[2-chloro-2-(p-tolylsulfinyl)ethene-1,1-diyl]dibenzene | 209391-60-6

• 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: [2-chloro-2-(p-tolylsulfinyl)ethene-1,1-diyl]dibenzene
• 英文别名: Benzene, 1-[(1-chloro-2,2-diphenylethenyl)sulfinyl]-4-methyl-；1-(1-chloro-2,2-diphenylethenyl)sulfinyl-4-methylbenzene
• CAS: 209391-60-6
• 化学式: C₂₁H₁₇ClOS
• 分子量: 352.884
• InChiKey: BVJZDNKVZDVNOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 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-chloro-2-(p-tolylsulfinyl)ethene-1,1-diyl]dibenzene 在 异丙基氯化镁 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 2.0h， 以99%的产率得到二苯基乙炔
  参考文献：
  名称：

  Fritsch-Buttenberg-Wiechell 镁亚烷基类碳化物的重排导致炔烃的形成

  摘要：

  制备了一系列 1-杂原子取代的乙烯基对甲苯基亚砜并用有机金属试剂处理，以评估亚砜和有机金属试剂的哪种组合最有效地产生炔烃。为此目的，使用 1-氯乙烯基对甲苯基亚砜和异丙基氯化镁是最佳的。各种1-氯乙烯基p -甲苯基砜从羰基化合物制备和氯p -甲苯基砜和被转换成可经由所得镁亚烷基卡宾的亚砜/镁交换反应和随后的弗里奇-Buttenberg-Wiechell（FBW）重排炔. 研究了镁亚烷基卡宾的FBW重排机理。13 C-标记的亚砜和通过使用 DFT 计算。

  DOI：

  10.3762/bjoc.17.94
• 作为产物：
  描述：

  chloromethyl p-tolyl sulfoxide 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 19.83h， 生成 [2-chloro-2-(p-tolylsulfinyl)ethene-1,1-diyl]dibenzene
  参考文献：
  名称：

  亚烷基镁类胡萝卜素：用格氏试剂从1-卤亚砜亚砜生成，并对其性质，机理和某些合成用途进行研究

  摘要：

  通过亚砜与格利雅试剂的配体交换反应，由酮和芳基卤代甲基亚砜衍生的1-卤代亚砜生成亚烷基镁的类胡萝卜素。发现生成的亚烷基镁类胡萝卜素在-78°C稳定超过30分钟。类胡萝卜素与醛反应生成加合物，产率中等。然而，发现它们与通常的亲电试剂没有反应。产生的亚烷基镁类胡萝卜素在α-卤代烯基格氏试剂与亚烷基卡宾-卤化镁络合物之间平衡存在。观察到亚烷基类胡萝卜素的卤素交换和几何异构化。1-氯丙烯基亚砜与过量的芳基格氏试剂反应，得到具有芳基的烯基格氏试剂。

  DOI：

  10.1016/s0040-4020(98)00243-9

文献信息

• A new synthesis of amides and γ-lactones based on the conjugate addition of lithium enolate of amides to 1-chlorovinyl p-tolyl sulfoxides
  作者：Tsuyoshi Satoh、Yuhki Kamide、Shimpei Sugiyama

  DOI：10.1016/j.tet.2004.09.113

  日期：2004.12

  Reaction of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from chloromethyl p-tolyl sulfoxide and ketones or aldehydes, with lithium enolate of N,N-dimethylacetamide gave the adducts in good to quantitative yields. The adducts were converted to several kinds of amides in high overall yields. Treatment of the adducts with trifluoroacetic anhydride in the presence of NaI resulted in the formation

  1-氯乙烯基反应p -甲苯基亚砜，这是从氯合成p -甲苯基砜和酮或醛，与锂的烯醇Ñ，Ñ二甲基乙酰胺，得到良好的加合物，以定量的产率。加合物以高总收率转化为几种酰胺。在NaI存在下用三氟乙酸酐处理加合物导致高产率地形成γ-甲苯基磺酰化的γ-内酯。还讨论了该方法的范围和局限性以及反应机理。这些程序提供了一种新的有效的方法，用于从N，N合成在β-碳上具有取代基的酰胺和γ-内酯-具有碳伸长率的-二甲基乙酰胺。
• Synthesis of cyclopentadienyl enaminonitriles from α-chlorovinyl p-tolyl sulfoxides and acetonitrile with three consecutive carboncarbon bond-formations
  作者：Tsuyoshi Satoh、Hiroyuki Ota

  DOI：10.1016/s0040-4039(99)00341-x

  日期：1999.4

  Treatment of α-chlorovinyl p-tolyl sulfoxides with 5-equivalents of lithium carbanion of acetonitrile at −78 °C to room temperature afforded cyclopentadienyl enaminonitriles in high yields with three consecutive carboncarbon bond-formations. The mechanism of this reaction and some reactions of the enaminonitriles are reported.

  在-78°C到室温下，用5当量的乙腈碳负离子处理α-氯乙烯基对甲苯基亚砜，可高收率得到环戊二烯基烯腈，具有三个连续的碳碳键形成。报道了该反应的机理和烯氨基腈的一些反应。
• Reaction of magnesium alkylidene carbenoids with lithium acetylides and lithium thiolates: a novel synthesis of conjugated enynes and vinyl sulfides
  作者：Masanori Watanabe、Masatomo Nakamura、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2005.02.084

  日期：2005.5

  carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at −78 °C in THF or toluene via the sulfoxide–magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion and

  亚烷基镁的类胡萝卜素是在1-78℃于THF或甲苯中，由1-氯乙烯基对甲苯基亚砜与i -PrMgCl经由亚砜-镁交换反应生成的。产生的亚烷基镁类胡萝卜素与乙炔化锂或硫醇锂反应，分别以中等至良好的产率得到共轭烯炔或乙烯基硫化物。发现该反应的中间体是链烯基阴离子，它可以被一些亲电试剂捕获，得到四取代的共轭烯炔和乙烯基硫化物。
• Alkenylation of 1- and 2-Naphthols by Using Magnesium Alkylidene Carbenoids as Electrophilic Alkenylating Agents
  作者：Tsuyoshi Satoh、Tsutomu Kimura、Masaya Watanabe、Gaku Kashiwamura、Jo Sakurada

  DOI：10.1055/s-0032-1318132

  日期：——

  1- and 2-Naphthols were successfully alkenylated in a regioselective manner by treating the corresponding lithium 1- and 2-naphtholates with magnesium alkylidene carbenoids. The magnesium alkylidene carbenoids were generated in situ by a sulfoxide-magnesium exchange reaction of 1-chlorovinyl 4-tolyl sulfoxides with isopropylmagnesium chloride. The reaction of magnesium alkylidene carbenoids with lithium 2-naphtholates took place at the 1-position of the naphthyl ring to give 1-(alk-1-enyl)-2-naphthols in respectable yields. The alkenylation of 1-naphthols proceeded at the 2-position of the naphthol ring to give 2-(alk-1-enyl)-1-naphthols in yields of 56-67%. In contrast to the reaction of lithium naphtholates with magnesium alkylidene carbenoids, the reaction of lithium phenolates gave low yields of the corresponding alk-1-enyl aryl ethers.
• A novel synthesis, including asymmetric synthesis, of 2,4,4-trisubstituted 2-cyclopentenones based on the reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues
  作者：Daisuke Wakasugi、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2004.11.040

  日期：2005.1

  Reaction of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from chloromethyl p-tolyl sulfoxide and ketones in high overall yields, with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) gave adducts in high to quantitative yields. The adducts were treated with LDA followed by lithium alpha-carbanion of the homologues of acetonitrile to give 3,5,5-trisubstituted enaminonitriles in good to high yields. Hydrolysis of the enaminonitriles under acidic conditions gave 2,4,4-trisubstituted 2-cyclopentenones in good yields. By using the optically active chloromethyl p-tolyl sulfoxide and unsymmetrical ketones, this procedure gave the optically pure 2,4,4-trisubstituted 2-cyclopentenones. The scope and limitations of this method and the mechanism of the reactions are also discussed. These procedures offer a new and effective method for the synthesis of 2,4,4-trisubstituted 2-cyclopentenones from four components, ketones, chloromethyl p-tolyl sulfoxide, acetonitrile, and its homologues. (C) 2004 Elsevier Ltd. All rights reserved.