3-(methylthio)-1,3-diphenylpropan-1-one | 21205-07-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 3-(methylthio)-1,3-diphenylpropan-1-one
• 英文别名: 3-Methylsulfanyl-1,3-diphenylpropan-1-one
• CAS: 21205-07-2
• 化学式: C₁₆H₁₆OS
• 分子量: 256.368
• InChiKey: VCMFSHGBJKABMW-UHFFFAOYSA-N

物化性质

• 熔点：
  59 °C(Solv: ethanol (64-17-5))
• 沸点：
  410.8±38.0 °C(Predicted)
• 密度：
  1.117±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(methylthio)-1,3-diphenylpropan-1-one 在 双氧水 、 乙酸酐 作用下， 生成 3-(methylsulfonyl)-1,3-diphenylpropan-1-one
  参考文献：
  名称：

  Becerro Ruiz, 1958, vol. 2, # 7, p. 9,36,47

  摘要：

  DOI：
• 作为产物：
  描述：

  苄基甲基硫醚 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 3-(methylthio)-1,3-diphenylpropan-1-one
  参考文献：
  名称：

  Schoellkopf,U. et al., Justus Liebigs Annalen der Chemie, 1970, vol. 737, p. 158 - 169

  摘要：

  DOI：

文献信息

• On the development of a nucleophilic methylthiolation methodology
  作者：Bernardo Basbaum Portinho de Puga Carvalho、Adriane Antonia Pereira Amaral、Pedro Pôssa de Castro、Fernanda Cerqueira Moreira Ferreira、Bruno Araújo Cautiero Horta、Giovanni Wilson Amarante

  DOI：10.1039/d0ob01149e

  日期：——

  yields. The reaction mechanism was investigated through several control experiments, as well as by theoretical calculations employing Density Functional Theory. The results strongly support that a sulfurane and a sulfonium ylide appear as key intermediates and that a Pummerer type rearrangement is also crucial for the formation of this novel reagent. Furthermore, the methylthiolation mechanism is likely

  通常使用甲硫醇（一种极易燃且有毒的化合物）来探索甲硫醇化反应，以获取有机硫化合物。在此，以低成本，无过渡金属的方法成功地将甲硫基甲基酯用作新型甲硫基化试剂。这些试剂可以对各种查尔酮，酰基酯衍生物和Morita–Baylis–Hillman乙酸盐进行甲基硫醇化，具有良好的基团耐受性，从而可以提供中等至优异收率的甲基硫醇化产品。通过一些控制实验以及采用密度泛函理论的理论计算，研究了反应机理。结果强烈支持了以硫烷和叶立德作为关键中间体出现，并且Pummerer型重排对于这种新型试剂的形成也至关重要。此外，甲硫醇化机理很可能是通过试剂的亲核攻击而进行的，随后是一个有利于熵的步骤，其中包括乙酸盐攻击带正电荷的物种，然后释放出产物。
• Thia-Michael Addition Reactions Using 2-[Bis(alkylthio)methylene]-3-oxo-<i>N</i>-<i>o</i>-tolylbutanamides as Odorless and Efficient Thiol Equivalents
  作者：Dewen Dong、Qun Liu、Haifeng Yu、Yan Ouyang、Xihe Bi、Yumei Lu

  DOI：10.1055/s-2005-923602

  日期：——

  A series of 2-[bis(alkylthio)methylene]-3-oxo-N-o-tolylbutanamides 1 have been investigated as nonthiolic and odorless thiol equivalents in thia-Michael addition reactions. The cleavage of compounds 1 is initiated by NaOHin EtOH; the in situ generated thiolate anions undergo facile conjugate addition to α,β-unsaturated carbonyl compounds 2 affording the corresponding β-keto sulfides 3 in very high

  一系列 2-[双(烷硫基) 亚甲基]-3-氧代-No-tolylbutanamides 1 已被研究为硫杂-迈克尔加成反应中的非硫醇和无味硫醇等价物。化合物1的裂解由NaOHin EtOH引发；原位生成的硫醇阴离子与 α,β-不饱和羰基化合物 2 进行简单的共轭加成，以非常高的产率提供相应的 β-酮硫化物 3。同时，化合物 1 的前体 3-oxo-No-tolylbutanamide 4 可以作为副产物以良好的收率从新型硫杂-迈克尔加成反应中回收。
• Methylsulfenylation of Electrophilic Carbon Atoms: Reaction Development, Scope, and Mechanism
  作者：Adriane A. Pereira、Amanda S. Pereira、Amanda C. de Mello、Arthur G. Carpanez、Bruno A. C. Horta、Giovanni W. Amarante

  DOI：10.1002/ejoc.201601613

  日期：2017.3.27

  An innovative methodology for methylsulfenylation of electrophilic carbons is presented. Cheaper and commercially available dimethylsulfoxide (DMSO) is now used as a source of -SCH3 group. Chalcone, dibenzylideneacetone (DBA) as well as Morita-Baylis-Hillman (MBH) adduct derivatives were successfully sulfenylated, giving the corresponding products with moderate to high isolated yields. Control experiments

  提出了一种用于亲电碳甲基亚磺酰化的创新方法。现在使用更便宜且可商购的二甲基亚砜 (DMSO) 作为 -SCH3 基团的来源。查尔酮、二亚苄基丙酮 (DBA) 以及 Morita-Baylis-Hillman (MBH) 加合物衍生物被成功地磺酰化，得到相应的产物，分离产率中等至高。对照实验和 DFT 计算揭示了 DMSO 过程的脱氧和硫中间体的亲核加成是整个机制中的关键步骤。
• Oxidative Generation of Thioalkyl Cations from 2-Tributylstannyl-1,3-dithianes and 1-(Tributylstannyl)alkyl Sulfides and Their Reactions with Olefinic Nucleophiles
  作者：Koichi Narasaka、Noriyoshi Arai、Tatsuo Okauchi

  DOI：10.1246/bcsj.66.2995

  日期：1993.10

  2-Tributylstannyl-1,3-dithianes and 1-(tributylstannyl)alkyl sulfides are oxidized with ammonium hexanitratocerate(IV) or ferrocenium hexafluorophosphate to generate their cation radicals, which dissociate into the carbocations and tributylstannyl radical. The carbocations thus generated react with olefinic nucleophiles to afford the corresponding addition products in good yield.

  2-三丁基甲锡烷基-1,3-二噻烷和 1-(三丁基甲锡烷基) 烷基硫化物被六硝酸铵 (IV) 或六氟磷酸二茂铁氧化生成它们的阳离子自由基，其离解成碳阳离子和三丁基锡烷基自由基。由此产生的碳正离子与烯烃亲核试剂反应，以良好的产率得到相应的加成产物。
• Design and synthesis of 1,3-biarylsulfanyl derivatives as new anti-breast cancer agents
  作者：Atul Kumar、Vishwa Deepak Tripathi、Promod Kumar、Lalit Prakash Gupta、Akanksha、Ritu Trivedi、Hemant Bid、V.L. Nayak、Jawed A. Siddiqui、Bandana Chakravarti、Ruchi Saxena、Anila Dwivedi、M.I. Siddiquee、U. Siddiqui、Rituraj Konwar、Naibedya Chattopadhyay

  DOI：10.1016/j.bmc.2011.07.056

  日期：2011.9

  A new series of 1,3-biarylsulfanyl derivatives (homodibenzyl core motif) have been designed and synthesized as new estrogen receptor ligands by chopping benzothiophene core of raloxifene to engender secoraloxifene scaffold. All the synthesized compounds were screened for anti-proliferative, anti-osteoporotic, and anti-implantation activity. Compounds (35, 36) having basic amino anti-estrogenic side chain were exhibiting potential anti-proliferative activity in MCF-7, MDA-MB-231 and ishikawa cell lines. Some of the synthesized compounds having homodibenzyl motif (5, 8, 10) have shown moderate anti-osteoporotic activity. (C) 2011 Elsevier Ltd. All rights reserved.