(Z)-1-chloro-2-phenyl-1-(p-tolylsulfinyl)ethene | 184705-44-0

• 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: (Z)-1-chloro-2-phenyl-1-(p-tolylsulfinyl)ethene
• 英文别名: (Z)-1-chloro-2-phenylvinyl p-tolyl sulfoxide；(Z)-4-[2-chloro-2-(p-tolylsulfinyl)ethenyl]benzene；1-[(Z)-1-chloro-2-phenylethenyl]sulfinyl-4-methylbenzene
• CAS: 184705-44-0
• 化学式: C₁₅H₁₃ClOS
• 分子量: 276.787
• InChiKey: IABIEGMYUFLKRU-RVDMUPIBSA-N

物化性质

• 沸点：
  468.2±45.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  (Z)-1-chloro-2-phenyl-1-(p-tolylsulfinyl)ethene 在 异丙基氯化镁 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.17h， 生成 C₁₂H₁₃ClO
  参考文献：
  名称：

  苯甲醇镁对腈基的4 -Exo-Dig亲核开环反应由1-氯-3-氰基烷基对甲苯基亚砜新合成多取代的α-氯环丁酮

  摘要：

  将1-氯-3-氰基p -甲苯基亚砜很容易从1-氯乙烯基制备p -甲苯基亚砜，这是从羰基化合物和氯合成p -甲苯基砜，用乙腈以良好产率的衍生物锂α氰基碳负离子。用i -PrMgCl处理这些亚砜导致通过4- Exo-Dig以高至高收率形成多取代的α-氯环丁酮生成的镁类拟南芥中间体与腈基的亲核开环。该方法为由羰基化合物和取代的乙腈在较短的时间内形成三个碳-碳键的合成多取代的α-氯环丁酮提供了一种新的好方法。

  DOI：

  10.1016/j.tetlet.2012.03.127
• 作为产物：
  描述：

  chloromethyl p-tolyl sulfoxide 在 甲基磺酰氯 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.67h， 生成 (Z)-1-chloro-2-phenyl-1-(p-tolylsulfinyl)ethene
  参考文献：
  名称：

  Reaction of 1-Chlorovinyl p-Tolyl Sulfoxides with Carbanion of Acetonitrile: A Novel Synthesis of Cyclopentanone Derivatives with Three Consecutive Carbon–Carbon Bond-Formations via the Enaminonitriles

  摘要：

  Treatment of 1-chlorovinyl p-tolyl sulfoxides derived from ketones with cyanomethyllithium gave cyclopentadienyl enamino-nitriles in high yields with three consecutive carbon-carbon bond-formations. However, the 1-chlorovinyl p-tolyl sulfoxides derived from aldehydes did not give good results. The mechanism of this reaction and the reaction of the enaminonitriles to convert cyclopentanone derivatives were investigated. Several alpha-carbanion of nitriles other than acetonitrile added to the 1-chlorovinyl p-tolyl sulfoxides at low temperature in good yield; however, they did not cyclize upon warming to room temperature. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00187-3

文献信息

• A novel consecutive reaction of lithium acetylides with 2-aryl-1-chlorovinyl p-tolyl sulfoxides leading to the formation of (Z)-enediynes
  作者：Tsutomu Kimura、Yuka Nishimura、Naoyuki Ishida、Hitoshi Momochi、Hironori Yamashita、Tsuyoshi Satoh

  DOI：10.1016/j.tetlet.2012.11.152

  日期：2013.2

  The reaction of (E)-2-aryl-1-chlorovinyl p-tolyl sulfoxides with lithium acetylides gave a variety of (Z)-3-arylhex-3-ene-1,5-diynes in yields of up to 80% with high stereoselectivity. The structure of the (Z)-enediyne was confirmed by X-ray molecular structure analysis. The result of the reaction with deuterium- and 13C-labeled sulfoxide suggested that the reaction proceeds through cleavage of the

  （E）-2-芳基-1-氯乙烯基对甲苯基亚砜与乙炔化锂的反应生成了多种（Z）-3-芳基己烯-3-烯-1,5-二炔，产率高达80％。高立体选择性。通过X射线分子结构分析确认了（Z）-烯二炔的结构。与氘和13 C标记的亚砜反应的结果表明，该反应通过在亚砜中的2-芳基-1-氯乙烯基单元的β位置处的C H键裂解来进行。
• A synthesis of di- and tri-substituted β,γ-unsaturated esters from aldehydes by the magnesium carbenoid 1,2-CH and 1,2-CC insertion as the key reaction
  作者：Hironori Yamashita、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2008.11.013

  日期：2009.1

  insertion reactions were observed in the latter reactions. When the addition reactions were quenched with iodoalkanes, the alkylated adducts were obtained in quantitative yields. Tri-substituted β,γ-unsaturated esters, or in some case γ,δ-unsaturated esters, were obtained by the treatment of the alkylated adducts with EtMgCl. These procedures provide a good way for a new synthesis of di- and tri-substituted

  源自醛的1-氯乙烯基对甲苯基亚砜与叔烯醇锂的加成反应在-78°C中的乙酸丁酯在THF中的收率高。用格氏试剂处理这些加合物会通过亚砜-镁交换反应形成类胡萝卜素镁。当加合物衍生自烷基醛或电子不足的芳族醛时，类胡萝卜素从类镁镁发生1,2-CH插入反应，得到在β-位具有取代基的β，γ-不饱和丁酸酯。另一方面，当加合物衍生自富含电子的芳族醛时，从羧甲基镁类化合物发生类胡萝卜素1,2-CC插入反应，得到在γ-位具有芳族基团的β，γ-不饱和丁酸酯。在后面的反应中观察到高度立体定向的1,2-CC插入反应。当加成反应用碘代烷烃淬灭时，烷基化的加合物以定量产率获得。通过用EtMgCl处理烷基化的加合物获得三取代的β，γ-不饱和酯，或在某些情况下为γ，δ-不饱和酯。这些程序为由具有两个或三个碳-碳键形成的醛合成二取代和三取代的β，γ-不饱和酯提供了一个好方法。
• A new synthesis of β,γ-unsaturated esters from three components, aldehydes, chloromethyl p-tolyl sulfoxide, and tert-butyl acetate, via magnesium carbenoid 1,2-CH and 1,2-CC insertion as the key reaction
  作者：Tsuyoshi Satoh、Hironori Yamashita、Jun Musashi

  DOI：10.1016/j.tetlet.2007.08.039

  日期：2007.10

  aromatic aldehydes, carbenoid 1,2-CH insertion reaction took place from the magnesium carbenoids to afford β,γ-unsaturated butyric esters having a substituent at the β-position. On the contrary, when the adducts were derived from electron-rich aromatic aldehydes, carbenoid 1,2-CC insertion reaction took place from the magnesium carbenoids to give β,γ-unsaturated butyric esters having the aromatic group

  衍生自各种醛的1-氯乙烯基对甲苯基亚砜与叔烯醇锂的加成反应在-78°C中的乙酸丁酯在THF中的收率高。镁类化合物是通过格氏试剂通过亚砜-镁交换反应处理这些加合物而生成的。当加合物衍生自烷基醛或电子不足的芳族醛时，类胡萝卜素从类镁镁发生1,2-CH插入反应，得到在β-位具有取代基的β，γ-不饱和丁酸酯。相反，当加合物衍生自富含电子的芳族醛时，类胡萝卜素镁发生了类胡萝卜素1,2-CC插入反应，从而生成了在γ位具有芳族基团的β，γ-不饱和丁酸酯。在后面的反应中观察到高度立体定向的1,2-CC插入反应。这个程序为合成β提供了一个很好的方法，
• 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。
• Stereoselective Horner-Wittig synthesis of (Z)-1-chlorovinyl sulfoxides
  作者：Pieter A. Otten、Honorine M. Davies、Jan Hein van Steenis、Syb Gorter、Arne van der Gen

  DOI：10.1016/s0040-4020(97)00665-0

  日期：1997.7

  This paper describes the synthesis of (Z)-I-chlorovinyl sulfoxides 1 by the Horner-Wittig reaction. The required [(alpha-chloro)sulfinylmethyl]diphenylphosphine oxides 2 (R-1=Me, c-Hex, Ph, p-Tol, p-(CF3)Ph), were prepared in high yields by selective monochlorination and subsequent mono-oxidation of (thiomethyl)diphenylphosphine oxides 3. The stable lithiated anions of 2 gave an efficient reaction with all structural types of aldehydes. Aromatic and alpha,beta-unsaturated aldehydes gave 1 with excellent Z-selectivity (>98%), irrespective of the nature of the substituent R-1 at sulfur. With straight chain aliphatic aldehydes, an aromatic substituent at sulfur was required to obtain high Z-selectivity. A mechanistic explanation for these observations is presented. An X-ray analysis of 1, R-1=Me, R-2=4-MeOC6H4 confirmed the Z-disposition of the chloro and aryl substituents. (C) 1997 Elsevier Science Ltd.