(tert-butylsulfinyl)benzene | 4170-71-2

• 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: (tert-butylsulfinyl)benzene
• 英文别名: tert-butyl phenyl sulfoxide；phenyl tert-butyl sulfoxide；tert-butylsulfinylbenzene
• CAS: 4170-71-2
• 化学式: C₁₀H₁₄OS
• mdl: MFCD02113283
• 分子量: 182.287
• InChiKey: AZUKVBVKGMKZIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  (tert-butylsulfinyl)benzene 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 溶剂黄146 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 1.17h， 生成 3-苯基-1,2-苯并噻唑
  参考文献：
  名称：

  Synthesis of 3-Substituted Aryl[4,5]isothiazoles through an All-Heteroatom Wittig-Equivalent Process

  摘要：

  Extending the previous use of tert-butyl sulfoxide as the sulfinyl source, intramolecular sulfinylation of sulfonamides was successfully performed. The resulting sulfinimides were not isolated and instead were believed to go through an all-heteroatom Wittig-equivalent process to eventually afford aryl[4,5]isothiazoles in high yields.

  DOI：

  10.1021/acs.orglett.6b01338
• 作为产物：
  描述：

  甲基苯基亚砜 在 N-氯代丁二酰亚胺 作用下， 以 二氯甲烷 、 甲苯 、 正戊烷 为溶剂， 反应 48.0h， 生成 (tert-butylsulfinyl)benzene
  参考文献：
  名称：

  On the nature of the chain-extending species in organolithium initiated stereospecific reagent-controlled homologation reactions using α-chloroalkyl aryl sulfoxides

  摘要：

  The reaction of an organolithium with an alpha-chloroalkyl aryl sulfoxide ostensibly generates an alpha-chloroalkyllithium by sulfoxide lithium exchange, but the actual identity of the chain-extending species in chlorosulfoxide-based StReCH reactions is not certain. To explore this issue, racemic 2-cyclohexyl (4R*, 5R*)-4,5-diphenyl-1,3,2-dioxaborolane was homologated by treatment with scalemic (S)-chloromethyl phenyl sulfoxide and n-BuLi (THF, -78 degrees C). The reaction proceeded without a detectable level of kinetic resolution, a finding consistent with chloromethyllithium being the active chain-extending species rather than a chiral sulfurane intermediate. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.08.123
• 作为试剂：
  描述：

  2-氯甲基吡啶盐酸盐 在 (tert-butylsulfinyl)benzene 、 potassium hydride 作用下， 反应 24.0h， 以39%的产率得到(E)-1,2-双(2-吡啶基)乙烯
  参考文献：
  名称：

  tert-Butyl Phenyl Sulfoxide: A Traceless Sulfenate Anion Precatalyst

  摘要：

  tert-Butyl phenyl sulfoxide is employed as a traceless precatalyst for the generation of sulfenate anions under basic conditions and has been used to catalyze the coupling of benzyl halides to trans-stilbenes. The advantage of this precatalyst over previous precatalysts is that the byproduct generated on catalyst formation is a gas, facilitating product isolation in high purity. Using this second generation catalyst, a variety of trans-stilbenes were generated in 39-98% isolated yield.

  DOI：

  10.1021/acs.orglett.5b00117

文献信息

• Synthesis of Sulfoxides by the Hydrogen Peroxide Induced Oxidation of Sulfides Catalyzed by Iron Tetrakis(pentafluorophenyl)porphyrin:  Scope and Chemoselectivity
  作者：Enrico Baciocchi、Maria Francesca Gerini、Andrea Lapi

  DOI：10.1021/jo049879h

  日期：2004.5.1

  The oxidation of sulfides with H2O2 catalyzed by iron tetrakis(pentafluorophenyl)porphyrin in EtOH is an efficient and chemoselective process. With a catalyst concentration 0.03−0.09% of that of the substrate, sulfoxides are obtained with yields generally around 90−95% of isolated product. With vinyl and allyl sulfides, no epoxidation is observed. With a catalyst concentration between 0.09% and 0.25%

  四（五氟苯基）卟啉铁在EtOH中催化的H 2 O 2氧化硫化物是一种有效的化学选择过程。在催化剂浓度为底物浓度的0.03-0.09％的情况下，获得的亚砜的收率通常约为分离产物的90-95％。对于乙烯基和烯丙基硫化物，未观察到环氧化。催化剂浓度为底物浓度的0.09％至0.25％，可以以几乎定量的产率获得砜，并且在亚砜的合成中观察到相同的高化学选择性。
• Electron-Deficient Heteroarenium Salts: An Organocatalytic Tool for Activation of Hydrogen Peroxide in Oxidations
  作者：Jiří Šturala、Soňa Boháčová、Josef Chudoba、Radka Metelková、Radek Cibulka

  DOI：10.1021/jo502865f

  日期：2015.3.6

  prepared and tested as simple catalysts of oxidations with hydrogen peroxide, using sulfoxidation as a model reaction. Their catalytic efficiency strongly depends on the type of substituent and is remarkable for derivatives with an electron-withdrawing group, showing reactivity comparable to that of flavinium salts which are the prominent organocatalysts for oxygenations. Because of their high stability

  制备了一系列的单取代的嘧啶鎓和吡嗪鎓三氟甲磺酸酯和3,5-二取代的吡啶鎓三氟甲磺酸酯，并使用硫氧化作为模型反应，对过氧化氢的简单氧化催化剂进行了测试。它们的催化效率在很大程度上取决于取代基的类型，并且对于具有吸电子基团的衍生物而言是显着的，其反应性与黄酮盐相当，后者是氧合作用的主要有机催化剂。由于它们的高稳定性和良好的可及性，4-（三氟甲基）嘧啶鎓和3,5-二硝基吡啶鎓三氟甲磺酸盐是选择的催化剂，并显示出催化脂肪族和芳香族硫化物氧化为亚砜的作用，定量转化率高，制备产率高，并且具有优异的性能。化学选择性。K R +值（p K R + <5）和较小的负还原电位（E red > -0.5 V）。在催化氧化过程中原位形成的过氧化氢加合物充当底物氧化剂。通过在B3LYP / 6-311 ++ g（d，p）水平上的计算获得的从这些杂环氢过氧化物到硫代苯甲醚的转移的吉布斯自由能表明，它们是比烷基氢过氧化
• Synthesis of New Sulfoxide-Containing Diselenides and Unexpected Cyclization Reactions to 2,3-Dihydro-1,4-benzoselenothiine 1-Oxides
  作者：Diana M. Freudendahl、Michio Iwaoka、Thomas Wirth

  DOI：10.1002/ejoc.201000514

  日期：——

  functionalization of alkenes. The influence of solvents and different nucleophiles on the outcome of the selenenylation reaction was studied. Besides the successful selenenylation reactions, one selenium electrophile showed an unexpected reactivity in forming a six-membered heterocyclic system upon reaction with alkenes. A mechanism for the formation of these 2,3-dihydro-1,4-benzoselenothiine 1-oxides is proposed

  制备了新型手性含亚砜的二硒化物，并将其相应的硒亲电试剂用于烯烃的立体选择性功能化。研究了溶剂和不同亲核试剂对硒基化反应结果的影响。除了成功的硒基化反应外，一种硒亲电试剂在与烯烃反应后形成六元杂环系统时表现出意想不到的反应性。提出了这些 2,3-二氢-1,4-苯硒代硒 1-氧化物的形成机制。
• Thermolysis-Induced Two- or Multicomponent Tandem Reactions Involving Isocyanides and Sulfenic-Acid-Generating Sulfoxides: Access to Diverse Sulfur-Containing Functional Scaffolds
  作者：Shengfeng Wu、Xiaofang Lei、Erkang Fan、Zhihua Sun

  DOI：10.1021/acs.orglett.7b03593

  日期：2018.2.2

  Direct reaction of isocyanides with some sulfenic-acid-generating sulfoxides led to the effective formation of the corresponding thiocarbamic acid S-esters in good to high yields. A multicomponent reaction involving isocyanide, sulfoxide, and a suitable nucleophile has also been developed, providing ready access to a diverse range of sulfur-containing compounds, including isothioureas, carbonimidothioic

  异氰酸酯与一些产生亚磺酸的亚砜的直接反应导致以高至高收率有效地形成相应的硫代氨基甲酸S-酯。还开发了涉及异氰酸酯，亚砜和合适的亲核试剂的多组分反应，可轻松获得各种范围的含硫化合物，包括异硫脲，碳亚氨基硫代酸酯和羧亚氨基硫代酸酯。
• Acid-Catalyzed Synthesis of Aryl[4,5]isothiazoles through a Sulfenic Acid Pathway
  作者：Hong Yuan、Zhihua Sun

  DOI：10.1055/s-0039-1690201

  日期：2019.10

  A new method to efficiently prepare 3-substituted aryl[4,5]isothiazoles by simply heating the starting materials with a catalytic amount of p-toluenesulfonic acid in toluene is reported. This simple procedure is well suitable for a variety of substrates that can tolerate substitution changes in the fusing aromatic ring, as well as at the 3-position. Substituted aryl rings of varying electronic properties

  报道了一种通过简单地加热原料与催化量的甲苯磺酸在甲苯中有效制备 3-取代芳基 [4,5] 异噻唑的新方法。这种简单的程序非常适用于可以容忍稠合芳环以及 3 位取代变化的各种底物。不同电子性质和烷基取代的取代芳环最终以高产率提供芳基[4,5]异噻唑。