methyloctyl sulfone | 7560-60-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 磺酰类
• 英文名称: methyloctyl sulfone
• 英文别名: methyl n-octyl sulfone；1-(methylsulfonyl)octane；1-methanesulfonyl-octane；Methyl-octyl-sulfon；Octane, 1-(methylsulfonyl)-；1-methylsulfonyloctane
• CAS: 7560-60-3
• 化学式: C₉H₂₀O₂S
• 分子量: 192.323
• InChiKey: KCFYSLQCXGEOHC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyloctyl sulfone 在 甲基三辛基氯化铵 sodium tetrahydroborate 、 sodium azide 、 十六烷基三丁基溴化磷 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 辛胺
  参考文献：
  名称：

  Sodium borohydride reactions under phase-transfer conditions: reduction of azides to amines

  摘要：

  DOI：

  10.1021/jo00143a031
• 作为产物：
  描述：

  1-octyl 2-(4-pyridyl)ethyl sulfide 在 sodium periodate 、 potassium carbonate 作用下， 以 水 为溶剂， 反应 31.0h， 生成 methyloctyl sulfone
  参考文献：
  名称：

  2-(4-Pyridyl)ethyl as a protective group for sulfur functionality

  摘要：

  DOI：

  10.1021/jo00375a029

文献信息

• Polyoxomolybdate-Calix[4]arene Hybrid: A Catalyst for Sulfoxidation Reactions with Hydrogen Peroxide
  作者：Sara Meninno、Alessandro Parrella、Giovanna Brancatelli、Silvano Geremia、Carmine Gaeta、Carmen Talotta、Placido Neri、Alessandra Lattanzi

  DOI：10.1021/acs.orglett.5b02607

  日期：2015.10.16

  polyoxomolybdate–calix[4]arene hybrid 1 has been synthesized and applied as a heterogeneous catalyst in the sulfoxidation of thioethers to sulfoxides and to sulfones under strictly stoichiometric amounts of 30% H2O2 in CH3CN as the solvent. This study represents the first promising example of successful employment of calixarenes–polyoxometalate (POM) hybrid materials in the area of catalytic oxidations.

  合成了一种容易获得的聚氧钼酸盐-杯[4]芳烃杂化物1，并作为非均相催化剂在严格化学计量的CH 3 CN中以30％H 2 O 2为溶剂将硫醚硫氧化为亚砜和砜。这项研究代表了在催化氧化领域成功使用杯芳烃-多金属氧酸盐（POM）杂化材料的第一个有希望的例子。
• Highly efficient oxidation of sulfides with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2−
  作者：Keigo Kamata、Tomohisa Hirano、Noritaka Mizuno

  DOI：10.1039/b907952a

  日期：——

  By using the selenium-containing dinuclear peroxotungstate at 0.005–0.1 mol%, various kinds of sulfides could be converted into the corresponding sulfoxides or sulfones in excellent yields with one or two equivalents of H2O2 with respect to the sulfide, respectively.

  通过使用含硒的双核过钨酸盐（硒含量为0.005－0.1摩尔百分比），各种硫化物能够分别以高产率转化为相应的亚砜或砜，所需过氧化氢的量为硫化物的一或两倍当量。
• Sulfoxidation with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2−
  作者：Keigo Kamata、Tomohisa Hirano、Ryo Ishimoto、Noritaka Mizuno

  DOI：10.1039/c002318c

  日期：——

  The selenium-containing dinuclear peroxotungstate, [(n-C4H9)4N]2[SeO4WO(O2)2}2] (I), acts as a homogeneous catalyst for the selective oxidation of various kinds of cyclic mono- and disulfides with 30% aqueous H2O2. The cyclic disulfides were selectively oxidized to the corresponding monosulfoxides with one equivalent of H2O2 with respect to the sulfides. In the presence of two equivalents of H2O2, the oxidation of dibenzothiophene gave the corresponding sulfone in 98% yield under the mild conditions. The negative Hammett ρ value (−0.62) for the competitive oxidation of p-substituted thioanisoles and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of 0.14 for the I-catalyzed oxidation of thianthrene 5-oxide (SSO) revealed that I is a strong electrophilic oxidant. The reactivities of the di- and tetranuclear peroxotungstates with XO4n− ligands (X = Se(VI), As(V), P(V), S(VI), and Si(IV)) were strongly dependent on the kinds of hetero atoms. The reaction rates for the sulfoxidation decreased with an increase in the XSO values and a peroxotungstate with a stronger electrophilicity was more active for the sulfoxidation. The kinetic and mechanistic investigations showed that the electrophilic attack of the peroxo oxygen at the sulfur atom is a key step in the sulfoxidation. The computational investigation supported the high chemoselectivitiy for the sulfoxidation of diallyl sulfide.

  含硒双核过钨酸盐[(n-C4H9)4N]2[SeO4WO(O2)2}2]（I）作为均相催化剂，可用于30%水溶液H2O2对各种环状单硫醚和二硫醚的选择性氧化。环状二硫醚被 选择性氧化为相应的单亚砜， 与硫醚的摩尔比为1:1。在 与硫醚摩尔比为2:1的情况下，二苯并噻吩在温和条件下被氧化为相应的砜，产率达98%。对于竞争氧化具有对位取代基的硫醚，负Hammett ρ值（-0.62）以及在I催化氧化噻蒽5-氧化物（SSO）过程中XSO（XSO =（亲核氧化）/（总氧化））值为0.14，表明I是一种强亲电氧化剂。具有XO4n-配体的双核和四核过钨酸盐（X = Se(VI)、As(V)、P(V)、S(VI)和Si(IV)）的反应活性强烈依赖于杂原子的种类。磺氧化反应速率随着XSO值的增加而降低，亲电性更强的过钨酸盐在磺氧化反应中表现出更高的活性。动力学和机理研究表明，过氧氧对硫原子的亲电攻击是磺氧化反应的关键步骤。计算研究表明，烯丙基硫醚的磺氧化反应具有高化学选择性。
• Copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water
  作者：Yu Yang、Yajie Bao、Qianqian Guan、Qi Sun、Zhenggen Zha、Zhiyong Wang

  DOI：10.1039/c6gc03142k

  日期：——

  A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP was efficiently developed, providing a variety of methyl sulfones with good to excellent yields. The reaction can be carried out in water...

  高效开发了铜与TBHP催化的磺酰肼的S-甲基化反应，从而提供了多种具有良好至极佳收率的甲基砜。该反应可以在水中进行。
• Copper-catalyzed conjugate additions of organozirconocenes. Synthetic and mechanistic studies.
  作者：Peter Wipf、Wenjing Xu、Jacqueline H. Smitrovich、Roman Lehmann、Luigi M. Venanzi

  DOI：10.1016/s0040-4020(01)85058-4

  日期：1994.2

  broad range of functional groups are tolerated in the conjugate addition process. Unsaturated N-acyl oxazolidinones give high diastereoselectivities for the formation of the new asymmetric carbon. The resulting zirconium enolates can be used for tandem aldol addition reactions to aldehydes. Depending on the type of copper salt used, slow or fast formation of copper mirror occurs, but no intermediate

  在3–10 mol％的Cu（l）盐（例如CuBr·S Me 2或CuCN）存在下，烷基锆茂金属很容易添加到α，β-不饱和酮，醛和砜中。反应产率对路易斯酸和碱的存在敏感。在共轭加成过程中可以耐受立体位阻以及广泛的官能团。不饱和氮-酰基恶唑烷酮类对形成新的不对称碳具有高的非对映选择性。所得的烯醇锆可用于醛醇的串联醇醛加成反应。根据所用铜盐的类型，会发生缓慢或快速形成铜镜的现象，但是在光谱学上没有检测到中间的铜物种。因此，提出了一种机理，该机理涉及路易斯酸性的锆茂并烯的烯酮络合，然后烷基取代基的内球转移到螯合的Cu（l）上。