1-(chloromethyl)-4-<(n-octylsulfinyl)methyl>benzene | 200259-02-5

• 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: 1-(chloromethyl)-4-<(n-octylsulfinyl)methyl>benzene
• 英文别名: α-chloro-α'-octylsulfinyl-p-xylene；(chloromethyl)-4-[(octylsulfinyl)methyl]benzene；1-(chloromethyl)-4-[(n-octylsulfinyl)methyl]benzene；1-(chloromethyl)-4-(octylsulfinylmethyl)benzene
• CAS: 200259-02-5
• 化学式: C₁₆H₂₅ClOS
• 分子量: 300.893
• InChiKey: SRDSTVPEVFVCPS-UHFFFAOYSA-N

物化性质

• 熔点：
  109.5-110.5 °C
• 沸点：
  466.1±33.0 °C(Predicted)
• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(chloromethyl)-4-<(n-octylsulfinyl)methyl>benzene 在 间氯过氧苯甲酸 、 sodium t-butanolate 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Kinetic and Mechanistic Study on p-Quinodimethane Formation in the Sulfinyl Precursor Route for the Polymerization of Poly(p-phenylenevinylene) (PPV)

  摘要：

  The kinetics of p-quinodimethane formation in the sulfinyl precursor route for the poly(p-phenylenevinylene) (PPV) polymerization was studied using stop-flow UV-vis spectroscopy and theoretical first principle calculations. Different sulfinyl monomers were studied by means of quantitative kinetic experiments regarding the p-quinodimethane formation in 2-butanol. The influence of the solvent, the nature of the aromatic moiety, and the substituents on the phenyl core was analyzed by means of qualitative experiments. Quantitative measurements, using pseudo-first-order reaction conditions, were performed in order to assess the effect of the polarizer and the leaving group on the reaction rates. To obtain additional fundamental insight into the pathway leading to p-quinodimethane formation, density functional theory calculations were performed and subsequent reaction rate coefficients were determined from a theoretical point of view, enabling a profound comparison with experiment. From all these data, an E-2 mechanism is proposed for the p-quinodimethane formation in the sulfinyl precursor route.

  DOI：

  10.1021/ma1013012
• 作为产物：
  描述：

  1,4-对二氯苄 在 盐酸 、 tellurium oxide 、 双氧水 、 sodium t-butanolate 作用下， 以 水 为溶剂， 生成 1-(chloromethyl)-4-<(n-octylsulfinyl)methyl>benzene
  参考文献：
  名称：

  通过亚磺酰基前体路线发现高分子量PPV衍生物的阴离子聚合机理

  摘要：

  已经研究了通过亚磺酰基前体途径进行的PPV聚合反应的机理。在几秒钟内聚合-丁醇，在大多数前体聚合路线中观察到纯自由基聚合机理。因此，反应温度的升高引起总产率的提高，同时聚合物的平均分子量降低。在添加碱NatBuO之前改变溶液中的单体浓度，观察到分子量增加，这表明聚合比两种反应组分的混合快。当将溶剂更改为NMP时，已经建立了阴离子和自由基聚合的竞争关系，而在THF中，阴离子聚合机理专门发生。为了防止终止反应，引入LDA和LHMDS作为基础，由于较高的位阻，LHMDS显示引发阴离子链增长的倾向较小。

  DOI：

  10.1021/ma201453s

文献信息

• Highly Selective Route for Producing Unsymmetrically Substituted Monomers toward Synthesis of Conjugated Polymers Derived from Poly(<i>p</i>-phenylene vinylene)
  作者：Albert J. J. M. van Breemen、Dirk J. M. Vanderzande、Peter J. Adriaensens、Jan M. J. V. Gelan

  DOI：10.1021/jo9821022

  日期：1999.4.1

  A new convenient route for producing unsymmetrically substituted sulfinyl monomers of precursor polymers toward poly(p-phenylene vinylene) is described. Upon treating a symmetrical bissulfonium salt with a thiolate anion, an unexpected high selectivity for the monosubstituted thioethers (90%) is obtained. Optimization of the reaction conditions showed that the stoichiometry of the reactants in this

  描述了一种制备前体聚合物的不对称取代的亚磺酰基单体向聚对苯撑亚乙烯基的简便方法。用硫醇盐阴离子处理对称的双s盐时，获得了对单取代硫醚的出乎意料的高选择性（90％）。反应条件的优化表明，该反应中反应物的化学计量对于确保高选择性和防止不希望的副反应很重要。等摩尔量的试剂在环境温度下反应可获得最佳结果。提出了与这些结果一致的机理，并得到了紫外线可见光实验的支持。硫醚的选择性氧化产生亚磺酰基单体。通过使用此新路线，可以将总产量提高2倍
• Scope and Limitations of a New Highly Selective Synthesis of Unsymmetrical Monomers for the Synthesis of Precursors toward Poly(arylenevinylene)s
  作者：Michael Van Der Borght、Dirk Vanderzande、Peter Adriaensens、Jan Gelan

  DOI：10.1021/jo990111k

  日期：2000.1.1

  In our laboratory a precursor route to poly(p-phenylenevinylene) derivatives is developed in which unsymmetrically substituted p-xylene derivatives, possessing a benzylic sulfinylalkyl group, are used as monomers. Because of this unsymmetry, we were forced to investigate thoroughly the synthesis of these sulfoxides, as we start from symmetric and readily accessible molecules, namely, bis(halomethyl)-p-xylene

  在我们的实验室中，开发了一种制备聚对对苯乙炔衍生物的前体路线，其中使用具有亚苄基亚磺酰基烷基的不对称取代的对二甲苯衍生物作为单体。由于这种不对称性，我们被迫彻底研究这些亚砜的合成，因为我们从对称且易于获得的分子即双（卤代甲基）-对二甲苯衍生物开始。在以前的出版物中，提出了生产这些不对称取代的亚磺酰基单体的极其有效的新途径。本文扩展了这些先前报告的结果。为了检查这种优雅路线的范围和局限性，将该新方法应用于初始工作中未包括的各种衍生物的合成。
• Complete assignment of1H and13C NMR spectra of a set of sulphinyl and sulphonyl monomers toward poly(p-phenylenevinylene) precursors
  作者：Albert J. J. M. van Breemen、Peter J. Adriaensens、Anna C. J. Issaris、Margreet M. de Kok、Dirk J. M. Vanderzande、Jan M. J. V. Gelan

  DOI：10.1002/(sici)1097-458x(200002)38:2<129::aid-mrc602>3.0.co;2-k

  日期：2000.2

  The complete assignment of the 1H and 13C NMR spectra of sulphinyl and sulphonyl monomers toward poly(p‐phenylenevinylene) precursors is presented. For all compounds the same protocol could be used. Resonance assignments were achieved by the use of one‐ and two dimensional NMR techniques such as 1H, 13C APT and 2D HETCOR (J = 8 Hz, J = 140 Hz), INADEQUATE and COSY. Copyright © 2000 John Wiley & Sons

  介绍了亚磺酰基和磺酰基单体的 1H 和 13C NMR 光谱对聚（对亚苯基亚乙烯基）前体的完整分配。对于所有化合物，可以使用相同的方案。共振分配是通过使用一维和二维 NMR 技术实现的，例如 1H、13C APT 和 2D HETCOR（J = 8 Hz，J = 140 Hz）、INADEQUATE 和 COSY。版权所有 © 2000 John Wiley & Sons, Ltd.
• Discovery of an Anionic Polymerization Mechanism for High Molecular Weight PPV Derivatives via the Sulfinyl Precursor Route
  作者：Inge Cosemans、Lieve Hontis、David Van Den Berghe、Arne Palmaerts、Jimmy Wouters、Thomas J. Cleij、Laurence Lutsen、Wouter Maes、Tanja Junkers、Dirk J. M. Vanderzande

  DOI：10.1021/ma201453s

  日期：2011.10.11

  of PPV via the sulfinyl precursor route has been investigated with respect to its mechanism. When polymerized in sec-butanol, a purely radical polymerization mechanism is observed as in most precursor polymerization routes. Accordingly, an increase in the reaction temperature induced an increase in the overall yield alongside with a reduction of the average molecular weight of the polymer. Upon changing

  已经研究了通过亚磺酰基前体途径进行的PPV聚合反应的机理。在几秒钟内聚合-丁醇，在大多数前体聚合路线中观察到纯自由基聚合机理。因此，反应温度的升高引起总产率的提高，同时聚合物的平均分子量降低。在添加碱NatBuO之前改变溶液中的单体浓度，观察到分子量增加，这表明聚合比两种反应组分的混合快。当将溶剂更改为NMP时，已经建立了阴离子和自由基聚合的竞争关系，而在THF中，阴离子聚合机理专门发生。为了防止终止反应，引入LDA和LHMDS作为基础，由于较高的位阻，LHMDS显示引发阴离子链增长的倾向较小。
• Kinetic and Mechanistic Study on <i>p-</i>Quinodimethane Formation in the Sulfinyl Precursor Route for the Polymerization of Poly(<i>p</i>-phenylenevinylene) (PPV)
  作者：Laura Hermosilla、Saron Catak、Veronique Van Speybroeck、Michel Waroquier、Joke Vandenbergh、Filip Motmans、Peter Adriaensens、Laurence Lutsen、Thomas Cleij、Dirk Vanderzande

  DOI：10.1021/ma1013012

  日期：2010.9.28

  The kinetics of p-quinodimethane formation in the sulfinyl precursor route for the poly(p-phenylenevinylene) (PPV) polymerization was studied using stop-flow UV-vis spectroscopy and theoretical first principle calculations. Different sulfinyl monomers were studied by means of quantitative kinetic experiments regarding the p-quinodimethane formation in 2-butanol. The influence of the solvent, the nature of the aromatic moiety, and the substituents on the phenyl core was analyzed by means of qualitative experiments. Quantitative measurements, using pseudo-first-order reaction conditions, were performed in order to assess the effect of the polarizer and the leaving group on the reaction rates. To obtain additional fundamental insight into the pathway leading to p-quinodimethane formation, density functional theory calculations were performed and subsequent reaction rate coefficients were determined from a theoretical point of view, enabling a profound comparison with experiment. From all these data, an E-2 mechanism is proposed for the p-quinodimethane formation in the sulfinyl precursor route.