2-(p-tolylsulfinyl)naphthalene | 136378-30-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-(p-tolylsulfinyl)naphthalene
• 英文别名: 2-naphthyl p-tolyl sulphoxide；2-naphthyl p-tolyl sulfoxide；2-naphthyl-p-tolyl sulfoxide；4-tolyl 2-naphthyl sulfoxide；2-(4-Methylphenyl)sulfinylnaphthalene
• CAS: 136378-30-8
• 化学式: C₁₇H₁₄OS
• 分子量: 266.364
• InChiKey: BCCQOBBTOZONKY-UHFFFAOYSA-N

物化性质

• 熔点：
  82-84 °C
• 沸点：
  461.5±24.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  2-(p-tolylsulfinyl)naphthalene 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 以33%的产率得到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
• 作为产物：
  描述：

  2-naphthalenesulfinyl chloride 以 吡啶 、 乙醚 为溶剂， 生成 2-(p-tolylsulfinyl)naphthalene
  参考文献：
  名称：

  碳水化合物在制备光学活性亚砜中的用途

  摘要：

  由芳烃亚磺酰氯和1,2：5,6-二-O-环己叉基-D-葡萄糖呋喃糖形成的非对映异构亚磺酸酯在用格氏试剂处理时提供旋光性亚砜。

  DOI：

  10.1039/c39810000505

文献信息

• Aryl Sulfoxides via Palladium-Catalyzed Arylation of Sulfenate Anions
  作者：Guillaume Maitro、Sophie Vogel、Guillaume Prestat、David Madec、Giovanni Poli

  DOI：10.1021/ol062315a

  日期：2006.12.1

  [Structure: see text] Palladium-catalyzed arylation of sulfenate anions generated from beta-sulfinyl esters can take place under biphasic conditions. This hitherto unknown reaction provides a simple, mild, and efficient route to aryl sulfoxides in good yields. The development of a new pseudo-domino type I procedure involving a sulfinylation followed by a Mirozoki-Heck coupling is also described.

  [结构：见正文]由β-亚磺酰基酯生成的亚硫酸根阴离子的钯催化芳基化反应可在两相条件下进行。迄今为止未知的反应提供了简单，温和且有效的途径，以高收率制备芳基亚砜。还描述了涉及亚磺酰基化然后进行Mirozoki-Heck偶联的新的假多米诺骨牌I型程序的开发。
• Palladium-Catalyzed Sulfinylation of Aryl- and Alkenylborons with Sulfinate Esters
  作者：Minori Suzuki、Kazuya Kanemoto、Yu Nakamura、Takamitsu Hosoya、Suguru Yoshida

  DOI：10.1021/acs.orglett.1c01292

  日期：2021.5.7

  An efficient, direct sulfinylation of organoborons catalyzed by palladium is disclosed. Treatment of organoborons and sulfinate esters in the presence of a palladium precatalyst provided a broad range of sulfoxides. Various organosulfur compounds having oxidizable functional groups were successfully prepared through the sulfoxide synthesis.

  公开了由钯催化的有机硼的有效的直接亚磺酰基化。在钯预催化剂的存在下处理有机硼和亚磺酸酯可提供广泛的亚砜。通过亚砜合成成功地制备了具有可氧化官能团的各种有机硫化合物。
• Aryl Sulfoxides from Allyl Sulfoxides via [2,3]-Sigmatropic Rearrangement and Domino Pd-Catalyzed Generation/Arylation of Sulfenate Anions
  作者：Elise Bernoud、Gaëtan Le Duc、Xavier Bantreil、Guillaume Prestat、David Madec、Giovanni Poli

  DOI：10.1021/ol902620t

  日期：2010.1.15

  Allylic sulfoxides, via [2,3]-sigmatropic rearrangement and oxidative addition of the resulting allylic sulfenate esters to Pd(0), are found to be excellent precursors of sulfenate anions. This hitherto unknown reactivity is applied in a new Pd(0)-catalyzed domino sequence involving sulfenate anion generation followed by arylation to afford aryl sulfoxides.

  烯丙基亚砜通过[2,3]-σ重排和氧化生成的烯丙基亚磺酸酯到Pd（0）的氧化添加被发现是亚硫酸根阴离子的优良前体。迄今未知的反应性被应用于新的Pd（0）催化的多米诺骨牌序列中，该序列涉及亚硫酸盐阴离子的产生，然后芳基化生成芳基亚砜。
• Metal-Free Cyclopropanol Ring-Opening C(sp³)–C(sp²) Cross-Couplings with Aryl Sulfoxides
  作者：Dengfeng Chen、Yuanyuan Fu、Xiaoji Cao、Jinyue Luo、Fei Wang、Shenlin Huang

  DOI：10.1021/acs.orglett.9b01908

  日期：2019.7.19

  A metal-free method for formal β-arylation/heteroarylation of ketones through efficient cyclopropanol ring-opening cross-couplings with aryl sulfoxides at room temperature has been developed. This protocol shows a broad substrate scope and promising scalability. In addition, the utility of the β-arylated ketones is further demonstrated through a variety of postcoupling transformations and synthetic

  已开发出一种无金属方法，可在室温下通过有效的环丙醇开环交叉偶联与芳基亚砜来进行酮的β-芳基化/杂芳基化反应。该协议显示了广泛的基板范围和有前途的可扩展性。另外，β-芳基化酮的用途通过各种后偶联转化和合成应用得到了进一步证明。
• Direct S-Arylation of Unactivated Arylsulfoxides Using [Pd(IPr*)(cin)Cl]
  作者：Frédéric Izquierdo、Anthony Chartoire、Steven P. Nolan

  DOI：10.1021/cs400533e

  日期：2013.10.4

  The direct S-arylation of unactivated arylsulfoxides catalyzed by [Pd(IPr*)(cin)Cl] is described. Several arylmethylsulfoxides were coupled to various aryl halides in moderate to good yields (17 examples, 34-85%). Scope, limitations, and reaction mechanism are discussed.