7-chloro-4-hydroxydithiocoumarin | 112519-37-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 7-chloro-4-hydroxydithiocoumarin
• CAS: 112519-37-6
• 化学式: C₉H₅ClOS₂
• 分子量: 228.723
• InChiKey: JHFAPTBGOXYMRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  13.0
• 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：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  7-chloro-4-hydroxydithiocoumarin 在 palladium on activated charcoal sodium hydroxide 作用下， 以 喹啉 、 二苯醚 、 氯仿 为溶剂， 反应 7.5h， 生成 7-chloro-3-ethyl-4H-thieno[2,3-b]thiochromen-4-one
  参考文献：
  名称：

  Synthesis of Sulfur Heterocycles by Thio- Claisen Rearrangement

  摘要：

  7-Chloro-4-hydroxydithiocoumarin was alkylated with allylic halides under phase transfer catalysis condition in the presence of TBAB or BTEAC in chloroform-aqueous NaOH (1%) at room temperature. 2,3-Dichloroprop-2-ene on similar treatment with 7-chloro-4-hydroxydithiocoumarin afforded 2-methylthieno[2,3-b]thiochromen-4-one in 65% yield. The S-alkylated thiochromen-4-ones were then refluxed in quinoline to give 7-chloro-2,3-dihydrothieno[2,3-b]thiochromen-4-ones or 7-chloro-2,3,4-trihydrothiopyrano[2,3-b]thiochromen-5-ones or 7-chloro-2,3-dihydro-3-vinylthieno[2,3-b]thiochromen-4-one.

  DOI：

  10.1007/s00706-003-0109-y
• 作为产物：
  描述：

  二硫化碳 、 2,4-二氯苯乙酮 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 1.5h， 以63%的产率得到7-chloro-4-hydroxydithiocoumarin
  参考文献：
  名称：

  Anderson-McKay, Janet E.; Liepa, Andris J., Australian Journal of Chemistry, 1987, vol. 40, # 7, p. 1179 - 1190

  摘要：

  DOI：

文献信息

• An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I₂ and TBHP: access to lead molecules for biomedical applications
  作者：Karuna Mahato、Neha Arora、Prasanta Ray Bagdi、Radhakrishna Gattu、Siddhartha Sankar Ghosh、Abu T. Khan

  DOI：10.1039/c7cc08502h

  日期：——

  operationally simple oxidative cross-coupling reaction has been developed for the direct synthesis of sulfenamides/sulfanes/disulfides from the reaction of 4-hydroxydithiocoumarin and amines/thiols. The novelties of the present protocol are unprecedented S–C bond formation in addition to S–N and S–S bonds, shorter reaction time, mild and environmentally benign reaction conditions, functional group tolerance

  已经开发了无金属的I 2 / TBHP诱导的高度原子经济和操作简单的氧化交叉偶联反应，用于由4-羟基二硫代香豆素与胺/硫醇的反应直接合成亚磺酰胺/亚砜/二硫化物。本协议的新颖之处在于，除了S–N和S–S键之外，还形成了前所未有的S–C键，反应时间更短，反应条件温和和环境温和，官能团耐受性好，产率中等至优异。此外，四种新合成的化合物即4q，6d，6e和7a对乳腺癌细胞系MCF7表现出抗增殖活性，并且可能是未来药物开发的先导分子。
• Synthesis of vinyl sulfides and thioethers <i>via</i> a hydrothiolation reaction of 4-hydroxydithiocoumarins and arylacetylenes/styrenes
  作者：Santa Mondal、Sabina Yashmin、Abu Taleb Khan

  DOI：10.1039/d1ob01729b

  日期：——

  The synthesis of vinyl sulfides (3a–m) and thioethers (7a–k), exclusive Markovnikov products, is reported by a copper(I) iodide catalyzed regioselective hydrothiolation reaction of terminal alkynes/alkenes and 4-hydroxydithiocoumarins. However, anti-Markovnikov hydrothiolation products (5a–f) were obtained in the case of 2-ethynylpyridine, with exclusive Z selectivity in good yields. The important

  通过碘化铜 ( I ) 催化末端炔烃/烯烃和 4-羟基二硫代香豆素的区域选择性氢硫基化反应合成乙烯基硫化物 ( 3a-m ) 和硫醚 ( 7a-k )，这是 Markovnikov 独有的产物。然而，在 2-乙炔基吡啶的情况下，获得了抗马尔可夫尼科夫氢硫醇化产物 ( 5a-f )，具有高产率的独家Z选择性。该协议的重要方面是没有昂贵的金属配合物和添加剂作为配体、温和的反应条件、高区域选择性、良好的收率和更短的反应时间。
• Green Synthesis of Benzopyran-Annulated Thiopyrano[2,3-b]thiochromen-5(4H)-ones by Domino Knoevenagel-Hetero-Diels-Alder Reaction
  作者：K. Majumdar、Abu Taher、Sudipta Ponra

  DOI：10.1055/s-0030-1258261

  日期：2010.12

  Benzopyran-annulated thiopyrano[2,3-b]thiochromen-5(4H)-ones have been synthesized by the domino Knoevenagel-hetero-Diels-Alder (DKHDA) reaction of 4-hydroxydithiocoumarin with O-allylated salicylaldehyde and O-propargylated salicyl­aldehyde in aqueous medium. The reaction requires only a single step operation and is highly regio- and stereoselective providing potentially bioactive polycyclic heterocycles in high yields.

  通过4-羟基二硫代香豆素与O-烯丙基水杨醛和O-丙炔基水杨醛在水相中进行多米诺Knoevenagel-异质-Diels-Alder（DKHDA）反应，合成了苯并吡喃-环硫吡喃[2,3-b]硫克罗门-5(4H)-酮。该反应仅需一步操作，具有很高的区域选择性和立体选择性，能够高产率提供具有潜在生物活性的多环杂环化合物。
• Newly synthesized 3-sulfenylindole derivatives from 4-hydroxydithiocoumarin using an oxidative cross dehydrogenative coupling reaction (OCDCR): potential lead molecules for antiproliferative activity
  作者：Santa Mondal、Karuna Mahato、Neha Arora、Dheerendra Kankane、Umed Pratap Singh、Saghir Ali、Aftab Hossain Khan、Siddhartha S. Ghosh、Abu T. Khan

  DOI：10.1039/d0ob00054j

  日期：——

  developed for the oxidative cross dehydrogenative coupling reaction between 4-hydroxydithiocoumarin and indole at the C-3 position regio-selectively using a combination of 10 mol% molecular iodine and TBHP in the presence of 10 mol% CuBr2 as an additive at room temperature. Mild reaction conditions, good yields and a broad substrate scope are some of the salient features of the present protocol. Additionally

  开发了一种简便有效的合成方法，用于在10 mol％CuBr 2存在下，使用10 mol％分子碘和TBHP的组合，选择性地在C-3位的4-羟基二硫代香豆素与吲哚之间进行氧化交叉脱氢偶联反应。在室温下作为添加剂。温和的反应条件，良好的收率和广泛的底物范围是本方案的一些突出特征。另外，将衍生自4-羟基二硫代香豆素的合成的3-亚磺酰基吲哚转化为具有生物活性的砜衍生物。有趣的是，由于活性氧（ROS）介导的细胞损伤，某些化合物对乳腺癌（MCF-7）细胞具有抗细胞增殖活性。
• Synthesis of biologically active fused 1,4-oxathiin derivatives from 4-hydroxydithiocoumarins, arylacetylenes and dimethyl sulfoxide by Cu(<scp>i</scp>)-catalyzed C–H functionalization and cross-dehydrogenative C–S coupling reactions
  作者：Santa Mondal、Sabina Yashmin、Rashid Ali、R Soundaram、Siddhartha S. Ghosh、Abu Taleb Khan

  DOI：10.1039/d1ob00846c

  日期：——

  hitherto unreported 2-aryl-10H-thiochromeno[3,2-b][1,4]oxathiin-10-one derivatives are obtained in a single pot from 4-hydroxydithiocoumarins, arylacetylenes and dimethyl sulfoxide in the presence of 10 mol% CuI and K2CO3 in an oil bath at 70 °C. The novelties of the present protocol are (i) selective C–H functionalization at the C-3 position of 4-hydroxydithiocoumarin, (ii) regioselective hydrothiolation

  迄今为止未报道的 2-aryl-10 H -thiochromeno[3,2- b ][1,4]oxathiin-10-one 衍生物是在 10 mol 存在下由 4-羟基二硫代香豆素、芳基乙炔和二甲亚砜在单锅中获得的% CuI 和 K 2 CO 3在 70 °C 的油浴中。本方案的新颖之处在于 (i) 在 4-羟基二硫代香豆素的 C-3 位置选择性 C-H 官能化，(ii) 与芳基乙炔的区域选择性氢化硫醇化和 (iii) 伴随的环化。主要优点是反应条件温和、底物范围广、收率好。在合成的化合物中，有以下五种化合物3aa、3bd、3ec、3fa, 和3fd对人乳腺癌细胞系 (MCF-7) 和宫颈癌细胞系 (HeLa) 显示出抗癌活性。