2-imino-3-phenylbenzothiazoline | 46493-66-7

• 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-imino-3-phenylbenzothiazoline
• 英文别名: 2(3H)-Benzothiazolimine, 3-phenyl-；3-phenyl-1,3-benzothiazol-2-imine
• CAS: 46493-66-7
• 化学式: C₁₃H₁₀N₂S
• 分子量: 226.302
• InChiKey: WMUQKQNUCODDCB-UHFFFAOYSA-N

物化性质

• 沸点：
  365.7±25.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-imino-3-phenylbenzothiazoline 在 氢氧化钾 作用下， 生成 2-苯胺基苯硫酚
  参考文献：
  名称：

  Kiprianow; Uschenko, Zhurnal Obshchei Khimii, 1947, vol. 17, p. 2201,2207

  摘要：

  DOI：
• 作为产物：
  描述：

  二苯胺盐酸盐 在 盐酸 、 溴 作用下， 以 氯仿 为溶剂， 生成 2-imino-3-phenylbenzothiazoline
  参考文献：
  名称：

  Experimental and Theoretical Studies on the Thermal Decomposition of Heterocyclic Nitrosimines¹

  摘要：

  A series of substituted 2-nitrosiminobenzothiazolines (2) were synthesized by the nitrosation of the corresponding 2-iminobenzothiazolines (6). Thermal decomposition of 2a-f and of the seleno analogue 7 in methanol and of 3-methyl-2-nitrosobenzothiazoline (2a) in acetonitrile, 1,4-dioxane, and cyclohexane followed first-order kinetics. The activation parameters for thermal deazetization of 2a were measured in cyclohexane (DeltaH(double dagger) = 25.3 +/- 0.5 kcal/mol, DeltaS(double dagger) = 1.3 +/- 1.5 eu) and in methanol (DeltaH(double dagger) = 22.5 +/- 0.7 kcal/mol, DeltaS(double dagger) = -12.9 +/- 2.1 eu). These results indicate a unimolecular decomposition and are consistent with a proposed stepwise mechanism involving cyclization of the nitrosimine, followed by loss of N-2. The ground-state conformations of the parent nitrosiminothiazoline (9a) and transition states for rotation around the exocyclic C=N bond, electrocyclic ring closure, and loss of N-2 were calculated using A initio molecular orbital theory at the MP2/6-31G* level. The calculated gas-phase barrier height for the loss of N-2 from 9a (25.2 kcal/mol, MP4(SDQ, FC)/6-31G*//MP2/6-31G* + ZPE) compares favorably with the experimental barrier for 2a of 25.3 kcal/mol in cyclohexane. The potential energy surface is unusual; the rotational transition state 9a-rot-ts connects directly to the orthogonal transition state for ring-closure 9aTS. The decoupling of rotational and pseudopericyclic bond-forming transition states is contrasted with the single pericyclic transition state (15TS) for the electrocyclic ring-opening of oxetene (15) to acrolein (16). For comparison, the calculated homolytic strength of the N-NO bond is 40.0 kcal/mol (MP4(SDQ, FC)/6-31G*//MP2/6-31G* + ZPE).

  DOI：

  10.1021/ja010659k
• 作为试剂：
  描述：

  bromo-(3-ethyl-3H-benzothiazol-2-ylidene)-amine 在 2-imino-3-phenylbenzothiazoline 作用下， 以 四氢呋喃 为溶剂， 生成 3-ethyl-2-iminobenzothiazoline
  参考文献：
  名称：

  REACTIONS OFN-BROMO DERIVATIVES OF 2-IMINOBENZOTHIAZOLINES WITH THEIRN-GRIGNARD-TYPE REAGENTS

  摘要：

  在 2-溴亚氨基-3-甲基苯并噻唑啉与 2-亚氨基-3-甲基苯并噻唑啉的 N-格氏型试剂反应中，可获得 67%的环扩大产物 3-(3′-甲基苯并噻唑啉亚氨基)-4-甲基-1,2,4-苯并噻二嗪。另一方面，2-亚氨基-3-甲基苯并噻唑啉与 2-亚氨基-3-甲基苯并噻唑啉的 N-格氏型试剂发生反应，通过硫酸盐与溴化物的氧化作用，前者通过 N-格氏型试剂的开环平衡生成双[邻（N-苯基氰基氨基）苯基]二硫化物，收率为 65-87%。

  DOI：

  10.1246/cl.1976.1111

文献信息

• NEW ROUTE FOR THE SYNTHESES OF SOME NOVEL DERIVATIVES OF 3-ARYL BENZO[d] THIAZOLE-2(3H)-IMINE FROM HIGH SUBSTITUTED THIOUREAS
  作者：Marzieh Miar、Khalil Pourshamsian、Abolfazl Shiroudi、Farhad Hatamjafari、Ahmad Reza Oliaey

  DOI：10.4067/s0717-97072020000204853

  日期：——

  We have developed herein a new approach to diverse synthesis of novel derivatives of 3-Aryl benzo[d]thiazole-2(3H)-imines (3a-g), by a two-component reaction between diazonium salt (2) and various synthesized N-acyl-N'-aryl thioureas (1a-g), in the presence of sodium tert butoxide as strong base. Finally, it resulted in the production of the desired product with a moderate yield. The chemical structures

  我们在这里开发了一种通过重氮盐（2）和各种合成的化合物之间的两组分反应，多样地合成3-芳基苯并[d]噻唑-2（3H）-亚胺（3a-g）新型衍生物的新方法N-酰基-N'-芳基硫脲（1a-g），在叔丁醇钠作为强碱存在下。最后，它以中等产率产生了所需的产物。这些合成化合物的化学结构通过各种物理化学方法证实。FT-IR，1H-NMR，13C-NMR和元素分析。
• Theoretical investigations on the HOMO–LUMO gap and global reactivity descriptor studies, natural bond orbital, and nucleus-independent chemical shifts analyses of 3-phenylbenzo[<i>d</i>]thiazole-2(3<i>H</i>)-imine and its <i>para</i>-substituted derivatives: Solvent and substituent effects
  作者：Marzieh Miar、Abolfazl Shiroudi、Khalil Pourshamsian、Ahmad Reza Oliaey、Farhad Hatamjafari

  DOI：10.1177/1747519820932091

  日期：2021.1

  relative stability of the studied compounds is influenced by the possibility of intramolecular interactions between substituents and the electron donor–acceptor centers of the thiazole ring. Furthermore, atomic charges, electron density, chemical thermodynamics, energetic properties, dipole moments, and nucleus-independent chemical shifts of the studied compounds and their relative stability are considered

  合成3-分子结构上对位的电子释放（–CH 3，–OH）和吸电子（–Cl，–NO 2，–CF 3）基团的自然键轨道分析，拯救和取代效应苯并[ d ]噻唑-2（3 H使用M06-2x方法和6-311 ++ G（d，p）方法研究了可极化连续体方法模型中所选溶剂（丙酮，甲苯和乙醇）中和气相中的）-亚胺及其衍生物组。所研究化合物的相对稳定性受取代基与噻唑环的电子供体-受体中心之间分子内相互作用的可能性影响。此外，还考虑了所研究化合物的原子电荷，电子密度，化学热力学，高能性质，偶极矩和与核无关的化学位移及其相对稳定性。偶极矩值和最高占据分子轨道-最低未占据分子轨道能隙显示了所考虑分子内不同的电荷转移可能性。最后，
• Chemistry of Nitrosoimines. XVI. A New Method for Facile Preparation of Azamonomethinecyanines<i>via</i>Nitrosoimines
  作者：Kin-ya Akiba、Kiyofumi Ishikawa、Naoki Inamoto

  DOI：10.1246/bcsj.51.535

  日期：1978.2

  The reaction of 3-substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) with Grignard-type reagents of 3-substituted 2-imino-2,3-dihydrobenzothiazoles (2) gave azamonomethinecyanines (3) in high yields (71–96%). This is a new type of reaction for the preparation of 3. Hydrolysis of 3 afforded ring-opened disulfides, bis[o-N-methyl-N-(3-methyl-2,3-dihydrobenzothiazol-2-ylidenecarbamoyl)amino}-phenyl]

  3-取代的 2-亚硝基-2,3-二氢苯并噻唑 (1) 与 3-取代的 2-亚氨基-2,3-二氢苯并噻唑 (2) 的格氏试剂反应得到高产率的氮杂单甲基花青 (3) (71– 96%）。这是制备 3 的新型反应。 水解 3 得到开环二硫化物，双[o-N-甲基-N-(3-甲基-2,3-二氢苯并噻唑-2-亚基氨基甲酰基)氨基} -苯基]二硫化物，产率高（78-85%）。副产物的形成可以通过 1 和 2 之间的亚硝基转移和 2-亚氨基-3-苯基-2,3-二氢苯并噻唑的格氏试剂的开环平衡来解释。
• ——
  作者：R. F. Ambartsumova、L. P. Kosmacheva

  DOI：10.1023/a:1012472112992

  日期：——
• Reactions of 2-aminobenzothiazoles with phenyl glycidyl ether
  作者：R. F. Ambartsumova、L. P. Kosmacheva

  DOI：10.1007/bf00474005

  日期：1991.5