过通过取代基使裂解键变弱，从而稳定自由基片段并施加立体阻碍，可以实现大于1×10^6 s^-1的裂解速率常数。通过密度泛函理论（DFT）计算，对自由基稳定与立体效应相对作用于使裂解的C-C键变弱的定量评估取得了成功。计算得到的活化焓与实验测定值相当吻合。热动力学分析显示，苯并噻唑啉自由基阳离子的裂解具有相对较大的固有动力学壁垒，归因于产物自由基和阳离子片段的离域性质。有趣的是，导致大固有壁垒的因素同时导致了裂解的大热力学驱动力，这应该导致较低的活化壁垒。这些效应在动力学上相互对立，并为设计快速自由基离子裂解反应提供了重要见解。关键词：苯并噻唑啉，自由基阳离子，裂解，立体效应，DFT。
• A new aspect on alkylation of benzothiazolines.
  作者：MIKIO HORI、TADASHI KATAOKA、HIROSHI SHIMIZU、YUTAKA IMAI

  DOI：10.1248/cpb.25.1482

  日期：——

  A striking difference between the reactions of 3-methylbenzothiazoline derivatives with trimethyloxonium tetrafluoroborate and with methyl iodide has been found. Especially, by the treatment of 2, 2, 3-trimethylbenzothiazoline with methyl iodide, N-methyl-N-(o-methylthiophenyl)-N-isopropylideneiminium iodide has been obtained. Mechanism for the reaction was also proposed.

  研究发现，3-甲基苯并噻唑啉衍生物与四氟硼酸三甲基鏻的反应和与碘甲烷的反应有显著的不同。特别是用碘甲烷处理 2，2，3-三甲基苯并噻唑啉后，得到了 N-甲基-N-（邻甲基噻吩基）-N-异丙基亚胺鎓碘化物。还提出了该反应的机理。
• Reductive lithiation of a trimethyl benzo-1,3-thiazoline: Generation of an α-amino tertiary carbanion and reactions with electrophiles
  作者：Saverlo Florio、Vito Capriati、Antonio Gallo、Theodore Cohen

  DOI：10.1016/0040-4039(95)00753-y

  日期：1995.6

  Trimethylbenzothiazoline 1 has been reductively lithiated by lithium 4,4′- di-t-butylbiphenylide (LDBB) leading to dianion 3, that has been trapped with electrophiles to give aminodisulfides 4, aminosulfide 8 and aminoalcohols 9.

  Trimethylbenzothiazoline 1已经由锂4,4'-二-被还原锂化吨-butylbiphenylide（LDBB），导致二价阴离子3，已俘获与亲电子给aminodisulfides 4，aminosulfide 8和氨基醇9。
• Thermolysis of quaternary salts of 2-methylbenzothiazole and their methylene bases
  作者：M. A. Al'perovich、V. G. Khesin、R. D. Raikhina、T. D. Medvedeva

  DOI：10.1007/bf00506989

  日期：1981.12
• Kiprianow; Portnjagina, Zhurnal Obshchei Khimii, 1955, vol. 25, p. 2257,2262; engl. Ausg. S. 2223, 2227
  作者：Kiprianow、Portnjagina

  DOI：——

  日期：——

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