6-methoxy-3-methylbenzo[d]thiazol-2(3H)-imine | 42040-25-5

• 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: 6-methoxy-3-methylbenzo[d]thiazol-2(3H)-imine
• 英文别名: 6-methoxy-3-methyl-2-iminobenzothiazoline；6-methoxy-3-methyl-3H-benzothiazol-2-ylideneamine；6-methoxy-3-methyl-3H-benzothiazol-2-one-imine；6-Methoxy-3-methyl-3H-benzothiazol-2-on-imin；6-methoxy-3-methylbenzothiazolon-(2)-imine；6-Methoxy-3-methyl-1,3-benzothiazol-2-imine
• CAS: 42040-25-5
• 化学式: C₉H₁₀N₂OS
• 分子量: 194.257
• InChiKey: KNTMUWQCLYTQAY-UHFFFAOYSA-N

物化性质

• 熔点：
  94 °C(Solv: ligroine (8032-32-4))
• 沸点：
  313.7±44.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  61.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-methoxy-3-methylbenzo[d]thiazol-2(3H)-imine 在 溶剂黄146 、 sodium nitrite 作用下， 以85.3%的产率得到6-methoxy-3-methyl-2-nitrosiminobenzothiazoline
  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
• 作为产物：
  描述：

  4-甲氧基-N-甲基苯胺盐酸盐 在 盐酸 、 溴 作用下， 生成 6-methoxy-3-methylbenzo[d]thiazol-2(3H)-imine
  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

文献信息

• Metal-free C(sp²)–H functionalization of azoles: K₂CO₃/I₂-mediated oxidation, imination, and amination
  作者：Ranajit Das、Mainak Banerjee、Rakesh Kumar Rai、Ramesh Karri、Gouriprasanna Roy

  DOI：10.1039/c8ob00535d

  日期：——

  available simple K2CO3/I2 reagent combination. The iodinated azole adduct, produced via the in situ generation of N-heterocyclic carbene, is the key intermediate for C2−H oxidation, imination, and amination of azoles. Significantly, these reactions proceed under mild conditions with high to excellent yields, are scalable to large quantity and exhibit a broad substrate scope. Interestingly, this direct

  通过使用可商购的简单K 2 CO 3 / I 2试剂组合，可以实现多种唑类的直接C2-H氧化和亚胺化。碘化唑加成物，产生通过所述原位生成N-杂环碳烯的，为C2-H氧化，亚胺化，和唑类的胺化的关键中间体。重要的是，这些反应在温和的条件下以高至优异的产率进行，可扩展至大量并显示出广泛的底物范围。有趣的是，这种直接的C2-H胺化方法使我们能够获得各种具有药理活性的N 6-烷基或N 6芳基取代的苯并咪唑并喹唑啉酮骨架通过分子内CH串联进行一锅反应。
• Green synthesis, structure and fluorescence spectra of new azacyanine dyes
  作者：Venelin Enchev、Nikolai Gadjev、Ivan Angelov、Stela Minkovska、Atanas Kurutos、Nadezhda Markova、Todor Deligeorgiev

  DOI：10.1016/j.molstruc.2017.06.119

  日期：2017.11

  irradiation. The compounds are derived from a condensation reaction between 2-thiomethylbenzotiazolium salts and 2-imino-3-methylbenzothiazolines proceeded under microwave irradiation. The synthetic approach involves the use of green solvent and absence of basic reagent. TD-DFT calculations were performed to simulate absorption and fluorescent spectra of synthesized dyes. Absorption maxima, λ max , of the

  摘要 采用微波辐照的新方法合成了一系列对称和不对称单次甲基氮杂菁染料（单次甲基氮杂菁和部花青磺基甜菜碱），收率中等至高。该化合物衍生自 2-硫代甲基苯并噻唑鎓盐和 2-亚氨基-3-甲基苯并噻唑啉在微波辐射下进行的缩合反应。合成方法涉及使用绿色溶剂和无碱性试剂。进行 TD-DFT 计算以模拟合成染料的吸收和荧光光谱。所研究染料的吸收最大值 λ max 位于 364-394 nm 范围内。在40300和59200mol -1 dm 3 cm -1 之间评估摩尔吸光度。在 350 nm 激发后，荧光最大值 λ fl 记录在 418-448 nm 附近。观察到根据实验估计的理论估计吸收最大值的轻微位移。差异很可能是因为 DFT 计算没有考虑溶剂效应。此外，部花青磺基甜菜碱在红色范围 (630–650 nm) 激发时也在蓝色光学范围 (420–480 nm) 发出荧光。
• Colorants comprising cationic azacyanine dyes
  申请人：Javet Manuela

  公开号：US20070000071A1

  公开（公告）日：2007-01-04

  The present invention relates to agents comprising cationic azacyanine dyes of the formula (I) for coloring keratin fibers, such as, for example, wool, silk or furs and in particular human hair (where X1 is N—R1, O or S and X2 is N—R2, O or S), and to a method of coloring hair with varying degrees of damage.

  本发明涉及含有阳离子性氮杂花青染料的剂，其化学式为(I)，用于染色角蛋白纤维，例如羊毛、丝绸或毛皮，特别是人类头发（其中X1是N-R1、O或S，而X2是N-R2、O或S），以及用于染色具有不同损伤程度的头发的方法。
• Hypotensive activity of 3-alkyl-2-iminobenzothiazolines
  作者：Stephen W. Horgan、James K. Woodward、Alfred Richardson、Albert A. Carr

  DOI：10.1021/jm00237a023

  日期：1975.3
• Oksengendler, Zhurnal Obshchei Khimii, 1953, vol. 23, p. 135,138; engl. Ausg. S. 133, 136
  作者：Oksengendler

  DOI：——

  日期：——