4-chloro-3,3-diphenyl-4-(p-tolylsulfinyl)butyronitrile | 289680-78-0

• 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: 4-chloro-3,3-diphenyl-4-(p-tolylsulfinyl)butyronitrile
• 英文别名: 4-Chloro-4-(4-methylphenyl)sulfinyl-3,3-diphenylbutanenitrile
• CAS: 289680-78-0
• 化学式: C₂₃H₂₀ClNOS
• 分子量: 393.937
• InChiKey: OAMSKAACXALFGR-UHFFFAOYSA-N

物化性质

• 沸点：
  617.2±55.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  60.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-chloro-3,3-diphenyl-4-(p-tolylsulfinyl)butyronitrile 在 氢气 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 2-ethyl-4,4-diphenyl-2-cyclopentenone
  参考文献：
  名称：

  A novel synthesis of 2,4,4-trisubstituted 2-cyclopentenones by consecutive reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues

  摘要：

  1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of ketones and chloromethyl p-tolyl sulfoxide in three steps in high overall yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) at low temperature gave the adducts in almost quantitative yields. The adducts were then treated with LDA followed by excess lithium alpha-carbanion of the homologues of acetonitrile to afford 3,5,5-trisubstituted cyclopentadienyl enaminonitriles, which were hydrolyzed and heated under acidic conditions to give 2,4,4-trisubstituted 2-cyclopentenones in good overall yields. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.004
• 作为产物：
  描述：

  lithioacetonitrile 、 [2-chloro-2-(p-tolylsulfinyl)ethene-1,1-diyl]dibenzene 以 四氢呋喃 为溶剂， 以93%的产率得到4-chloro-3,3-diphenyl-4-(p-tolylsulfinyl)butyronitrile
  参考文献：
  名称：

  A novel synthesis of 2,4,4-trisubstituted 2-cyclopentenones by consecutive reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues

  摘要：

  1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of ketones and chloromethyl p-tolyl sulfoxide in three steps in high overall yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) at low temperature gave the adducts in almost quantitative yields. The adducts were then treated with LDA followed by excess lithium alpha-carbanion of the homologues of acetonitrile to afford 3,5,5-trisubstituted cyclopentadienyl enaminonitriles, which were hydrolyzed and heated under acidic conditions to give 2,4,4-trisubstituted 2-cyclopentenones in good overall yields. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.004

文献信息

• New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions
  作者：Hideki Saitoh、Tatsuya Watanabe、Tsutomu Kimura、Yuichi Kato、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2012.01.059

  日期：2012.3

  2-arylcyanocyclopropanes by the 1,3-carbon–carbon (1,3-CC) insertion reaction of the generated magnesium carbenoid intermediates. This reaction was found to proceed in a highly stereospecific manner. The key reactions, intramolecular SN2 alkylation and 1,3-CC insertion reaction of the magnesium carbenoids, are the first examples for the reaction of the magnesium carbenoids bearing a nitrile functional group.

  由酮和醛衍生的1-氯乙烯基对甲苯基亚砜与α-氰基碳负离子锂的加成反应以高收率或定量收率得到腈加合物。用过量的i- PrMgCl在THF中处理乙腈衍生的腈加合物，通过生成的镁类胡萝卜素的分子内S N 2烷基化反应生成氰基环丙烷。证明该反应的中间体是环丙基氯化镁，并且与亲电试剂反应，得到多取代的氰基环丙烷。在另一方面，腈加合物的反应从arylacetonitriles衍生与我-PrMgCl通过生成的镁类马鞭草中间体的1,3-碳-碳（1,3-CC）插入反应导致2-芳基氰基环丙烷的形成。发现该反应以高度立体定向的方式进行。关键反应，即镁类胡萝卜素的分子内S N 2烷基化和1，3-CC插入反应，是带有腈官能团的镁类胡萝卜素反应的第一个例子。
• A new synthesis of cyanocyclopropanes by the intramolecular alkylation of magnesium carbenoids as the key reaction
  作者：Hideki Saitoh、Tsuyoshi Satoh

  DOI：10.1016/j.tetlet.2010.04.090

  日期：2010.6

  Addition reaction of 1-chlorovinyl p-tolyl sulfoxides, derived from ketones and chloromethyl p-tolyl sulfoxide, with cyanomethyllithium gave adducts in quantitative yields. Treatment of the adducts with i-PrMgCl in THF resulted in the formation of cyanocyclopropanes via the intramolecular alkylation of the generated magnesium carbenoids. The intermediate of this reaction was proved to be a cyclopropylmagnesium

  衍生自酮的1-氯乙烯基对甲苯基亚砜和氯甲基对甲苯基亚砜与氰基甲基锂的加成反应以定量收率得到加合物。用i- PrMgCl在THF中处理加合物导致生成的镁类类胡萝卜素通过分子内烷基化形成氰基环丙烷。证明该反应的中间体是环丙基氯化镁，并且发现它与亲电试剂反应，得到多取代的氰基环丙烷。关键反应，类胡萝卜素镁的分子内烷基化，是镁类胡萝卜素与腈稳定化碳负离子反应的第一个例子。
• 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.
• 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
  作者：Tsuyoshi Satoh、Hiroyuki Ota

  DOI：10.1016/s0040-4020(00)00187-3

  日期：2000.7

  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.
• A novel synthesis of 2,4,4-trisubstituted 2-cyclopentenones by consecutive reaction of 1-chlorovinyl p-tolyl sulfoxides with acetonitrile and its homologues
  作者：Tsuyoshi Satoh、Daisuke Wakasugi

  DOI：10.1016/j.tetlet.2003.08.004

  日期：2003.9

  1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of ketones and chloromethyl p-tolyl sulfoxide in three steps in high overall yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium (lithium alpha-carbanion of acetonitrile) at low temperature gave the adducts in almost quantitative yields. The adducts were then treated with LDA followed by excess lithium alpha-carbanion of the homologues of acetonitrile to afford 3,5,5-trisubstituted cyclopentadienyl enaminonitriles, which were hydrolyzed and heated under acidic conditions to give 2,4,4-trisubstituted 2-cyclopentenones in good overall yields. (C) 2003 Elsevier Ltd. All rights reserved.