tert-butyl 4-methylphenyl sulfoxide | 67501-10-4

• 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: tert-butyl 4-methylphenyl sulfoxide
• 英文别名: 1-(tert-butylsulfinyl)-4-methylbenzene；tert-butyl p-tolyl sulfoxide；t-butyl p-tolyl sulfoxide；t-Butyl p-methylphenyl sulfoxide；1-tert-butylsulfinyl-4-methylbenzene
• CAS: 67501-10-4
• 化学式: C₁₁H₁₆OS
• 分子量: 196.313
• InChiKey: CUHLCVDOSQPTSU-UHFFFAOYSA-N

物化性质

• 熔点：
  91-93 °C
• 沸点：
  311.7±21.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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-butyl 4-methylphenyl sulfoxide 在 四氯化钛 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以90%的产率得到叔丁基(4-甲基苯基)硫醚
  参考文献：
  名称：

  Ph 3 P /路易斯酸组合介导的亚砜的脱氧作用及其在旋光膦动力学拆分中的应用

  摘要：

  发现Ph 3 P / TiCl 4的组合是亚砜脱氧的有效促进剂，并且在温和的条件下以良好的收率（最高97％）提供了相应的硫化物。将该方法应用于外消旋膦与（R）-甲基对甲苯基亚砜之间的反应，发现在中等选择性下实现了动力学拆分。

  DOI：

  10.1016/j.tet.2005.01.127
• 作为产物：
  描述：

  (-)-menthyl p-toluenesulfinate 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.25h， 生成 tert-butyl 4-methylphenyl sulfoxide
  参考文献：
  名称：

  Extremely facile ligand-exchange and disproportionation reactions of diaryl sulfoxides, selenoxides, and triarylphosphine oxides with organolithium and Grignard reagents

  摘要：

  Diaryl sulfoxides undergo unusually rapid ligand-exchange reaction upon treatment with organolithium reagents at -95-degrees-C. Optically pure phenyl p-tolyl sulfoxide (4b) reacted with organolithium reagents at the range from -20 to -95-degrees-C to give facile ligand-exchange and disproportionation products, i.e., diphenyl sulfoxide (7), recovered 4b, and di-p-tolyl sulfoxide (8) in a statistical ratio of 1:2:1 in quantitative yields, and the recovered 4b was completely racemized. This facile ligand exchange was observed in the similar reactions using only diaryl selenoxides and triarylphosphine oxides. The reactions of O-18-labeled phenyl p-tolyl sulfoxide (4c) with organolithium reagents gave products in a statistical ratio without O-18 scrambling, indicating that only the C-S bond cleavage took place under low temperature. It is suggested that the ligand exchange reactions occur by the nucleophilic attack by organolithium reagent at the sulfinyl sulfur atom, giving sigma-sulfurane as an intermediate that collapses rapidly. These results suggest that the treatment of arylic sulfoxides, selenoxides, and phosphine oxides with strong bases should be effected with caution.

  DOI：

  10.1021/jo00022a024

文献信息

• Racemization of sulfinic esters with trichloroacetic anhydride
  作者：Jozef Drabowicz、Shigeru Oae

  DOI：10.1016/0040-4020(78)88037-5

  日期：1978.1

  Both alkane- and arene-sulfinates undergo racemization and oxygen exchange reaction with trich-loroacetic anhydride. The rate of racemization of (−)menthyl (−)p-toluenesulfinate was found to be twice that of oxygen exchange, suggesting the reaction involves a Walden inversion. When reaction was carried out in benzene, the rate of racemization was found to be first order with respect to both sulfinic

  链烷烃和芳烃亚磺酸盐均与外消旋-氯代乙酸酐发生消旋和氧交换反应。发现（-）薄荷基（-）对甲苯磺酸盐的外消旋速率是氧交换速率的两倍，这表明该反应涉及Walden转化。当在苯中进行反应时，发现对于亚磺酸酯和三氯乙酸酐而言，外消旋化的速度都是一级的。取代基效应大（p = -1.53​​），表明初始的酰化作用是决定速率的步骤。发现通过加入全卤代乙酸可抑制外消旋化的速率，同时观察到氯化汞的催化作用很小。
• Generation of oxiranyllithiums and oxiranyl Grignard reagents having a carbanion-destabilizing group from sulfinyloxiranes: Their property and an application to asymmetric synthesis of epoxides and alcohols
  作者：Tsuyoshi Satoh、Shigeko Kobayashi、Shino Nakanishi、Kyoko Horiguchi、Shiro Irisa

  DOI：10.1016/s0040-4020(99)00038-1

  日期：1999.2

  The first generation of oxiranyllithiums and oxiranyl Grignard reagents having a carbanion-destabilizing group (alkyl group) was realized from sulfinyloxiranes via the ligand exchange reaction of sulfoxides with tert-butyllithium or ethylmagnesium chloride in THF at −80 to −100°C. The generated oxiranyllithiums were found to be very unstable; however, these anions reacted with several electrophiles

  通过亚砜与叔丁基锂或乙基氯化镁在THF中于-80至-100°C下进行的亚砜配位体交换反应，由亚磺酰基氧杂环戊烷实现了具有碳负离子稳定基团（烷基）的第一代环氧乙烷基锂和环氧乙烷基格氏试剂。发现生成的环氧乙烷基锂非常不稳定。然而，这些阴离子与几种亲电试剂反应生成环氧化物，收率高达86％。发现环氧乙烷基格氏试剂比环氧乙烷基锂更稳定且反应性更差。研究了具有几个烷基的环氧乙烷基锂的反应性。作为该方法的应用，由光学活性的氯甲基对苯二酚合成了光学活性的三和四取代的环氧化物和醇-经由甲苯氧基锂的甲苯基亚砜。
• One-Pot Sulfoxide Synthesis Exploiting a Sulfinyl-Dication Equivalent Generated from a DABSO/Trimethylsilyl Chloride Sequence
  作者：Danny C. Lenstra、Vincent Vedovato、Emmanuel Ferrer Flegeau、Jonathan Maydom、Michael C. Willis

  DOI：10.1021/acs.orglett.6b00712

  日期：2016.5.6

  sulfinate intermediate. In situ conversion of the sulfinate to a sulfinate silyl ester, using TMS-Cl (trimethylsilyl chloride), generates a second electrophile, allowing addition of a second organometallic reagent. Organolithium or Grignard reagents can be employed, delivering sulfoxides in good to excellent yields.

  描述了一种使用有机金属亲核试剂合成不对称亚砜的一锅法。从替代DABSO（DABCO- bis（二氧化硫））输送的二氧化硫用作初始亲电试剂，并与第一种有机金属试剂结合生成亚磺酸盐中间体。使用TMS-Cl（三甲基甲硅烷基氯）将亚磺酸盐原位转化为亚磺酸盐甲硅烷基酯可生成第二亲电试剂，从而可添加第二有机金属试剂。可以使用有机锂或格氏试剂，以高至极好的收率递送亚砜。
• <i>tert</i>-Butyl Sulfoxides: Key Precursors for Palladium-Catalyzed Arylation of Sulfenate Salts
  作者：Fabien Gelat、Jean-François Lohier、Annie-Claude Gaumont、Stéphane Perrio

  DOI：10.1002/adsc.201500368

  日期：2015.6.15

  clean generation of sulfenate salts (R1SO−) by pyrolysis of readily available tert‐butyl sulfoxides to give sulfenic acids (R1SOH) and traceless isobutene, followed by hydrogen abstraction with a weak inorganic base (K3PO4). The relevance of this process was exemplified through an in situ palladium‐catalyzed cross‐coupling reaction with aryl halides/triflates leading to aryl sulfoxides. The operationally

  本报告描述了一种高效洁净代次磺酸的盐（R 1 SO - ）通过热解容易获得的叔丁基亚砜，得到次磺酸（R 1 SOH）和无痕迹的异丁烯，随后夺氢用弱无机碱（ K 3 PO 4）。该过程的相关性通过与芳基卤化物/三氟甲磺酸酯生成芳基亚砜的原位钯催化交叉偶联反应得到了例证。开发的操作简单的CS键形成协议使用Pd（dba）2作为催化剂，Xantphos作为甲苯或甲苯/ H 2中的配体O混合物。进一步的扩展包括使用二叔丁基亚砜作为一氧化硫二价阴离子（SO 2−）的等同物，并开发了[2.2]对环环烷和联芳基系列的非对映选择性形式。
• Palladium-Catalyzed Amination of Aryl Sulfoxides
  作者：Yuto Yoshida、Shinya Otsuka、Keisuke Nogi、Hideki Yorimitsu

  DOI：10.1021/acs.orglett.8b00060

  日期：2018.2.16

  Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C–S bond amination reactions. This amination

  在钯/ N-杂环卡宾（NHC）催化下，已用苯胺和烷基胺对二芳基亚砜进行了胺化。由于其电子缺乏，与先前的C-S键胺化反应相比，在较温和的反应条件下，离开的芳烃磺酸根阴离子会从钯中心平稳释放，从而导致催化剂的转换平稳。该胺化容纳更广泛的官能团，例如甲硅烷基，硼烷基，甲基硫烷基和卤素部分。不对称二芳基亚砜的区域选择性胺化也通过空间偏倚进行。