<(p-chlorophenyl)sulfinyl>acetonitrile | 63923-60-4

• 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: <(p-chlorophenyl)sulfinyl>acetonitrile
• 英文别名: [(4-chlorophenyl)sulfinyl]methylcyanide；4-chlorophenylsulfinylacetonitrile；(4-chloro-benzenesulfinyl)-acetonitrile；(4-Chlor-benzolsulfinyl)-acetonitril；<4-Chlor-phenylsulfinyl>-acetonitril；Acetonitrile, [(4-chlorophenyl)sulfinyl]-；2-(4-chlorophenyl)sulfinylacetonitrile
• CAS: 63923-60-4
• 化学式: C₈H₆ClNOS
• 分子量: 199.661
• InChiKey: XEMPZMVELWPETE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  60.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-香茅醛 、 <(p-chlorophenyl)sulfinyl>acetonitrile 在 N,N-diethylaminopropylated silica gel 作用下， 以 水 为溶剂， 反应 19.0h， 生成
  参考文献：
  名称：

  Sequential Knoevenagel Reaction/Mislow-Evans Rearrangement Catalyzed by Heterogeneous Amine Grafted on Silica in Water, Leading to γ-Hydroxy-α,β-unsaturated Nitrile

  摘要：

  通过在水中用N,N-二乙基氨基丙基化硅胶催化的反应，将α-芳基亚磺酰乙腈与醛反应得到γ-羟基-α,β-不饱和腈。整个转化过程经过五个连续反应，包括乙腈的1,2-加成、脱水（克诺文-阿盖尔缩合）、双键异构化、亚磺酰基重排（米斯洛-埃文斯重排）和亚磺酰酯的水解。反应条件温和，使得AcO、TBMDSO或OTHP基团在产物中保持完整。

  DOI：

  10.1055/s-2006-941590
• 作为产物：
  描述：

  (4-氯苯基硫)乙腈 在 Amberlyst 15 双氧水 作用下， 以 甲醇 为溶剂， 反应 9.0h， 以85%的产率得到<(p-chlorophenyl)sulfinyl>acetonitrile
  参考文献：
  名称：

  离子交换树脂使用过氧化氢催化硫化物选择性氧化为亚砜

  摘要：

  在室温下，在Amberlyst 15和Amberlite IR-400的存在下，使用过氧化氢可实现在温和且环境安全的条件下将硫化物选择性氧化为亚砜的有效方法。该方法可用于具有各种官能团的二烷基硫化物和二芳基硫化物。诸如羟基，甲氧基，氨基，醛和烯属双键的官能团保持完整。

  DOI：

  10.1007/s00706-006-0563-4

文献信息

• Highly Efficient Selective Oxygenation of Sulfides to Sulfoxides by Oxalic Acid Dihydrate in the Presence of H₂O₂
  作者：Masoud Mokhtary、Mohammad Qandalee、Masoumeh Rastegar Niaki

  DOI：10.1155/2012/412798

  日期：——

  A highly efficient method for the oxidation of sulfides to sulfoxides using oxalic acid dihydrate in the presence of hydrogen peroxide has been developed. A versatile procedure for the oxidation of sulfides to sulfoxides without any over-oxidation to sulfones has been reported. This procedure cleanly oxidizes sulfides to the corresponding sulfoxides in excellent yields at ambient temperature.

  已开发出一种在过氧化氢存在下使用草酸二水合物氧化硫醚为亚砜的高效方法。报道了一种将硫醚氧化为亚砜的多功能程序，无需过氧化为砜。该程序在室温下将硫醚清洁地氧化为相应的亚砜，收率极高。
• Intramolecular Stereospecific Pummerer Reactions of Aryl (Substitutedmethyl) Sulfoxides Bearing Electron-withdrawing Groups with Acetic Anhydride
  作者：Tatsuo Numata、Osamu Itoh、Toshiaki Yoshimura、Shigeru Oae

  DOI：10.1246/bcsj.56.257

  日期：1983.1

  optically active cyanomethyl aryl sulfoxides with acetic anhydride gave the corresponding α-acetoxy sulfides which were induced with a partial asymmetry nearly 30% at α-carbon, while the 18O-label of the original sulfoxides was retained in more than 85% in the resulting ester, the Pummerer reaction product. Kinetic experiments with cyanomethyl (p-substituted phenyl) sulfoxides and α,α-dideuterated cyanomethyl

  旋光性氰甲基芳基亚砜与乙酸酐的普默勒反应得到相应的 α-乙酰氧基硫化物，其在 α-碳上的部分不对称性接近 30%，而原始亚砜的 18O-标记保留在 85% 以上在所得酯中，Pummerer 反应产物。氰甲基（对取代苯基）亚砜和 α,α-二氘代氰甲基对甲苯基亚砜与含有少量乙酸的乙酸酐反应的动力学实验表明，这些速率与哈米特 σ 值和 ρ 值相关得到-0.70，而动力学同位素效应几乎为零，即kH⁄kD=1.01。这些观察结果清楚地表明，重排是分子内的，通过形成非常紧密的离子对进行，决定速率的步骤被认为是初始可逆酰化和去质子化后的 S-O 键断裂。通过Elcb型Pro...
• HIO₃in the Presence of Wet SiO₂: A Mild and Efficient Reagent for Selective Oxidation of Sulfides to Sulfoxides under Solvent‐Free Conditions
  作者：M. M. Lakouraj、M. Tajbakhsh、F. Shirini、M. V. Asady Tamami

  DOI：10.1081/scc-200050940

  日期：2005.3

  In the presence of wet SiO2, HIO3 is highly efficient for the selective oxidation of sulfides to sulfoxides. It may be applied to any type of dialkyl and alkyl aryl sulfides. It develops under solvent-free conditions, and gives high yield in the presence of different functional groups on the sulfide at room temperature.
• Intramolecular palladium-catalyzed trimethylenemethane cycloadditions: initial studies
  作者：Barry M. Trost、Timothy A. Grese、Dominic M. T. Chan

  DOI：10.1021/ja00019a036

  日期：1991.9

  The potential application of [3 + 2] cycloadditions to polycarbocycle construction is considerably enhanced by the ability to perform such reactions intramolecularly. The feasibility of such processes is explored in the context of Pd-catalyzed cycloadditions of 2-[(trimethylsilyl)methyl]allyl carboxylates, wherein trimethylenemethane (TMM) precursor fragment (donor) and the electron-deficient olefin (acceptor) is joined by a tether of simple methylene groups of 3, 4, 5, and 8 members. Several versatile synthetic routes to these substrates were developed. 2-Bromo-3-(trimethylsilyl)propene proves to be a key reagent for construction of the donor portion. Acceptors bearing esters, cyano groups, and especially sulfones have been examined. The diastereoselectivity of the reaction has been explored both in terms of ring juncture and the diastereofacial selectivity with respect to an oxygen substituent at the allylic position of the acceptor. Excellent cycloadditions to give the bicyclo[3.3.0] octyl and bicyclo[4.3.0]nonyl systems are observed, whereas larger rings cannot be obtained in this series. The choice of catalyst proves critical, the most useful being either tetrakis(triphenylphosphine)palladium and DPPE or, more generally, triisopropyl phosphite and palladium acetate. The first cycloaddition of a 1,1-dialkylated TMM precursor, which fails in intermolecular cases, has been observed in this intramolecular series to give a bridgehead-substituted bicycle. A rationale for the observed diastereoselectivity is presented.
• Rudorf, Wolf-Dieter; Uhlig, Gabriele; Dargatz, Manfred, Liebigs Annalen der Chemie, 1992, # 4, p. 395 - 398
  作者：Rudorf, Wolf-Dieter、Uhlig, Gabriele、Dargatz, Manfred

  DOI：——

  日期：——