(E)-1-(chloro-cyclohex-2-enylidene-methanesulfinyl)-4-methylbenzene | 644977-03-7

• 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: (E)-1-(chloro-cyclohex-2-enylidene-methanesulfinyl)-4-methylbenzene
• 英文别名: 1-[(E)-chloro(cyclohex-2-en-1-ylidene)methyl]sulfinyl-4-methylbenzene
• CAS: 644977-03-7
• 化学式: C₁₄H₁₅ClOS
• 分子量: 266.792
• InChiKey: OMQLVNXIYPNQMK-WYMLVPIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  (E)-1-(chloro-cyclohex-2-enylidene-methanesulfinyl)-4-methylbenzene 在 叔丁基氯化镁 、 异丙基氯化镁 、 氯化铵 作用下， 以 甲苯 为溶剂， 反应 0.08h， 以51%的产率得到(E)-2-(chloromethylene)cyclohexene
  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
• 作为产物：
  描述：

  chloromethyl p-tolyl sulfoxide 在 吡啶 、 4-二甲氨基吡啶 、 lithium diphenylamide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 (E)-1-(chloro-cyclohex-2-enylidene-methanesulfinyl)-4-methylbenzene
  参考文献：
  名称：

  螺的新合成，包括不对称合成[4。n ]烯酮，由三部分组成：环酮，氯甲基对甲苯基亚砜和乙腈；和外消旋可乐酮的正式全合成

  摘要：

  由几种环酮和氯甲基对甲苯基亚砜合成了1-氯代戊酰基对甲苯基亚砜，收率很高。在-78°C到室温下，用氰基甲基锂处理1-氯乙烯基对甲苯基亚砜，可以高收率得到螺环烯腈。烯丙腈的酸性处理可得到螺[4]。n ]烯酮，收率高。通过使用不对称的环状酮，α-四氢萘酮和光学活性的氯甲基p-甲苯基亚砜，此方法可提供对映体纯的螺[4.5]癸烯酮，收率高，并且从亚砜手性中心具有出色的不对称诱导性。通过使用该方法，实现了外消旋的螺环倍半萜烯，阿科隆的正式全合成。

  DOI：

  10.1016/j.tet.2003.09.099

文献信息

• A synthesis of bicyclo[n.1.0]alkanes having tert-butyl carboxylate or acetamide moiety via the intramolecular 1,3-CH insertion of magnesium carbenoids
  作者：Shingo Ogata、Hideki Saitoh、Daisuke Wakasugi、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2008.04.024

  日期：2008.6

  enolate of carboxylic acid tert-butyl esters or N,N-dimethylacetamide gave adducts in high yields. The adducts were treated with ether solution of isopropylmagnesium chloride in dry toluene to give bicyclo[n.1.0]alkane derivatives having tert-butyl carboxylate or acetamide moiety on the bridgehead carbon in high to quantitative yields via magnesium carbenoid 1,3-CH insertion reaction. The 1,3-CH insertion

  1-氯乙烯基治疗p -甲苯基砜，来自各种环酮和氯甲基衍生的p -甲苯基砜，与锂羧酸的烯醇叔丁基酯或Ñ，ñ二甲基乙酰胺，得到高收率的加合物。该加合物在干燥的甲苯与异丙基氯化镁的乙醚溶液处理，得到双环[ Ñ .1.0]具有烷衍生物叔通过羧甲基1,3-CH插入反应，桥头碳上的羧酸丁酯或乙酰胺部分以高产率或定量产率产生。1,3-CH插入反应被证明具有区域选择性和立体特异性。讨论了反应机理以及选择性和特异性的起源。
• Direct alkenylation of arylamines at the ortho-position
  作者：Tsuyoshi Satoh、Yumi Ogino、Masatomo Nakamura

  DOI：10.1016/j.tetlet.2004.06.024

  日期：2004.7

  gave ortho-alkenylated arylamines in moderate to good yields. The reaction was found to proceed in a highly stereospecific manner at the carbenoid carbon. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic ring.

  镁烷叉卡宾的治疗，这是从1氯乙烯基生成p -甲苯基砜与异丙基氯化镁在甲苯中-78℃下，用Ñ -lithio芳基胺，得到邻-alkenylated芳基胺在中度至良好的产率。发现该反应在类胡萝卜素碳上以高度立体定向的方式进行。该反应在芳环的邻位提供芳胺的相当新颖和直接的烯基化。
• 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。