[chloro-(p-tolylsulfinyl)methylidene]cyclodecane | 596118-86-4

• 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: [chloro-(p-tolylsulfinyl)methylidene]cyclodecane
• 英文别名: Cyclodecane, [chloro[(4-methylphenyl)sulfinyl]methylene]-；[chloro-(4-methylphenyl)sulfinylmethylidene]cyclodecane
• CAS: 596118-86-4
• 化学式: C₁₈H₂₅ClOS
• 分子量: 324.915
• InChiKey: OGVPDYNFMBLILM-UHFFFAOYSA-N

物化性质

• 沸点：
  497.3±38.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  [chloro-(p-tolylsulfinyl)methylidene]cyclodecane 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 生成 1-Methyl-2-(toluene-4-sulfinyl)-spiro[2.9]dodecane-1-carbonitrile
  参考文献：
  名称：

  A novel route to fully substituted cyanoallenes from three components, ketones, chloromethyl p-tolyl sulfoxide, and nitriles, via α-bromocyclopropyl p-tolyl sulfoxides

  摘要：

  Treatment of 1-chlorovinyl p-tolyl sulfoxides. which were derived front ketones and chloromethyl p-tolyl sulfoxide in high yields, with lithium alpha-carbanion of nitriles gave the adducts in quantitative yields. The adducts were converted to alpha-bromocyclopropyl p-tolyl sulfoxides in two steps in good yields. Finally, the sulfoxides were treated with excess lithium carbanion of isobutyronitrile to afford fully Substituted cyanoallenes in high to quantitative yields via sulfoxide-lithium exchange reaction. This procedure offers a novel synthetic method for fully substituted cyanoallenes with coupling of three components (ketones, chloromethyl p-tolyl sulfoxide, and nitriles) in good overall yields. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.01.161
• 作为产物：
  描述：

  Acetic acid 1-[chloro-(toluene-4-sulfinyl)-methyl]-cyclodecyl ester 在 lithium anion of δ-valerolactam 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以77%的产率得到[chloro-(p-tolylsulfinyl)methylidene]cyclodecane
  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。
• A new synthesis of amides and γ-lactones based on the conjugate addition of lithium enolate of amides to 1-chlorovinyl p-tolyl sulfoxides
  作者：Tsuyoshi Satoh、Yuhki Kamide、Shimpei Sugiyama

  DOI：10.1016/j.tet.2004.09.113

  日期：2004.12

  Reaction of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from chloromethyl p-tolyl sulfoxide and ketones or aldehydes, with lithium enolate of N,N-dimethylacetamide gave the adducts in good to quantitative yields. The adducts were converted to several kinds of amides in high overall yields. Treatment of the adducts with trifluoroacetic anhydride in the presence of NaI resulted in the formation

  1-氯乙烯基反应p -甲苯基亚砜，这是从氯合成p -甲苯基砜和酮或醛，与锂的烯醇Ñ，Ñ二甲基乙酰胺，得到良好的加合物，以定量的产率。加合物以高总收率转化为几种酰胺。在NaI存在下用三氟乙酸酐处理加合物导致高产率地形成γ-甲苯基磺酰化的γ-内酯。还讨论了该方法的范围和局限性以及反应机理。这些程序提供了一种新的有效的方法，用于从N，N合成在β-碳上具有取代基的酰胺和γ-内酯-具有碳伸长率的-二甲基乙酰胺。
• Conjugate addition of lithium ester enolates to 1-chlorovinyl p-tolyl sulfoxides: a novel synthesis of functionalized esters and lactones having a tertiary or a quaternary carbon at the β-position
  作者：Tsuyoshi Satoh、Shimpei Sugiyama、Yuhki Kamide、Hiroyuki Ota

  DOI：10.1016/s0040-4020(03)00636-7

  日期：2003.6

  Addition of the lithium ester enolates to 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from chloromethyl p-tolyl sulfoxide and ketones or aldehydes, gave esters having a tertiary or a quaternary carbon at the 3-position, and chlorine and sulfinyl groups at the 4-position in high to quantitative yields. The adducts were converted to various esters having methyl, formyl, and hydroxycarbonyl

  的锂酯烯醇化物加成到1-氯乙烯基p -甲苯基亚砜，这是从氯合成p -甲苯基砜和酮或醛，得到具有叔或在3-位置上的季碳，并在氯和亚磺酰基酯高产量到定量产量的4位。加合物被转化为在3-位具有甲基，甲酰基和羟羰基的各种酯。从加合物中以良好的总收率实现了一种新的合成γ-内酯的方法，包括螺型γ-内酯和α-亚甲基γ-内酯。还讨论了该方法的范围和局限性以及反应机理。
• A novel route to fully substituted cyanoallenes from three components, ketones, chloromethyl p-tolyl sulfoxide, and nitriles, via α-bromocyclopropyl p-tolyl sulfoxides
  作者：Tsuyoshi Satoh、Youhei Gouda

  DOI：10.1016/j.tetlet.2006.01.161

  日期：2006.4

  Treatment of 1-chlorovinyl p-tolyl sulfoxides. which were derived front ketones and chloromethyl p-tolyl sulfoxide in high yields, with lithium alpha-carbanion of nitriles gave the adducts in quantitative yields. The adducts were converted to alpha-bromocyclopropyl p-tolyl sulfoxides in two steps in good yields. Finally, the sulfoxides were treated with excess lithium carbanion of isobutyronitrile to afford fully Substituted cyanoallenes in high to quantitative yields via sulfoxide-lithium exchange reaction. This procedure offers a novel synthetic method for fully substituted cyanoallenes with coupling of three components (ketones, chloromethyl p-tolyl sulfoxide, and nitriles) in good overall yields. (c) 2006 Elsevier Ltd. All rights reserved.
• A new synthesis, including asymmetric synthesis, of spiro[4.n]alkenones from three components: cyclic ketones, chloromethyl p-tolyl sulfoxide, and acetonitrile; and a formal total synthesis of racemic acorone
  作者：Tsuyoshi Satoh、Tadashi Kawashima、Satoru Takahashi、Ken Sakai

  DOI：10.1016/j.tet.2003.09.099

  日期：2003.11

  synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at −78°C to room temperature gave spirocyclic enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an unsymmetrical cyclic ketone, α-tetralone, and optically active

  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。