2-phenylethyl 4-nitrophenyl sulfide | 60091-82-9

• 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: 2-phenylethyl 4-nitrophenyl sulfide
• 英文别名: p-nitrophenyl 2-phenylethyl sulfide；(4-nitrophenyl)(phenethyl)sulfane；1-nitro-4-[(2-phenylethyl)sulfanyl]benzene；4-(2'-Phenyl-aethylthio)-nitrobenzol；4-(2'-phenyl-ethylthio)-nitrobenzene；1-nitro-4-(2-phenylethylsulfanyl)benzene
• CAS: 60091-82-9
• 化学式: C₁₄H₁₃NO₂S
• 分子量: 259.329
• InChiKey: BYZMQPUNDQFGTK-UHFFFAOYSA-N

物化性质

• 沸点：
  419.3±38.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-phenylethyl 4-nitrophenyl sulfide 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 2-phenylethyl 4-nitrophenyl sulfone
  参考文献：
  名称：

  Photooxidation of Alkyl 4-Nitrophenyl Sulfides and Sulfoxides. Observation of Oxidative C-S Bond Cleavage and Rearrangement Reactions

  摘要：

  Alkyl 4-nitrophenyl sulfides and sulfoxides undergo a self-photoinduced, singlet oxygen oxidation to produce a variety of products, including sulfonates and carbonyl compounds formed by the oxidative cleavage of the C-S bond of the sulfides and sulfoxides. Structural rearrangements are observed in the resulting carbonyl compounds formed in the oxidative cleavage of the C-S bond in the tert-amyl and 2-phenylethyl sulfides. An overall mechanism is proposed which involves the formation of peroxysulfoxides and peroxysulfones which undergo heterolytic C-S bond cleavage to form ion pairs which recombine to form persulfenates or persulfinates which then undergo photo- and/or thermally-induced homolytic O-O bond cleavage to form alkoxy and sulfinyl or sulfonyl radicals. The alkoxy radicals undergo beta-scission, disproportionation, or recombination with the sulfonyl radical to form the observed products. These C-S oxidative cleavage reactions have only been rarely observed in the earlier studies on the singlet oxygen oxidation studies of dialkyl sulfides, and are attributed, in part, to the presence of the 4-nitro group on the aromatic ring which greatly affects the susceptibility of the sulfur atom of the sulfides and sulfoxides toward nucleophilic attack, and on the reactivity of the peroxysulfoxides and peroxysulfones toward heterolytic cleavage of the O-S bond.

  DOI：

  10.1021/ja00099a015
• 作为产物：
  描述：

  4-硝基苯乙烯 、 4-甲苯硫酚 在 三(五氟苯基)硼烷 作用下， 反应 1.5h， 以76%的产率得到2-phenylethyl 4-nitrophenyl sulfide
  参考文献：
  名称：

  一种无过渡金属催化的不饱和烯烃制备硫醚的方法

  摘要：

  本发明涉及一种无过渡金属催化不饱和烯烃与硫酚反应制备硫醚的合成方法。该方法如下：在向反应管中加入不饱和烯烃底物和硫酚底物，然后加入催化量的三五氟苯基硼，在30‑80℃时反应1‑24小时后得到硫醚化合物。本发明的主要创新点在于不使用过渡金属催化剂即可高效制备硫醚化合物，避免了重金属污染。该方法具有绿色无溶剂、操作简便、条件温和、反应迅速、底物普适性好、和反应收率及选择性高等优点。

  公开号：

  CN111087331B

文献信息

• Pyrolysis of (2-Phenylethyl)phenylsulfonium Ylides.
  作者：Toshiaki Yoshimura、Atsushi Motoyama、Akiko Morishige、Eiichi Tsukurimichi、Choichiro Shimasaki、Kiyoshi Hasegawa

  DOI：10.1246/bcsj.66.174

  日期：——

  In order to obtain information concerning the reaction mechanism of the pyrolysis of sulfonium ylides bearing a substituted phenyl group on the 2-position in the S-ethyl group of ethylphenylsulfonium ylide, (2-phenylethyl)phenylsulfonium bis(methoxycarbonyl)methylide (1) and dicyanomethylide (2) were subjected to pyrolysis in benzene. The reaction rates of 1 and 2 at 140 °C were 6.0- and 3.2-times faster than those of ethylphenylsulfonium bis(methoxycarbonyl)methylide and dicyanomethylide, respectively. The activation parameters for 1 were ΔH‡ = 125 kJ mol−1 and ΔS‡ = −3.8 J K−1 mol−1, while those for 2 were ΔH‡ = 124 kJ mol−1 and ΔS‡ = −2.5 J K−1 mol−1. Substituent effects on the β-phenyl groups in 1 and 2 afforded positive Hammett ρ-values: ρ = 0.49 (γ = 0.997) and ρ = 0.26 (γ = 0.993), respectively.From the obtained results, it was suggested that the pyrolysis proceeds through essentially a concerted intramolecular cis-elimination inclined toward a slightly carbanion-like type from an E1-like type by introducing a phenyl substituent at the 2-position of the ethyl group in the ethylphenylsulfonium ylide.

  为了获取有关乙基苯基亚磺酸乙酯中乙基的2-位上带有取代苯基的磺酸亚磺酸分解反应机理的信息，将（2-苯乙基）苯基亚磺酸双（甲氧基羰基）甲亚基（1）和双氰基甲亚基（2）在苯中进行分解。在140°C时，1和2的反应速率分别比乙基苯基亚磺酸双（甲氧基羰基）甲亚基和双氰基甲亚基快6.0倍和3.2倍。1的活化参数为ΔH‡ = 125 kJ mol−1，ΔS‡ = -3.8 J K−1 mol−1，而2的活化参数为ΔH‡ = 124 kJ mol−1，ΔS‡ = -2.5 J K−1 mol−1。1和2中β-苯基的取代效应提供了正的Hammett ρ值：ρ = 0.49（γ = 0.997）和ρ = 0.26（γ = 0.993）。从得到的结果可以看出，通过在乙基苯基亚磺酸乙的乙基的2-位引入苯基取代基，基本上是通过倾向于稍微类似于碳负离子的顺式消除过程，从而类似于E1型反应。
• Pyrolysis of Sulfoxide Bearing Electron-Withdrawing Substituents on β-Position in<i>S</i>-Ethyl Group of Ethyl Phenyl Sulfoxide
  作者：Toshiaki Yoshimura、Masaki Yoshizawa、Eiichi Tsukurimichi

  DOI：10.1246/bcsj.60.2491

  日期：1987.7

  In order to obtain information concerning the reaction mechanism of the pyrolysis of a sulfoxide bearing an electron-withdrawing substituent on the β-position in the S-ethyl group of ethyl phenyl sulfoxide, 2-(substituted phenyl)ethyl aryl sulfoxides(1) and 2-cyanoethyl (substituted phenyl) sulfoxides(2) were pyrolyzed. The rate-enhancing effect of the β-phenyl group of 1 was small. The activation

  为了获得有关在乙基苯基亚砜的 S-乙基基团的 β-位上带有吸电子取代基的亚砜热解反应机理的信息，2-（取代苯基）乙基芳基亚砜（1）和2-氰乙基（取代苯基）亚砜（2）被热解。1的β-苯基基团的速率增强效果很小。发现 1 的活化焓和熵分别为 110 kJ mol-1 和 -45 JK-1 mol-1。1 的哈米特图给出了取代基的正趋势，在 β-苯基 (ρ=0.76) 和 S-苯基 (ρ=0.32) 上，尽管后者的 ρ 值约为前者的一半. 另一方面，2 的哈米特图没有给出一条直线，但是一个凹曲线，其中从 p-OCH3 到 p-Cl 基团的一系列取代基呈现负趋势（ρ=-0.49），而 p-NO2 基团呈现正趋势。发现 2 的热解速率在 100 °C 时比 1 的热解速率快约 23 倍。这 ...
• The use of aminoiminomethanesulfinic acid (thiourea dioxide) under phase transfer conditions for generating organochalcogenate anions. Synthesis of sulfides, selenides and tellurides
  作者：J.V. Comasseto、E.S. Lang、J. Tercio、B. Ferreira、F. Simonelli、V.R. Correia

  DOI：10.1016/0022-328x(87)80095-5

  日期：1987.11

  quenched by alkyl and activated aryl halides to give the corresponding sulfides and selenides in high yield (77–97%). The aryltellurolates react with alkyl halides giving the aryl alkyl tellurides in 81–96% yield. The procedure could not be successfully used for the synthesis of dialkylselenides and dialkyl tellurides; low yields and mixture of products were formed.

  描述了一种方法，该方法允许在相转移条件下从相应的二有机二硫代碳酸酯开始原位合成芳基烷基，二芳基和二烷基硫属化物。在碱性介质中，氨基亚氨基甲烷亚磺酸（二氧化硫脲）可还原二氰化物，并由季铵盐催化。对于二芳基二硫化物和二芳基二硒化物，在氢氧化钠浓度为13％时，还原很容易进行；二芳基二碲化物需要50％的氢氧化钠溶液以生成芳基碲酸根阴离子。二烷基二硒化物和二烷基二碲化物更难以还原。用烷基和活化的芳基卤化物淬灭中间体芳基硫醇盐和芳基硒酸酯，可以高产率（77-97％）得到相应的硫化物和硒化物。芳碲酸铝盐与烷基卤化物反应，得到芳基烷基碲化物，收率为81–96％。该方法不能成功地用于合成二烷基硒化物和二烷基碲化物。收率低并且形成了产物的混合物。
• Arylisothiocyanate for the regulation of plant growth
  申请人：Ciba-Geigy Corporation

  公开号：US04004907A1

  公开（公告）日：1977-01-25

  New arylisothiocyanates corresponding to the formula ##STR1## wherein R represents alkyl, alkoxy or halogen X represents oxygen or sulfur and P represents an integer of from 2 to 5 are disclosed. They can be used for the regulation of plant growth especially for the dessication and defoliation of unlignified parts of plants above the soil.

  揭示了符合以下公式##STR1##的新芳基异硫氰酸酯，其中R代表烷基、烷氧基或卤素，X代表氧或硫，P代表从2到5的整数。它们可用于植物生长的调节，尤其适用于植物地上无木质化部分的脱水和落叶。
• Few‐layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low‐valence Metals
  作者：María Tejeda‐Serrano、Vicent Lloret、Bence G. Márkus、Ferenc Simon、Frank Hauke、Andreas Hirsch、Antonio Doménech‐Carbó、Gonzalo Abellán、Antonio Leyva‐Pérez

  DOI：10.1002/cctc.201902276

  日期：2020.4.20

  only in the fundamentals but also in the economic and ecological fingerprint of organic reactions. Here we show that few-layer black phosphorous (FL-BP), a recently discovered and now readily available 2D material, catalyzes different radical additions to alkenes with an initial turnover frequency (TOF0) up to two orders of magnitude higher than representative state-of-the-art metal complex catalysts

  用p区主要元素替代催化金属不仅对有机反应的基本原理而且对经济和生态指纹产生巨大影响。在这里，我们展示了少层黑磷（FL-BP），一种最近发现且现在容易获得的二维材料，可以催化烯烃的不同自由基加成，其初始周转频率（TOF0）比代表性状态高出两个数量级 -室温下最先进的金属配合物催化剂。相应的富电子 BP 插层化合物 (BPIC) KP6 的 TOF0 相对于 FL-BP 增加了近两倍。相对于中性对应物，催化活性的增加也发生在其他 2D 材料（石墨烯与 KC8）和金属络合物催化剂（Fe0 与 Fe2-一氧化碳络合物）中。这种反应性并行性为有机合成中二维材料和金属催化剂之间的交叉应用打开了大门。