2-hydroxythiochromen-4-one | 16854-67-4

• 物质功能分类: 化学农药原药 - 杀虫剂 - 杀鼠剂中间体
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫色烯
• 英文名称: 2-hydroxythiochromen-4-one
• 英文别名: 4-hydroxythiocumarin；4-hydroxy-2H-1-benzothiopyran-2-one；4-hydroxybenzo[b]thiopyran-2-one；4-hydroxy-2H-thiochromen-2-one；1-thio-4-hydroxycoumarin；4-hydroxy-1-thiocoumarin；4-hydroxy-1-thioumarin
• CAS: 16854-67-4
• 化学式: C₉H₆O₂S
• mdl: MFCD21107028
• 分子量: 178.211
• InChiKey: XPSUDKVCLBDZFL-UHFFFAOYSA-N

物化性质

• 熔点：
  209 °C(Solv: water (7732-18-5))
• 沸点：
  304.9±42.0 °C(Predicted)
• 密度：
  1.478±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于DMSO（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  1.69
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

安全信息

• 海关编码：
  2932209090
• 储存条件：
  室温且干燥

制备方法与用途

化学性质
本品为白色固体，熔点为207～208℃，难溶于水。

用途
4-羟基-2H-苯并硫吡喃-2-酮又称4-羟基-1-硫香豆素，是杀鼠剂噻鼠灵的中间体。

生产方法
其制备方法如下：将硫酚、丙二酸和三氯氧磷在反应锅中加热回流0.5小时，得到丙二酸二硫苯酯。然后冷却、水洗，并用10%氢氧化钠溶液洗涤，最终得到结晶。该晶体与无水三氯化铝在180～185℃的温度下反应25分钟，冷却后使用冰水和盐酸进行分解。再经过冷却、过滤、溶于10%氢氧化钠溶液，并用盐酸沉淀，即可得到产品。

反应信息

• 作为反应物：
  描述：

  2-hydroxythiochromen-4-one 在 羟胺 作用下， 生成 1,2-苯并异噻唑-3-乙酸
  参考文献：
  名称：

  Sato, Kazuo; Honma, Toyokuni; Sugai, Soji, Agricultural and Biological Chemistry, 1985, vol. 49, # 12, p. 3563 - 3568

  摘要：

  DOI：
• 作为产物：
  描述：

  S-[2-(氯甲酰基)苯基]硫代乙酸酯 在 盐酸 、 magnesium 作用下， 以 四氯化碳 、 乙醚 、 乙醇 、 水 为溶剂， 反应 9.0h， 生成 2-hydroxythiochromen-4-one
  参考文献：
  名称：

  Synthesis and characterization of an anticoagulant 4-hydroxy-1-thiocoumarin by FTIR, FT-Raman, NMR, DFT, NBO and HOMO–LUMO analysis

  摘要：

  Experimental and theoretical investigations on the molecular structural, electronic and the vibrational characteristics of 4-hydroxy-1-thiocoumarin are presented. Conformational analysis was carried out to obtain the more stable configuration of the compound. The vibrational frequencies were obtained by DFT/B3LYP calculations employing 6-311++G(d,p), 6-31G(d,p), cc-pVTZ basic sets and B3PW91 method with 6-311++G(d,p) basis set and are compared with FTIR and FT-Raman spectral data recorded in the region of 4000-400 and 4000-100 cm(-1), respectively. The total electron density and molecular electrostatic potential surfaces of the molecule were constructed to display electrostatic potential (electron + nuclei) distribution. The electronic properties HOMO and LUMO energies were measured. H-1 and C-13 NMR spectra were recorded and H-1 and C-13 nuclear magnetic resonance chemical shifts of the molecule were calculated by using the Gauge-Independent Atomic Orbital (GIAO) method and analyzed. The picture of localized bonds and lone pairs, stabilization energy of the delocalization of electrons, the charge and hybridisation of the atoms of 4-hydroxy-1-thiocoumarin were clearly explained by NBO analysis. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2013.01.014

文献信息

• Design, synthesis, and anticonvulsant evaluation of 4-GABA-3-nitrocoumarines, 1-thiocoumarines, quinolone-2-ones, and their derivatives
  作者：G. V. Mokrov、S. A. Litvinova、T. A. Voronina、L. N. Nerobkova、I. S. Kutepova、I. G. Kovalev、T. A. Gudasheva、A. D. Durnev

  DOI：10.1007/s00044-019-02422-5

  日期：2019.11

  The novel group of 4-GABA-3-nitrocoumarines, 1-thiocoumarines, quinolone-2-ones, and their derivatives was designed as potential anticonvulsants using GABA pharmacophore and corresponding heterocyclic moieties. A number of compounds of this group were synthesized and studied in the maximum electroshock seizure (MES) test and in the model of primary-generalized convulsions caused by subcutaneous pentylenetetrazole

  使用GABA药效团和相应的杂环部分，将新型的4-GABA-3-硝基香豆素，1-硫代香豆素，喹诺酮-2-酮及其衍生物设计为潜在的抗惊厥药。合成了该组中的许多化合物，并在最大电击惊厥（MES）测试中以及在小鼠皮下戊四氮（scPTZ）引起的原发性惊厥模型中进行了研究。在MES测试中发现活性最高的化合物是1a（N-（3-硝基香豆素-4-基）-4-氨基丁酸），剂量范围为60-80 mg / kg，可增加存活动物的数量与对照组的60％相比，后者的存活率为10％。化合物1d（N-（3,6-二硝基香豆素-4-基）-4-氨基丁酸甲酯）剂量为10–40 mg / kg和3a（N-（3-硝基-2-氧代-1,2-二氢喹啉） 12.5 mg / kg剂量的-4-基）-4-氨基丁酸甲酯）在scPTZ测试中具有最明显的抗惊厥作用。
• Highly Enantioselective Michael Addition of Cyclic 1,3-Dicarbonyl Compounds to α,β-Unsaturated Ketones
  作者：Jian-Wu Xie、Lei Yue、Wei Chen、Wei Du、Jin Zhu、Jin-Gen Deng、Ying-Chun Chen

  DOI：10.1021/ol062718a

  日期：2007.2.1

  [reaction: see text] The highly enantioselective Michael addition of 1,3-cyclic dicarbonyl compounds to alpha,beta-unsaturated ketones was reported to be catalyzed by an organic primary amine derived from quinine. A chiral anticoagulant drug, (S)-warfarin, was directly prepared in 96% ee, and other related important adducts were also obtained in excellent enantioselectivity (89-99% ee).

  [反应：见正文]据报道，α-β-不饱和酮对1,3-环二羰基化合物的高对映选择性迈克尔加成反应是由奎宁衍生的有机伯胺催化的。直接在96％ee中制备了手性抗凝药（S）-华法林，并且还获得了具有相关对映体选择性（89-99％ee）的其他相关重要加合物。
• Enantioselective Synthesis of Coumarin Derivatives by PYBOX-DIPH-Zn(II) Complex Catalyzed Michael Reaction
  作者：Sumit K. Ray、Pradeep K. Singh、Nagaraju Molleti、Vinod K. Singh

  DOI：10.1021/jo301513x

  日期：2012.10.5

  A potential pharmacologically active chiral 3-substituted 4-hydroxy-2-oxo-2H-chromene skeleton has been synthesized by enantioselective Michael addition catalyzed by PYBOX-DIPH-Zn(OTf)2 complex. The methodology has successfully been employed in the synthesis of (R)-Warfarin and another related compounds.

  通过PYBOX-DIPH-Zn（OTf）2配合物催化的对映选择性迈克尔加成反应，合成了潜在的药理活性的手性3-取代的4-羟基-2-氧代-2 H-亚甲基骨架。该方法已成功地用于合成（R）-华法林和另一种相关化合物。
• Direct enantioselective allylic substitution of 4-hydroxycoumarin derivatives with branched allylic alcohols <i>via</i> iridium catalysis
  作者：Ruigang Xu、Kai Li、Jiaqi Wang、Jiamin Lu、Lina Pan、Xiaofei Zeng、Guofu Zhong

  DOI：10.1039/d0cc02832k

  日期：——

  A highly efficient direct asymmetric allylic substitution (AAS) reaction of 4-hydroxycoumarin derivatives with branched allylic alcohols was realized by combining a chiral iridium complex catalyst with a Lewis acid under mild reaction conditions, delivering various chiral allylation products in remarkably high yields and excellent enantioselectivities. The salient features of this transformation include

  通过在温和的反应条件下将手性铱配合物催化剂与路易斯酸结合，以高收率提供各种手性烯丙基化产物，实现了4-羟基香豆素衍生物与支链烯丙基醇的高效直接不对称烯丙基取代（AAS）反应。 。该转化的显着特征包括温和的反应条件，一般的底物范围，良好的官能团耐受性，高收率，优异的选择性和易于扩大规模。此外，所获得的产物可以容易地转化成几种生物活性化合物。
• Chiral Primary Amine Tagged to Ionic Group as Reusable Organocatalyst for Asymmetric Michael Reactions of C-Nucleophiles with α,β-Unsaturated Ketones
  作者：Alexander S. Kucherenko、Dmitry E. Siyutkin、Albert G. Nigmatov、Alexander O. Chizhov、Sergei G. Zlotin

  DOI：10.1002/adsc.201200338

  日期：2012.11.12

  The first primary amine-derived organocatalyst modified with an ionic group for asymmetric Michael reactions of C-nucleophiles with α,β-unsaturated ketones was synthesized. In the presence of this catalyst and an acidic co-catalyst (AcOH), hydroxycoumarin and its sulfur-containing analogue reacted with benzylideneacetone derivatives or cyclohexenone to afford the corresponding Michael adducts in high

  合成了第一个用离子基团改性的伯胺衍生的有机催化剂，用于C-亲核试剂与α，β-不饱和酮的不对称迈克尔反应。在这种催化剂和酸性助催化剂（AcOH）存在下，羟基香豆素及其含硫类似物与亚苄基丙酮衍生物或环己烯酮反应，以高收率（最高97％）和合理的对映选择性（最高UP）获得相应的迈克尔加合物。到80％）。该催化剂易于回收，可有效重复使用三遍，其活性和立体分化能力逐渐下降。通过ESI-MS对回收的催化剂样品进行分析，使我们能够检测出会毒化催化剂的不良副反应，并提出了将其重新活化的方法。