1-chlorovinyl p-tolyl sulfoxide | 184705-48-4

• 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: 1-chlorovinyl p-tolyl sulfoxide
• 英文别名: 1-[(1-chloroethenyl)sulfinyl]-4-methylbenzene；1-(1-Chloroethenylsulfinyl)-4-methylbenzene
• CAS: 184705-48-4
• 化学式: C₉H₉ClOS
• 分子量: 200.689
• InChiKey: LQLYWEZXRATRIA-UHFFFAOYSA-N

物化性质

• 沸点：
  365.3±35.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  1-chlorovinyl p-tolyl sulfoxide 在 三氟乙酸酐 、 sodium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 生成 trans-3-(2-phenylethyl)-5-(p-tolylsulfanyl)dihydrofuran-2-one
  参考文献：
  名称：

  The first example of γ-chloromagnesio γ-lactones: their generation from γ-tolylsulfinyl γ-lactones with isopropylmagnesium chloride, stability, and reaction with electrophiles

  摘要：

  The treatment of gamma-lactones having a sulfinyl group at the gamma-position, which were synthesized from I-chlorovinyl p-tolyl sulfoxides with lithium enolate of carboxylic esters, with isopropyl magnesium chloride in THF at -78 degrees C gave gamma-chloromagnesio gamma-lactones by the sulfoxide-magnesium exchange reaction in high yields. The generated gamma-chloromagnesio gamma-lactones were found to be stable at below -50 degrees C for at least 2 h. The reaction of these gamma-chloromagnesio gamma-lactones with electrophiles and the stereochemistry of the reactions were investigated. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.09.165
• 作为产物：
  描述：

  氯甲基对甲苯硫醚 在 N-氯代丁二酰亚胺 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 、 氯苯 为溶剂， 生成 1-chlorovinyl p-tolyl sulfoxide
  参考文献：
  名称：

  A Horner-Wittig Synthesis of 1-Chlorovinyl Sulfoxides.

  摘要：

  DOI：

  10.1080/10426509608545187

文献信息

• Multisubstituted α,β-Unsaturated γ-Lactones from 1-Chlorovinyl p-Tolyl Sulfoxides and tert-Butyl Carboxylates Using Pummerer-Type Cyclization as the Key Reaction
  作者：Tsuyoshi Satoh、Takashi Katae、Shimpei Sugiyama

  DOI：10.1055/s-0030-1259987

  日期：2011.5

  The addition reaction of 1-chlorovinyl p-tolyl sulfoxides, derived from aldehydes and chloromethyl p-tolyl sulfoxide, with the lithium enolate of tert-butyl carboxylates gave adducts in quantitative yields. Treatment of the adducts with trifluoroacetic anhydride in the presence of sodium iodide resulted in the formation of γ-lactones bearing a p-tolylsulfanyl group at the γ-position through Pummerer-type cyclization. Oxidation of the sulfanyl group to the sulfinyl group followed by thermal syn-elimination gave α,β-unsaturated γ-lactones (γ-butenolides) in moderate to good yields. Trapping the intermediates of the addition reaction with iodoalkanes gave alkylated adducts, from which α,γ- and β,γ-disubstituted γ-butenolides were obtained. These procedures provide a good way to synthesize multisubstituted γ-butenolides from aldehydes.

  由醛和氯甲基对甲苯亚砜衍生的1-氯乙烯基对甲苯亚砜与叔丁基羧酸锂烯醇的加成反应，以定量产率得到了加成物。在碘化钠存在下，将这些加成物与三氟乙酸酐处理后，通过Pummerer型环化反应形成了在γ位带有对甲苯硫基的γ-内酯。将硫基氧化为亚砜基，随后进行热顺式消除反应，得到中等到良好产率的α,β-不饱和γ-内酯（γ-丁烯内酯）。通过碘烷捕获加成反应的中间体，得到烷基化加成物，从中获得了α,γ-和β,γ-二取代的γ-丁烯内酯。这些方法为从醛合成多取代的γ-丁烯内酯提供了一条有效途径。
• γ-Chloromagnesio γ-Lactones and δ-Chloromagnesio δ-Lactones: Generation, Properties, and Synthetic Uses
  作者：Shimpei Sugiyama、Hitomi Shimizu、Shigehiko Fukuda、Tsuyoshi Satoh

  DOI：10.1055/s-0028-1088019

  日期：2009.4

  respectively, by the sulfoxide-magnesium exchange reaction in high yields. Comparing the stability of the γ-chloromagnesio γ-lactones with that of the δ-chloromagnesio δ-lactones, the former was found to be much more stable. The reaction of these γ-chloromagnesio γ-lactones and δ-chloromagnesio δ-lactones with electrophiles and the stereochemistry of the reactions are discussed. γ-chloromagnesio γ-lactone

  在异丙醇中于-78℃下用异丙基氯化镁处理在γ和δ位具有亚磺酰基的γ和δ内酯，分别通过亚砜处理得到γ-氯镁γ-内酯和δ-氯镁δ-内酯。 -镁交换反应的收率很高。通过比较γ-氯镁γ-内酯和δ-氯镁δ-内酯的稳定性，发现前者更加稳定。讨论了这些γ-氯镁γ-内酯和δ-氯镁δ-内酯与亲电试剂的反应以及反应的立体化学。 γ-氯镁γ-内酯-δ-氯镁δ-内酯-亚砜-镁交换反应-有机镁化合物-格氏试剂
• Use of 1-chlorovinyl p-tolyl sulfoxides as alkynylmagnesium chloride sources
  作者：Koto Sekiguchi、Tsutomu Kimura

  DOI：10.1016/j.tet.2023.133439

  日期：2023.6

  A method for generating alkynylmagnesium chlorides from 1-chlorovinyl p-tolyl sulfoxides and an isopropylmagnesium chloride–lithium chloride complex (turbo Grignard reagent) has been developed. The method consists of a sulfoxide/magnesium exchange reaction of 1-chlorovinyl p-tolyl sulfoxides and a turbo Grignard reagent, a Fritsch–Buttenberg–Wiechell rearrangement of the resulting magnesium alkylidene

  开发了一种从 1-氯乙烯基对甲苯基亚砜和异丙基氯化镁-氯化锂络合物（涡轮格氏试剂）生成炔基氯化镁的方法。该方法包括 1-氯乙烯基对甲苯基亚砜和涡轮格氏试剂的亚砜/镁交换反应，所得镁亚烷基类胡萝卜素的 Fritsch-Buttenberg-Wiechell 重排，以及末端炔烃用涡轮格氏试剂的去质子化反应。生成的炔基氯化镁与各种亲电试剂反应生成内部炔烃。
• Efficient one-pot synthesis of 1-chlorovinyl <i>p</i> -tolyl sulfoxides from aldehydes and ketones by the Horner-Wadsworth-Emmons reaction
  作者：Tsutomu Kimura、Gen Kobayashi、Shiori Ijima、Sae Saito、Aki Imafuji、Tsuyoshi Satoh

  DOI：10.1002/hc.21395

  日期：2017.9

  AbstractA variety of 2‐monosubstituted and 2,2‐disubstituted 1‐chlorovinyl p‐tolyl sulfoxides was synthesized through a one‐pot procedure by the Horner‐Wadsworth‐Emmons reaction of carbonyl compounds with [chloro(diethoxyphosphoryl)(p‐tolylsulfinyl)methyl]lithium, which was generated from diethyl chlorophosphate, chloromethyl p‐tolyl sulfoxide, and lithium diisopropylamide in advance. The in situ‐prepared sulfoxides were directly converted into alkynes via the sulfoxide/magnesium exchange reaction with i‐PrMgCl and the subsequent Fritsch‐Buttenberg‐Wiechell rearrangement of the resulting magnesium alkylidene carbenoids.
• A Horner-Wittig Synthesis of 1-Chlorovinyl Sulfoxides.
  作者：P.A. Otten、H.M. Davies、A. Van Der Gen

  DOI：10.1080/10426509608545187

  日期：1996.1