<(p-Tolylsulfonyl)methylene>cyclohexane | 136828-02-9

• 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: <(p-Tolylsulfonyl)methylene>cyclohexane
• 英文别名: 1-[(cyclohexylidenemethyl)sulfonyl]-4-methylbenzene；1-(Cyclohexylidenemethylsulfonyl)-4-methylbenzene
• CAS: 136828-02-9
• 化学式: C₁₄H₁₈O₂S
• 分子量: 250.362
• InChiKey: QMQHQQGXZIMJFC-UHFFFAOYSA-N

物化性质

• 沸点：
  419.6±28.0 °C(Predicted)
• 密度：
  1.194±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  <(p-Tolylsulfonyl)methylene>cyclohexane 、 8-[Chloro-(toluene-4-sulfinyl)-methylene]-1,4-dioxa-spiro[4.5]decane 在 lithium diisopropyl amide 、 叔丁基氯化镁 、 异丙基氯化镁 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 以79%的产率得到8-[2-(cyclohex-1-en-1-yl)vinylidene]-1,4-dioxaspiro[4.5]decane
  参考文献：
  名称：

  镁亚炔基类胡萝卜素与α-磺酰基烯丙基锂的偶联反应：多取代乙烯基烯丙烯的有效途径

  摘要：

  摘要 从1-氯乙烯基对甲苯基亚砜和烯丙基或乙烯基砜成功地合成了各种乙烯基烯丙基。由羰基化合物分三步或四步以良好的总收率制备用作α-磺酰基烯丙基锂的烯丙基和乙烯基砜。α-磺酰基烯丙基锂与由1-氯乙烯基对甲苯基亚砜和异丙基氯化镁生成的亚烷基镁类胡萝卜素的偶合反应以高达88％的产率提供了多取代的乙烯基烯。 从1-氯乙烯基对甲苯基亚砜和烯丙基或乙烯基砜成功地合成了各种乙烯基烯丙基。由羰基化合物分三步或四步以良好的总收率制备用作α-磺酰基烯丙基锂的烯丙基和乙烯基砜。α-磺酰基烯丙基锂与由1-氯乙烯基对甲苯基亚砜和异丙基氯化镁生成的亚烷基镁类胡萝卜素的偶合反应以高达88％的产率提供了多取代的乙烯基烯。

  DOI：

  10.1055/s-0032-1317507
• 作为产物：
  描述：

  对甲基苯磺酰氟 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 <(p-Tolylsulfonyl)methylene>cyclohexane
  参考文献：
  名称：

  Sulfonylation of organometallic reagents with arenesulfonyl fluorides: a simple one-step synthesis of sulfones

  摘要：

  Sulfonylation of organometallic reagents was accomplished with arenesulfonyl fluorides to provide a wide variety of alkylaryl- and diaryl sulfones. Organolithium and diorganocopper lithium reagents react smoothly with arenesulfonyl fluorides to give sulfones in high yields. Alkyl Grignard reagents often lead to mixtures of monosulfonylated and disulfonylated products. However, allylmagnesium chloride and phenylmagnesium chloride provide the corresponding sulfones in excellent yields. Organocopper reagents were also found to yield sulfones upon treatment with arenesulfonyl fluorides. By utilizing this methodology, synthetically useful alkyl, (trimethylsilyl)methyl, and allyl sulfones are easily prepared in high yields.

  DOI：

  10.1021/jo00028a053

文献信息

• A NEW METHOD FOR SYNTHESIS OF ALKYLIDENE SULFONES VIA DIRECT ALKYLIDENATING REACTION OF KETONES WITH<i>GEM</i>-DIBROMOMETHYL SULFONES PROMOTED BY THE Sm/SmI₂SYSTEM IN THE PRESENCE OF A CATALYTIC AMOUNT OF CrCl₃
  作者：Yunkui Liu、Huayue Wu、Yongmin Zhang

  DOI：10.1081/scc-100000178

  日期：2001.1

  Alkylidene sulfones were prepared in moderate to good yields via direct alkylidenating reaction of ketones with geminal dibromomethyl sulfones promoted by Sm/SmI2 system in the presence of a catalytic amount of CrCl3 under mild conditions.

  在温和条件下，在催化量的 CrCl3 存在下，通过 Sm/SmI2 系统促进的酮与孪生二溴甲基砜的直接烷基化反应，以中等至良好的收率制备亚烷基砜。
• Synthesis of small ring-containing conjugated dienes via the coupling reaction of cyclopropyl- and cyclobutylmagnesium carbenoids with α-sulfonylallyllithiums
  作者：Tsutomu Kimura、Mio Inumaru、Takuma Migimatsu、Masashi Ishigaki、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2013.03.019

  日期：2013.5

  synthesized via the coupling reaction of cyclopropyl- and cyclobutylmagnesium carbenoids with α-sulfonylallyllithiums. Small ring cycloalkylmagnesium carbenoids were generated from aryl 1-chlorocycloalkyl sulfoxides and a Grignard reagent, and the resultant magnesium carbenoids were reacted with α-sulfonylallyllithiums, which were prepared via the deprotonation of p-tolyl vinyl sulfones or allyl p-tolyl

  通过环丙基和环丁基镁类胡萝卜素与α-磺酰基烯丙基锂的偶联反应，合成了各种烯丙基环丙烷和烯丙基环丁烷。由芳基1-氯环烷基亚砜和格利雅试剂生成小环环烷基镁类胡萝卜素，然​​后使生成的镁类胡萝卜素与α-磺酰基烯丙基锂反应，后者是通过对甲苯基乙烯基砜或烯丙基p的去质子化反应制得的。-甲苯基砜。亚芳基环烷烃的收率中等至良好，而亚芳基环烷烃与四氰基乙烯的Diels-Alder反应提供了螺环化合物。无环烷基镁类胡萝卜素与α-磺酰基烯丙基锂的偶联反应提供了作为几何异构体混合物的共轭二烯。DFT计算的结果表明，相对于相应的氯环烷烃，小环环烷基镁类胡萝卜素具有较长的C–Cl键，并且C–Cl键的背面具有扩展的键角。
• New synthesis of allylidenecyclobutanes by the reaction of cyclobutylmagnesium carbenoids with vinyl sulfones
  作者：Masashi Ishigaki、Mio Inumaru、Tsuyoshi Satoh

  DOI：10.1016/j.tetlet.2011.08.018

  日期：2011.10

  The reaction of cyclobutylmagnesium carbenoids, which were generated from 1-chlorocyclobutyl p-tolyl sulfoxides with EtMgCl via the sulfoxide–magnesium exchange reaction at low temperature, with carbanions derived from vinyl sulfones with n-BuLi or LDA resulted in the formation of allylidenecyclobutanes in moderate to good yields. The actual reactive species of the sulfones in this reaction were proved

  1-氯环丁基对甲苯基亚砜通过低温下的亚砜-镁交换反应，由1-氯环丁基对甲苯基亚砜与EtMgCl生成的环丁基镁类化合物，与乙烯基砜与n- BuLi或LDA衍生的碳负离子在中等温和的条件下形成烯丙基亚环丁烷高产。在该反应中砜的实际反应物种被证明是通过与所用碱的双键迁移而衍生自乙烯基砜的烯丙基砜的α-磺酰基碳负离子。可以通过使用多种乙烯基砜来获得单取代和二取代的烯丙基亚环丁烷。
• Sulfonylation of organometallic reagents with arenesulfonyl fluorides: a simple one-step synthesis of sulfones
  作者：Leah L. Frye、Eileen L. Sullivan、Kevin P. Cusack、John M. Funaro

  DOI：10.1021/jo00028a053

  日期：1992.1

  Sulfonylation of organometallic reagents was accomplished with arenesulfonyl fluorides to provide a wide variety of alkylaryl- and diaryl sulfones. Organolithium and diorganocopper lithium reagents react smoothly with arenesulfonyl fluorides to give sulfones in high yields. Alkyl Grignard reagents often lead to mixtures of monosulfonylated and disulfonylated products. However, allylmagnesium chloride and phenylmagnesium chloride provide the corresponding sulfones in excellent yields. Organocopper reagents were also found to yield sulfones upon treatment with arenesulfonyl fluorides. By utilizing this methodology, synthetically useful alkyl, (trimethylsilyl)methyl, and allyl sulfones are easily prepared in high yields.
• Coupling Reaction of Magnesium Alkylidene Carbenoids with α-Sulfonyl­allyllithiums: An Efficient Route to Multi-Substituted Vinylallenes
  作者：Tsuyoshi Satoh、Tsutomu Kimura、Gen Kobayashi、Masashi Ishigaki、Mio Inumaru、Jo Sakurada

  DOI：10.1055/s-0032-1317507

  日期：——

  sulfoxides and allyl or vinyl sulfones. Allyl and vinyl sulfones served as α-sulfonylallyllithium sources were prepared from carbonyl compounds in three or four steps in good overall yields. The coupling reaction of α-sulfonylallyllithiums with magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides and isopropylmagnesium chloride, afforded multi-substituted vinylallenes

  摘要 从1-氯乙烯基对甲苯基亚砜和烯丙基或乙烯基砜成功地合成了各种乙烯基烯丙基。由羰基化合物分三步或四步以良好的总收率制备用作α-磺酰基烯丙基锂的烯丙基和乙烯基砜。α-磺酰基烯丙基锂与由1-氯乙烯基对甲苯基亚砜和异丙基氯化镁生成的亚烷基镁类胡萝卜素的偶合反应以高达88％的产率提供了多取代的乙烯基烯。 从1-氯乙烯基对甲苯基亚砜和烯丙基或乙烯基砜成功地合成了各种乙烯基烯丙基。由羰基化合物分三步或四步以良好的总收率制备用作α-磺酰基烯丙基锂的烯丙基和乙烯基砜。α-磺酰基烯丙基锂与由1-氯乙烯基对甲苯基亚砜和异丙基氯化镁生成的亚烷基镁类胡萝卜素的偶合反应以高达88％的产率提供了多取代的乙烯基烯。