2-(甲硫基甲基)-2,3-二氢苯并呋喃 | 81077-71-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 中文名称: 2-(甲硫基甲基)-2,3-二氢苯并呋喃
• 英文名称: 2,3-dihydro-2-((methylthio)methyl)benzofuran
• 英文别名: 2-((methylthio)methyl)-2,3-dihydrobenzofuran；2-(methylthiomethyl)-2,3-dihydrobenzofuran；2-methylthiomethyl-2,3-dihydrobenzofuran；(r,s)-2-Methylsulfanylmethyl-2,3-dihydro-benzofuran；2-(methylsulfanylmethyl)-2,3-dihydro-1-benzofuran
• CAS: 81077-71-6
• 化学式: C₁₀H₁₂OS
• 分子量: 180.271
• InChiKey: KLILPDVVTZYTRP-UHFFFAOYSA-N

物化性质

• 沸点：
  283.8±9.0 °C(Predicted)
• 密度：
  1.118±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(甲硫基甲基)-2,3-二氢苯并呋喃 在 环己硫醇 、 二甲基氧化锡 作用下， 以 四氢呋喃 、 N,N-二甲基乙酰胺 、 1,2-二氯乙烷 为溶剂， 反应 24.0h， 生成 2-烯丙基酚
  参考文献：
  名称：

  三烷基锍盐的镍催化根岸型芳基化

  摘要：

  三烷基锍盐与芳基锌试剂的 Negishi 型芳基化反应已在镍催化下完成。发现使用环己硫醇作为额外的配体对于促进 C-S 裂解特别重要。本反应通过与 MeOTf 的 S-甲基化相结合，实现了二烷基硫醚的一锅芳基化。机理实验表明，C-S 裂解将通过单电子转移 (SET) 进行以产生最稳定的以碳为中心的自由基，并且硫醇盐配体将促进 C-S 裂解和自由基重组步骤。

  DOI：

  10.1055/s-0040-1707817
• 作为产物：
  描述：

  DMTST 、 2-烯丙基酚 以 二氯甲烷 为溶剂， 反应 2.0h， 以260 mg的产率得到2-(甲硫基甲基)-2,3-二氢苯并呋喃
  参考文献：
  名称：

  Novel formation of indoles and 3,1-benzoxazines from o-alkenylanilides and dimethyl(methylthio)sulfonium trifluoromethanesulfonate

  摘要：

  The reaction of dimethyl(methylthio)sulfonium trifluoromethanesulfonate (DMTST) with o-allylphenol gave 2-methylthiomethyl-2,3-dihydrobenzofuran in 97% yield. The reaction of DMTST with N-tosyl-o-isopropenylanilide followed by the addition of aq sodium carbonate afforded N-tosyl-3-methylindole in 88% yield, whereas N-tosyl-o-vinylanilide afforded N-tosylindoline in 85% yield. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.05.111

文献信息

• Copper-Catalyzed Oxysulfenylation of Enolates with Sodium Sulfinates: A Strategy To Construct Sulfenylated Cyclic Ethers
  作者：Yinglan Gao、Yang Gao、Xiaodong Tang、Jianwen Peng、Miao Hu、Wanqing Wu、Huanfeng Jiang

  DOI：10.1021/acs.orglett.6b00272

  日期：2016.3.4

  A new copper-catalyzed oxysulfenylation reaction of enolates with sodium sulfinates has been disclosed. A series of sulfenylated heterocycles including four- and seven-membered cyclic ether were obtained in mild to good yields. This reaction is proposed to go through a radical process, and the sulfur radical (RS•) may be a reactive species.

  已经公开了一种新的铜催化的烯醇盐与亚磺酸钠的氧磺酰化反应。以中等至良好的产率获得了一系列包括四元和七元环醚的亚磺酰基化杂环。建议该反应经过自由基过程，硫自由基（RS •）可能是反应性物质。
• Intramolecular cyclization using methyl(bismethylthio)sulphonium salts. Part 1. 2,3-Dihydrobenzofurans
  作者：Giuseppe Capozzi、Vittorio Lucchini、Franco Marcuzzi、Giorgio Modena

  DOI：10.1039/p19810003106

  日期：——

  Methyl(bismethylthio)sulphonium hexachloroantimonate (1a) reacts under mild conditions with 2-allylphenol (3a) to give 2-(methylthiomethyl)-2,3-dihydrobenzofuran (4a). Methylthiolation at position 5 in the heterocycle may also occur. With 4-substituted 2-allylphenols (3b–d)(substituents: methyl,chloro,nitro) only the corresponding 5-substituted 2-(methylthiomethyl)-2,3-dihydrobenzofurans (4b–d) are

  六氯锑酸甲基（双甲硫基）磺酸ium（1a）与2-烯丙基苯酚（3a）在温和条件下反应，生成2-（甲硫基甲基）-2,3-二氢苯并呋喃（4a）。杂环中第5位的甲硫醇也可能发生。用4-取代的2-烯丙基苯酚（3b-d）（取代基：甲基，氯，硝基）只能得到相应的5-取代的2-（甲硫基甲基）-2,3-二氢苯并呋喃（4b-d）。
• NH₄I-Promoted and H₂O-Controlled Intermolecular Bis-sulfenylation and Hydroxysulfenylation of Alkenes via a Radical Process
  作者：Runfa He、Xiuwen Chen、Yibiao Li、Qiang Liu、Chunshu Liao、Lu Chen、Yubing Huang

  DOI：10.1021/acs.joc.9b01047

  日期：2019.7.5

  An NH4I-promoted and H2O-controlled intermolecular difunctionalization of alkenes for the synthesis of bis-methylsulfane and beta-hydroxysulfides is presented. Mechanistic investigation revealed the reaction proceeds via methylthiyl radical addition to C=C of alkenes to give a carbon-centered radical and immediately cyclize to a thiiranium ion, followed by combination with H2O to afford beta-hydroxysulfides in 52-89% yields with chemo- and regioselectivities. In the absence of water, 1,2-disulfenylation takes place to give bis-methylsulfane in moderate to good yields.
• CAPOZZI, G.;LUCCHINI, V.;MARCUZZI, F.;MODENA, G., J. CHEM. SOC. PERKIN TRANS., 1981, N 12, 3106-3110
  作者：CAPOZZI, G.、LUCCHINI, V.、MARCUZZI, F.、MODENA, G.

  DOI：——

  日期：——
• Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts
  作者：Hideki Yorimitsu、Hiroko Minami、Keisuke Nogi

  DOI：10.1055/s-0040-1707817

  日期：2021.9

  Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C–S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S-methylation with MeOTf. Mechanistic experiments suggest that C–S cleavage

  三烷基锍盐与芳基锌试剂的 Negishi 型芳基化反应已在镍催化下完成。发现使用环己硫醇作为额外的配体对于促进 C-S 裂解特别重要。本反应通过与 MeOTf 的 S-甲基化相结合，实现了二烷基硫醚的一锅芳基化。机理实验表明，C-S 裂解将通过单电子转移 (SET) 进行以产生最稳定的以碳为中心的自由基，并且硫醇盐配体将促进 C-S 裂解和自由基重组步骤。