4,4-dimethyl-2-pentenyl p-tolyl sulfone | 121034-02-4

• 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: 4,4-dimethyl-2-pentenyl p-tolyl sulfone
• 英文别名: 1-[(E)-4,4-dimethylpent-2-enyl]sulfonyl-4-methylbenzene
• CAS: 121034-02-4
• 化学式: C₁₄H₂₀O₂S
• 分子量: 252.378
• InChiKey: JGBUVOSCMBQQPG-BJMVGYQFSA-N

物化性质

• 沸点：
  379.5±35.0 °C(Predicted)
• 密度：
  1.050±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4,4-二甲基-1-戊烯 在 碘 、 sodium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 26.0h， 生成 4,4-dimethyl-2-pentenyl p-tolyl sulfone
  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

• “<i>Syn-Effect</i>” in the Desilylation Reaction of γ-Silylated Allylic and Vinylic Sulfones
  作者：Samar Kumar Guha、Yutaka Ukaji、Katsuhiko Inomata

  DOI：10.1246/cl.2003.1158

  日期：2003.12

  The desilylation reaction of γ-silylated allylic sulfones was found to proceed through γ-silylated (E)-vinylic sulfones to afford the corresponding allylic sulfones by treatment with DBU and H2O. The Z/E ratio of the resulting allylic sulfones varied according to the γ-substituents of the γ-silylated sulfones. This stereochemical outcome was rationalized by “syn-effect.”

  研究发现，γ-硅烷化的烯丙基砜通过γ-硅烷化的（E）-乙烯基砜的脱硅反应，在DBU和H2O处理下得到相应的烯丙基砜。所得烯丙基砜的Z/E比率会根据γ-硅烷化砜的γ-取代基的不同而变化。这一立体化学结果可以通过“顺效应”来解释。
• Stereochemistry of the Conversion of γ-Substituted (<i>E</i>)-Vinylsulfones to the Corresponding Allylsulfones. Determination of the Relative Degree of “Syn-Effect”
  作者：Katsuhiko Inomata、Takaki Hirata、Hiroshi Suhara、Hideki Kinoshita、Hiroshi Kotake、Hitoshi Senda

  DOI：10.1246/cl.1988.2009

  日期：1988.12.5

  The relative degree of “syn-effect” for the γ-substituted vinylsulfones in their conversion to the corresponding allylsulfones with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was determined by observing E/Z ratios of the resulting allylsulfones as follows: CH3O– ≥ AcO– > CH3– > –CH2– >> t-Bu– and Ph–.

  通过观察所得烯丙基砜的 E/Z 比值，确定了 γ-取代的乙烯基砜在与 1,8-二氮杂双环[5.4.0]十一-7-烯（DBU）一起转化为相应的烯丙基砜时的 "协同效应 "相对程度如下：CH3O- ≥ AcO- > CH3- > -CH2- >> t-Bu- 和 Ph-。
• Palladium catalyzed hydrosulfination of allenes with tosylhydrazine leading to allylsulfones
  作者：Shin Kamijo、Mohammad Al-Masum、Yoshinori Yamamoto

  DOI：10.1016/s0040-4039(97)10637-2

  日期：1998.2

  The palladium catalyzed reaction of allenes 1 with tosylhydrazine in the presence of 1 equiv AcOH and 10 mol% dppf gave the corresponding allylsufones 2 in moderate to good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Remote participation during photooxidation at sulfur. Evidence for sulfurane intermediates
  作者：E. L. Clennan、Kang Yang

  DOI：10.1021/jo00042a031

  日期：1992.7

  The photooxidations of geminally substituted gamma-hydroxy sulfides results in formation of unusual oxidative elimination products. Detailed spectral data and the independent synthesis of a close analogue provide compelling evidence for the structures of these olefins. The formation of the olefins is attributed to decomposition of sulfurane intermediates. This conclusion is supported by a detailed kinetic study which separated the chemical, k(r), and physical, k(q), components to the overall deactivation of singlet oxygen. Those sulfides with the best geometry for sulfide-hydroxyl interaction are also the substrates which react most rapidly with singlet oxygen to give oxidation products. In addition, sulfone yields are in excess of 50% for the hydroxy-substituted sulfides but less than 5% for their hydrocarbon analogues. Several mechanisms that provide explanations for these unusually high sulfone yields are presented.
• INOMATA, KATSUHIKO;HIRATA, TAKAKI;SUHARA, HIROSHI;KINOSHITA, HIDEKI;KOTAK+, CHEM. LETT.,(1988) N2, C. 2009-2012
  作者：INOMATA, KATSUHIKO、HIRATA, TAKAKI、SUHARA, HIROSHI、KINOSHITA, HIDEKI、KOTAK+

  DOI：——

  日期：——