p-trifluoromethyl(sulfinylaniline) | 74653-66-0

• 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: p-trifluoromethyl(sulfinylaniline)
• 英文别名: 3-Trifluormethylphenylsulfinylimin；1-(Sulfinylamino)-4-(trifluoromethyl)benzene
• CAS: 74653-66-0
• 化学式: C₇H₄F₃NOS
• mdl: MFCD26792669
• 分子量: 207.176
• InChiKey: VNJWEMMDNLQZKC-UHFFFAOYSA-N

物化性质

• 沸点：
  194 °C
• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  30.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  p-trifluoromethyl(sulfinylaniline) 以 正己烷 、 乙腈 为溶剂， 反应 4.0h， 生成 C₇H₄F₃N₂S^(1-)*C₆H₁₈N₃S⁽¹⁺⁾
  参考文献：
  名称：

  Arylthiazylamides: Syntheses, Structures, and Bonding Properties

  摘要：

  Air-sensitive, thermally unstable tris(dimethylamino)sulfonium (TAS) salts (3) of the title anions [ArNSN](-) have been prepared from corresponding sulfurdiimides Ar-N=S=N-SiMe3 (2) by Si-N bond cleavage with [(Me2N)(3)S](+)[Me3SiF2](-)(TASF). They are characterized by low-temperature X-ray crystallography as Z isomers. Because of the very short terminal S-NI distance (144.2 (3h) - 147.9 (3i) pm) and the relatively long internal S-N distance (158.3 (3i) - 160.3 (3c) pm) the [ArNSN](-) ions should be regarded as thiazylamides 1b, rare species containing a SN triple bond. A bonding model is developed and the experimental results are compared with those of restricted Hartree-Fock (R drop HF), density functional theory (DFT), and Moller-Plesset second-order (MP2) calculations.

  DOI：

  10.1002/1521-3765(20010817)7:16<3504::aid-chem3504>3.0.co;2-e
• 作为产物：
  描述：

  对三氟甲基苯胺 在 氯化亚砜 作用下， 以 苯 为溶剂， 反应 8.0h， 以86%的产率得到p-trifluoromethyl(sulfinylaniline)
  参考文献：
  名称：

  关于取代基对对位取代亚磺酰基苯胺的结构和振动性质的影响的研究：对对三氟甲基亚磺酰基苯胺的研究

  摘要：

  对的结构和振动性质替代效应研究对位取代的sulfinylanilines前进用的前进研究一个步骤p -trifluoromethylsulfinylaniline，合成和表征通过NMR，拉曼光谱，红外光谱和质谱。比较和分析了实验光谱，并考虑了在不同理论水平上通过量子化学计算获得的理论光谱。光谱结果表明存在该分子的单一形式，根据计算的分子结构，该分子具有与环平面共面的NSO基团。另外，NSO基团的顺式构象也来自实验和理论数据。CF 3的存在芳环对位的芳基基团影响N S O基团的性质，与其他对位取代的亚磺酰苯胺报道的结果相比，NS键比S O键受到的影响更大。

  DOI：

  10.1016/j.jfluchem.2018.02.013

文献信息

• Cycloadditions of Donor–Acceptor Cyclopropanes and ‐butanes using S=N‐Containing Reagents: Access to Cyclic Sulfinamides, Sulfonamides, and Sulfinamidines
  作者：Gwyndaf A. Oliver、Maximilian N. Loch、André U. Augustin、Pit Steinbach、Mohammed Sharique、Uttam K. Tambar、Peter G. Jones、Christoph Bannwarth、Daniel B. Werz

  DOI：10.1002/anie.202106596

  日期：2021.12

  By employing (3+2)- and (4+2)-cycloadditions of donor–acceptor (D–A) cyclopropanes and cyclobutanes with N-sulfinylamines and sulfur diimides, a variety of isothiazolidines and thiazinanes were synthesized. Use of a sulfinylamine bearing a leaving group, followed by oxidation, led to formal insertion of HNSO2 providing γ-sultams with no N-substitution.

  通过供体-受体（D-A）环丙烷和环丁烷与N-亚磺酰胺和硫二酰亚胺的（3+2）-和（4+2）-环加成，合成了多种异噻唑烷和噻嗪烷。使用带有离去基团的亚磺酰胺，然后进行氧化，导致HNSO 2的正式插入，提供没有N-取代的γ-磺内酰胺。
• Aminolysis of sulfinamoyl-esters, -sulfonamides and -sulfones. Thiooxamate and thiourea formation via a sulfine intermediate. Thiophilic or carbophilic reaction?
  作者：M. Baltas、K. Raouf-Benchekroun、A. De Blic、L. Cazaux、P. Tisnès、L. Gorrichon、K. Hussein、J.-C. Barthelat

  DOI：10.1016/0040-4020(96)00919-2

  日期：1996.11

  The aminolysis process of sulfinamoyl derivatives was investigated with sulfinamoyl esters. An intermediate sulfine was unambiguously evidenced by formation of a Diels-Alder type adduct. The aminolysis leads to final thiooxamate products. A carbophilic addition was suggested for the reaction with secondary amines. With sulfinamoyl, -sulfones and -sulfonamides, a thiourea is formed resulting from a

  用亚磺酰胺基酯研究亚磺酰胺基衍生物的氨解过程。通过形成狄尔斯-阿尔德型加合物，明确地证明了中间亚砜。氨解产生最终的硫代草酸酯产物。提出了与仲胺反应的嗜碳性加成。与亚磺酰基，-砜和-磺酰胺一起，由双重氨基分解形成硫脲。
• Photoredox Alkylation of Sulfinylamine Enables the Synthesis of Highly Functionalized Sulfinamides and S(VI) Derivatives
  作者：Ling Li、Shi-qi Zhang、Yue Chen、Xin Cui、Gang Zhao、Zhuo Tang、Guang-xun Li

  DOI：10.1021/acscatal.2c05169

  日期：2022.12.16

  Sulfinamides have widespread applications in organic synthesis, especially for the preparation of S(VI) derivatives such as sulfonimidamide and sulfonimidate ester. The previous methods for the preparation of these compounds are restricted to an aryl substituent or Grignard reagent with limited functional groups. Here, we disclosed a photocatalyzed approach for obtaining these compounds with high functionalization

  亚磺酰胺在有机合成中有着广泛的应用，特别是用于制备磺酰亚胺和磺酰亚胺酯等S(VI)衍生物。以前制备这些化合物的方法仅限于芳基取代基或具有有限官能团的格氏试剂。在这里，我们公开了一种获得这些具有高官能化水平的化合物的光催化方法。易于获得的 1,4-二氢吡啶，可提供以 C sp 3为中心的烷基自由基，与易于获得的N顺利反应-亚磺酰胺以良好的产率生产相应的亚磺酰胺。此外，通过在一锅中连续添加卤素试剂和N-或O-中心的亲核试剂，可以将产生的亚磺酰胺转化为相应的磺酰亚胺和磺酰亚胺酯。该方法不仅可以实现克级亚磺胺类药物的制备，而且保证了一系列药物或天然产物的后修饰。
• Synthesis of sulfinamides <i>via</i> photocatalytic alkylation or arylation of sulfinylamine
  作者：Ming Yan、Si-fan Wang、Yong-po Zhang、Jin-zhong Zhao、Zhuo Tang、Guang-xun Li

  DOI：10.1039/d3ob01782f

  日期：——

  Sulfinamides are a versatile class of compounds that find applications in both organic synthesis and pharmaceuticals. Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. Commercially available potassium trifluoro(organo)borates and readily available sulfinyl amines are rationally used and converted to a series of alkyl or aryl sulfinamides in moderate to high

  亚磺酰胺是一类用途广泛的化合物，在有机合成和制药领域都有应用。在这里，我们开发了一种有效的光催化方法，可以方便地制备亚磺酰胺。合理使用市售三氟（有机）硼酸钾和容易获得的亚磺酰胺，并以中等至高产率转化为一系列烷基或芳基亚磺酰胺。该反应允许克级规模制备亚磺酰胺。此外，还可一锅获得磺酰亚胺类、磺酰亚胺酯类和磺酰酰胺类。
• N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned
  作者：Nathan D. D. Hill、René T. Boeré

  DOI：10.1002/chem.202400563

  日期：——

  The synthesis and extensive characterization of nine aryl sulfur diimides (SDIs, Ar−NSN−Ar) are presented with a robust computational and experimental investigation of the fundamental properties of these important members of the thiazyl family of compounds, with particular attention paid to their highly tunable electrochemical behaviour. This is the first work to undertake a systematic comparison of the electrochemical profiles of a coherent series of SDIs to demonstrate and quantify the response of their reduction potentials to substituent electron‐donating and ‐withdrawing properties. This effect is found to be not only exceptionally strong, but also correlates very closely with computed orbital energies. Electron paramagnetic resonance spectroscopy is used to determine the nature, localization, and qualitative lifetimes of the radical anions of SDIs. This work also addresses significant misconceptions about physical properties of SDIs. Experimental data and modern computational methods are employed to provide a resolute answer to the long‐standing contention of the solution‐state conformations of SDIs, and to correct historical mistakes in the assignment of infrared spectroscopic data. High‐quality crystal structures of all SDIs in this work showcase the utility of the recently introduced structural refinement software NoSpherA2, enabling full anisotropic refinement of H‐atoms with accurate C−H bond lengths.

  摘要 本文介绍了九种芳基硫二亚胺（SDIs，Ar-NSN-Ar）的合成和广泛表征，并对这些噻唑族化合物重要成员的基本性质进行了深入的计算和实验研究，尤其关注它们高度可调的电化学行为。这是首次对一系列连贯的 SDI 的电化学特性进行系统比较，以展示和量化它们的还原电位对取代基电子供取特性的响应。研究发现，这种效应不仅异常强烈，而且与计算出的轨道能量密切相关。电子顺磁共振光谱法用于确定 SDIs 自由基阴离子的性质、定位和定性寿命。这项研究还解决了有关 SDI 物理性质的重大误解。通过实验数据和现代计算方法，对 SDIs 溶液态构象的长期争论给出了明确的答案，并纠正了红外光谱数据赋值方面的历史性错误。这项研究中所有 SDIs 的高质量晶体结构都展示了最近推出的结构细化软件 NoSpherA2 的实用性，该软件可以对具有精确 C-H 键长度的 H 原子进行完全各向异性细化。