4--3-phenylisoxazol-5(4H)-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 4--3-phenylisoxazol-5(4H)-one
• 英文别名: 4-[bis(methylthio)methylene]-3-phenylisoxazol-5(4H)-one；4-[Bis(methylsulfanyl)methylidene]-3-phenyl-1,2-oxazol-5-one
• 化学式: C₁₂H₁₁NO₂S₂
• 分子量: 265.357
• InChiKey: QBQHYZXSBZWOFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  89.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4--3-phenylisoxazol-5(4H)-one 生成 1,2-双(甲硫基)乙炔
  参考文献：
  名称：

  Polycarbon Disulfides SCnS (n = 1-3) and Their Protonated and Methylated Forms (HCnS2+ and CH3CnS2+): Tandem Mass Spectrometry and ab Initio MO Study

  摘要：

  Dissociative ionization of 4,5-bis(methylthio)-1,2-dithiole-3-thione (1) has allowed the detection of a series of carbon disulfide radical cations, SCnS.+ (n = 1-3), and their S-methylated forms, CH3SCnS+, in the gas phase of a mass spectrometer. The connectivities and stabilities of these ions and the corresponding neutrals have been probed by collisional activation (CA) and neutralization-reionization (NR) mass spectrometry. Moreover, the sites of protonation and cationic methylation of the polycarbon disulfides have been investigated by a combination of flash vacuum pyrolysis, chemical ionization, and CAMS (FVP/CI/MS/MS). The experimental results are supported by ab initio MO calculations at the QCISD(T)/6-311+G(2d,p) + ZPVE level. Both experiments and calculations indicate that the most favorable site of protonation and methylation is the carbon atom for C2S2 and C3S2 but a sulfur atom for CS2. The proton affinities (298 K) of C2S2 and C3S2 are predicted to be 842 and 818 kJ mol(-1), respectively.

  DOI：

  10.1021/j100046a010

文献信息

• Highly Twisted C=C Double Bonds in 4-Methyleneisoxazolones
  作者：David Kvaskoff、Paul V. Bernhardt、Rainer Koch、Curt Wentrup

  DOI：10.1071/ch09359

  日期：——

  As determined by X-ray crystallography, isoxazol-5(4H)-one derivatives 12–19 feature dihedral angles around the exocyclic C4=C6 double bonds of 26–90°. In the most highly twisted bis-tert-butylamino derivatives 18 and 19, the C4–C6 bonds are essentially single bonds. Density functional theory calculations at the B3LYP/6-31G(d) level with inclusion of a simulated solvent field, which helps stabilize

  如通过X射线晶体学，异恶唑-5-（4-确定ħ） -酮衍生物12 - 19围绕环外C4特征二面角=的26-90°C6双键。在高度扭曲的双叔丁基氨基衍生物18和19中，C4-C6键本质上是单键。在B3LYP / 6-31G（d）级别上的密度泛函理论计算，包括模拟的溶剂场，有助于稳定两性离子结构，与实验晶体学数据非常吻合。观察到键长与计算出的π/π*轨道占有商之间具有良好的相关性。还观察到扭曲角和电荷分离之间的良好相关性，该相关性是通过在异恶唑酮部分上计算出的负电荷测得的。低障碍绕扭转环外双键C4 = C6化合物在13，20，和21（Δ ģ ‡ = 15-16千卡摩尔-1（63-67千焦耳摩尔-1））是通过动态1 H NMR聚结测量确定的。估计17的旋转势垒小于10 kcal mol –1。化合物10和18的旋转势垒经计算为〜8 kcal mol –1。
• Iminoethenethiones, RN:C:C:S: Characterization by Neutralization-Reionization Mass Spectrometry and G2(MP2) Theory
  作者：Robert Flammang、Dinzeyi Landu、Sophie Laurent、Monique Barbieux-Flammang、C. Oliver Kappe、Ming Wah Wong、Curt Wentrup

  DOI：10.1021/ja00084a046

  日期：1994.3

  (Methylimino)ethenethione (2) and iminoethenethione (4) are stable molecules on the microsecond time scale of neutralization-reionization mass spectrometry experiments. The corresponding radical cations were generated by fragmentation of thiazolopyrimidinedione molecular ions 1(.+) and 3(.+). Iminoethenethione (4) does not tautomerize to thioformyl cyanide (H-CS-CN, 5) under the wall-less conditions

  (甲基亚氨基)乙烯硫酮 (2) 和亚氨基乙烯硫酮 (4) 在中和-再电离质谱实验的微秒时间尺度上是稳定的分子。相应的自由基阳离子是由噻唑并嘧啶二酮分子离子 1(.+) 和 3(.+) 裂解产生的。亚氨基乙硫酮 (4) 在 MS 实验的无壁条件下不会互变异构为硫甲酰氰 (H-CS-CN, 5)，但在 FVP 条件下由异恶唑酮生成时会发生互变异构。 6. IR 明确鉴定了硫甲酰氰和质谱。2、4 和 4(.+) 的结构和稳定性在 G2(MP2) 理论水平通过从头计算进行了研究。预测 2 和 4 都具有单线态基态，而 O 双键 C 双键 C 双键 S 则优选三线态。单线态三线态间隙约为 40 kJ mol(-1)。与实验结果一致，计算出两种亚氨基乙硫酮都是热力学和动力学稳定的物种，位于能量井中，至少有 100 kJ mol(-1) 障碍才能解离成 HNC（或 CH3NC）+ CS。预测了 2 和 4