(E)-1-methyl-4-((3-phenoxyprop-1-en-1-yl)sulfonyl)benzene | 132625-33-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-1-methyl-4-((3-phenoxyprop-1-en-1-yl)sulfonyl)benzene
• 英文别名: (E)-3-phenoxy-1-tosyl-1-propene；1-methyl-4-[(E)-3-phenoxyprop-1-enyl]sulfonylbenzene
• CAS: 132625-33-3
• 化学式: C₁₆H₁₆O₃S
• 分子量: 288.367
• InChiKey: JEEUMSXFFKWQJO-WLRTZDKTSA-N

物化性质

• 沸点：
  494.2±45.0 °C(Predicted)
• 密度：
  1.189±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-1-methyl-4-((3-phenoxyprop-1-en-1-yl)sulfonyl)benzene 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 96.0h， 以3%的产率得到1-Methyl-4-((E)-3-phenoxy-prop-2-ene-1-sulfonyl)-benzene
  参考文献：
  名称：

  Crystallographic Approach to the Origin of “Syn-Effect”

  摘要：

  X射线晶体学显示，α-未取代（E）-乙烯基砜具有顺式构象，这似乎是（E）-乙烯基砜在温和条件下与碱反应转化为相应的烯丙基砜时产生“顺式效应”的原因。 固态末端烯烃的顺式构象也得到了证实。

  DOI：

  10.1246/cl.1990.2153
• 作为产物：
  描述：

  烯丙基苯基醚 在 吡啶 、 碘 作用下， 以 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 6.0h， 生成 (E)-1-methyl-4-((3-phenoxyprop-1-en-1-yl)sulfonyl)benzene
  参考文献：
  名称：

  “Syn-Effect” in the Conversion of (E)-Vinylic Sulfones to the Corresponding Allylic Sulfones

  摘要：

  研究发现，在温和条件下通过碱性处理，(E)-乙烯基砜类化合物倾向于优先形成动力学控制的(Z)-烯丙基砜类产物，而(Z)-乙烯基砜则生成(E)-烯丙基砜。这种立体化学关系可通过“邻位效应”来解释，并且通过观察相应的γ-单取代或γ,γ-双取代乙烯基砜所生成的烯丙基砜的E/Z比率，确定了不同取代基的相对程度如下：RO–（R=CH3, C2H5）＞ ArO–（Ar=p-CH3OC6H4, p-CH3C6H4, C6H5, p-NO2C6H4）≥ AcO–＞ Cl– ≥ Br–＞ CH3–＞ CH3S– ≥ –CH2–（环状和非环状）＞(CH3)2CH–>＞(CH3)3C–, C6H5–。对一些乙烯基砜进行了X射线晶体学分析，以揭示“邻位效应”的起源。

  DOI：

  10.1246/bcsj.65.75

文献信息

• Water-mediated radical C–H tosylation of alkenes with tosyl cyanide
  作者：Dongyan Hu、Yang Zhang、Jianwei Li、Kangjiang Liang、Chengfeng Xia

  DOI：10.1039/d2cc06101e

  日期：——

  alkenes with tosyl cyanide was discovered. Experimental investigations revealed that the reaction was initiated by the in situ formation of sulfinyl sulfone in the presence of water. The sulfinyl sulfone species decomposed to a sulfonyl radical and a sulfinyl radical through homolytic fission. The vinyl sulfone was afforded via sequential addition of the alkene to the sulfonyl radical and the sulfinyl

  发现了水介导的烯烃与甲苯磺酰氰化物的甲苯磺酰化反应。实验研究表明，反应是由在水存在下原位形成亚磺酰砜引发的。亚磺酰基砜物种通过均裂裂变分解为磺酰基和亚磺酰基。乙烯基砜是通过将烯烃依次加成到磺酰基和亚磺酰基上，然后通过β-消除亚磺酰基部分得到的。
• Crystallographic Approach to the Origin of “Syn-Effect”
  作者：Katsuhiko Inomata、Takaki Hirata、Yoshihiro Sasada、Takahiro Asada、Hitoshi Senda、Hideki Kinoshita

  DOI：10.1246/cl.1990.2153

  日期：1990.12

  It was revealed by X-ray crystallography that α-unsubstituted (E)-vinyl sulfones have syn-conformation which seems to be the cause of “syn-effect” found in the conversion of (E)-vinyl sulfones to the corresponding allyl sulfones with a base under mild conditions. Syn-conformation of a terminal olefin in solid state was also confirmed.

  X射线晶体学显示，α-未取代（E）-乙烯基砜具有顺式构象，这似乎是（E）-乙烯基砜在温和条件下与碱反应转化为相应的烯丙基砜时产生“顺式效应”的原因。 固态末端烯烃的顺式构象也得到了证实。
• Silver Nitrate Catalyzed Sulfonylation of O-Propargyl Alkynes
  作者：Paulo H. Menezes、Bárbara G. Sátiro、Igor M. R. Moura、Cláudia L. A. Almeida、Queila P. B. Freitas、Roberta A. Oliveira

  DOI：10.1055/a-2205-5806

  日期：——

  lower-cost metals under environmentally friendly conditions is still a challenge. Herein, we report an efficient strategy for the synthesis of vinyl sulfones from O-propargyl alkynes and sodium salts of sulfinic acids using silver nitrate, an inexpensive and readily available catalyst, under air atmosphere using aqueous conditions. The products were obtained in good to moderate yields, and the mechanism

  在环境友好的条件下开发基于低成本金属的新催化方法仍然是一个挑战。在此，我们报告了一种使用硝酸银（一种廉价且易于获得的催化剂）在空气气氛下使用水性条件从O-炔丙基炔和亚磺酸钠盐合成乙烯基砜的有效策略。产物以良好到中等的收率获得，并且还研究了反应机理。
• An Improved Synthesis of Vinyl- and β-Iodovinyl Sulfones by a Molecular Iodine-Mediated One-Pot Iodosulfonation-Dehydroiodination Reaction
  作者：Tassaporn Sawangphon、Praewpan Katrun、Korbua Chaisiwamongkhol、Manat Pohmakotr、Vichai Reutrakul、Thaworn Jaipetch、Darunee Soorukram、Chutima Kuhakarn

  DOI：10.1080/00397911.2012.663448

  日期：2013.6.18

  An improved one-pot method to synthesize vinyl sulfones from unsaturated systems by using molecular iodine/sodium arenesulfinate/sodium acetate as reagents was described. Vinyl sulfones derived from styrene derivatives were generally obtained in good to excellent yields except for those bearing strong electron releasing substituent. Aliphatic alkenes and activated alkenes gave the corresponding vinyl sulfone products in moderate to good yields. Arylacetylenes yielded the respective -iodovinyl sulfones in good yields while low yield was observed with aliphatic terminal alkyne. The potentials of the method entail simplicity, short reaction time, non-anhydrous reaction conditions, employing inexpensive, non-metallic reagent and integrating two reactions that are commonly accomplished separately into a single operation.
• “<i>Syn-Effect</i>” in the Conversion of (<i>E</i>)-Vinylic Sulfones to the Corresponding Allylic Sulfones
  作者：Takaki Hirata、Yoshihiro Sasada、Takashi Ohtani、Takahiro Asada、Hideki Kinoshita、Hitoshi Senda、Katsuhiko Inomata

  DOI：10.1246/bcsj.65.75

  日期：1992.1

  It was found that (E)-vinylic sulfones preferentially afford (Z)-allylic sulfones as kinetically-controlled products by treatment with a base under mild conditions, while (Z)-vinylic sulfones give (E)-allylic sulfones. Such stereochemical relationship was rationalized by “syn-effect”, and its relative degree for various substituents was determined by observation of E/Z ratios of the allylic sulfones resulted from the corresponding γ-mono- or γ,γ-disubstituted vinylic sulfones as follows: RO– (R = CH3, C2H5) ArO– (Ar = p-CH3OC6H4, p-CH3C6H4, C6H5, p-NO2C6H4) ≥ AcO– > Cl– ≥ Br– > CH3– > CH3S– ≥ –CH2– (cyclic and acyclic) > (CH3)2CH– >> (CH3)3C–, C6H5–. X-Ray crystallography was performed for some vinylic sulfones to reveal the origin of the “syn-effect”.

  研究发现，在温和条件下通过碱性处理，(E)-乙烯基砜类化合物倾向于优先形成动力学控制的(Z)-烯丙基砜类产物，而(Z)-乙烯基砜则生成(E)-烯丙基砜。这种立体化学关系可通过“邻位效应”来解释，并且通过观察相应的γ-单取代或γ,γ-双取代乙烯基砜所生成的烯丙基砜的E/Z比率，确定了不同取代基的相对程度如下：RO–（R=CH3, C2H5）＞ ArO–（Ar=p-CH3OC6H4, p-CH3C6H4, C6H5, p-NO2C6H4）≥ AcO–＞ Cl– ≥ Br–＞ CH3–＞ CH3S– ≥ –CH2–（环状和非环状）＞(CH3)2CH–>＞(CH3)3C–, C6H5–。对一些乙烯基砜进行了X射线晶体学分析，以揭示“邻位效应”的起源。