(Z)-1-chloro-2-methyl-1-(p-tolylsulfinyl)-1,3-butadiene | 866089-67-0

• 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-methyl-1-(p-tolylsulfinyl)-1,3-butadiene
• 英文别名: 1-[(1Z)-1-chloro-2-methylbuta-1,3-dienyl]sulfinyl-4-methylbenzene
• CAS: 866089-67-0
• 化学式: C₁₂H₁₃ClOS
• 分子量: 240.754
• InChiKey: XNSDIHYNWBYEET-ZRDIBKRKSA-N

物化性质

• 熔点：
  77-78 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  414.6±38.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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-methyl-1-(p-tolylsulfinyl)-1,3-butadiene 在 lithium anion of δ-valerolactam 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以52%的产率得到2-[1-Chloro-1-p-tolylsulfanyl-meth-(Z)-ylidene]-but-3-en-1-ol
  参考文献：
  名称：

  Mislow–Braverman–Evans重排的第一个示例将硫原子保留在原始碳上

  摘要：

  的1-氯-2- methylalkenyl治疗p与甲苯基砜Ñ -lithio -2-哌啶酮在THF中在室温下导致的1-氯-2-（羟甲基）的形成烯p以良好的收率甲苯基硫化物。该反应是Mislow-Braverman-Evans重排保留硫原子在原始碳原子上的第一个例子。

  DOI：

  10.1016/j.tetlet.2006.01.068
• 作为产物：
  描述：

  chloromethyl p-tolyl sulfoxide 在 lithium anion of δ-valerolactam 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 15.84h， 生成 (Z)-1-chloro-2-methyl-1-(p-tolylsulfinyl)-1,3-butadiene
  参考文献：
  名称：

  亚烷基镁类胡萝卜素在邻位直接取代芳基胺的烯基化反应及一些理论研究

  摘要：

  由酮和氯甲基对甲苯基亚砜以高收率合成了1-氯罗维酰基对甲苯基亚砜。在-78°C下于甲苯中用异丙基氯化镁处理亚砜，得到亚烷基镁类化合物（α-氯烯基氯化镁），将其用N-硫代芳基胺处理，以中等收率得到邻链烯基化芳基胺。在某些情况下，该反应以高度立体定向的方式在带有氯和亚磺酰基的碳上进行。α-氯烯基氯化镁的结构与N-硫代间位的反应性用6-31（+）G *基集在理论的B3LYP和MP2水平上研究了取代的苯胺。该反应在芳族环的邻位提供芳胺的相当新颖和直接的烯基化。

  DOI：

  10.1016/j.tet.2005.08.035

文献信息

• A method for the synthesis of cyclopropanes by regiospecific and regioselective magnesium carbenoid 1,3-CH insertion as the key reactions
  作者：Hiroyuki Watanabe、Shingo Ogata、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2010.05.061

  日期：2010.7

  i-PrMgCl resulted in the formation of magnesium carbenoid. Highly regiospecific 1,3-CH insertion reaction was found to take place from each magnesium carbenoid to afford cyclopropanes. On the other hand, when the unsymmetrical ketones bearing an oxygen- or a nitrogen-functional group on the α-carbon were used in this procedure, the regioselective 1,3-CH insertion reaction proceeded mainly. Stereochemistry

  衍生自不对称酮和氯甲基对甲苯基亚砜的1-氯乙烯基对甲苯基亚砜的两个几何异构体与乙酸叔丁酯的烯醇锂的加成反应分别得到加合物的单一非对映异构体。用i处理每个非对映异构体-PrMgCl导致形成类镁镁。发现每个镁类胡萝卜素都发生高度区域特异性的1,3-CH插入反应，从而生成环丙烷。另一方面，当在该方法中使用在α-碳上带有氧或氮官能团的不对称酮时，区域选择性的1，3-CH插入反应主要进行。讨论了加合物的立体化学，反应机理以及特异性和选择性的实质。
• 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.
• Direct N- and C-alkenylation of nitrogen-containing heterocycles with magnesium alkylidene carbenoids
  作者：Jo Sakurada、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2007.02.072

  日期：2007.4

  Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at -78 degrees C in toluene, with N-lithio nitrogen-containing heterocycles gave N-alkenylated products in moderate to good yields. Also, the reaction of C-lithio indoles, which were generated from N-protected indoles, with magnesium alkylidene carbenoids gave C-2 or C-3 alkenylated products, corresponding to the protective group. The intermediate of these reactions were found to be the alkenyl anion, which could be trapped with electrophiles to give the heterocycles having fully substituted alkenes. (C) 2007 Elsevier Ltd. All rights reserved.
• Direct alkenylation of arylamines at the ortho-position with magnesium alkylidene carbenoids and some theoretical studies of the reactions
  作者：Tsuyoshi Satoh、Yumi Ogino、Kaori Ando

  DOI：10.1016/j.tet.2005.08.035

  日期：2005.10

  1-Chlorovinyl p-tolyl sulfoxides were synthesized from ketones and chloromethyl p-tolyl sulfoxide in high yields. Treatment of the sulfoxides with isopropylmagnesium chloride at −78 °C in toluene gave magnesium alkylidene carbenoids (α-chloro alkenylmagnesium chlorides), which were treated with N-lithio arylamines to afford ortho-alkenylated arylamines in moderate yields. The reaction, in some cases, proceeded

  由酮和氯甲基对甲苯基亚砜以高收率合成了1-氯罗维酰基对甲苯基亚砜。在-78°C下于甲苯中用异丙基氯化镁处理亚砜，得到亚烷基镁类化合物（α-氯烯基氯化镁），将其用N-硫代芳基胺处理，以中等收率得到邻链烯基化芳基胺。在某些情况下，该反应以高度立体定向的方式在带有氯和亚磺酰基的碳上进行。α-氯烯基氯化镁的结构与N-硫代间位的反应性用6-31（+）G *基集在理论的B3LYP和MP2水平上研究了取代的苯胺。该反应在芳族环的邻位提供芳胺的相当新颖和直接的烯基化。
• First example of the Mislow–Braverman–Evans rearrangement retaining the sulfur atom on the original carbon
  作者：Tsuyoshi Satoh、Toshifumi Miyagawa

  DOI：10.1016/j.tetlet.2006.01.068

  日期：2006.3

  temperature resulted in the formation of 1-chloro-2-(hydroxymethyl)alkenyl p-tolyl sulfides in good yields. This reaction is the first example of the Mislow–Braverman–Evans rearrangement retaining the sulfur atom on the original carbon.

  的1-氯-2- methylalkenyl治疗p与甲苯基砜Ñ -lithio -2-哌啶酮在THF中在室温下导致的1-氯-2-（羟甲基）的形成烯p以良好的收率甲苯基硫化物。该反应是Mislow-Braverman-Evans重排保留硫原子在原始碳原子上的第一个例子。