1,4-cyclohexanedione diethylenethioacetal | 311-37-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 1,4-cyclohexanedione diethylenethioacetal
• 英文别名: 1,4,9,12-Tetrathiadispiro[4.2.4.2]tetradecane；1,4,9,12-tetrathiadispiro[4.2.48.25]tetradecane
• CAS: 311-37-5
• 化学式: C₁₀H₁₆S₄
• 分子量: 264.501
• InChiKey: MBMSLTQBQYVSOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲基碘化镁 、 1,4-cyclohexanedione diethylenethioacetal 在 bis(triphenylphosphine)nickel(II) chloride 作用下， 以 乙醚 、 苯 为溶剂， 生成 8-methylene-1,4-dithia-spiro[4.5]decane 、 8-Methyl-1,4-dithia-spiro[4.5]dec-7-ene
  参考文献：
  名称：

  A chelation approach toward activation of Csp3-S bonds. Nickel-catalyzed selective cross coupling of bisdithioacetals with Grignard reagents

  摘要：

  DOI：

  10.1021/ja00044a060
• 作为产物：
  描述：

  1,4-环己二酮双乙二醇二缩酮 、 1,2-乙二硫醇 在 三氯异氰尿酸 作用下， 以 氯仿 为溶剂， 反应 2.5h， 以90%的产率得到1,4-cyclohexanedione diethylenethioacetal
  参考文献：
  名称：

  Trichloroisocyanuric Acid as a Mild and Efficient Catalyst for Thioacetalization and Transthio-acetalization Reactions

  摘要：

  三氯异氰尿酸（1），一种廉价的工业化学品，催化温和且高效的硫缩醛化和硫转移缩醛化反应。此外，该催化剂在这一用途上具有非常高的选择性。

  DOI：

  10.1055/s-2001-17451

文献信息

• A Simple and Practical Synthetic Protocol for Acetalisation, Thioacetalisation and Transthioacetalisation of Carbonyl Compounds under Solvent-Free Conditions
  作者：Abu T. Khan、Ejabul Mondal、Subrata Ghosh、Samimul Islam

  DOI：10.1002/ejoc.200300685

  日期：2004.5

  corresponding dithioacetals under identical conditions. Some of the major advantages are mild reaction conditions, a high degree of efficiency, compatibilty with other protecting groups and the lack of solvents, particularly for thioacetalisation. In addition, no brominations occur at the double bond or α to the keto position or even in the aromatic ring under these experimental conditions. (© Wiley-VCH Verlag

  在室温下，在催化量的（溴二甲基）溴化锍存在下，用醇或二醇和原甲酸三乙酯处理后，多种羰基化合物可以顺利转化为相应的缩醛。类似地，在室温下使用相同的催化剂而无需任何溶剂，各种羰基化合物可以在与硫醇或二硫醇反应时转化为相应的二硫缩醛。此外，O,O-缩醛也可以在相同条件下转化为相应的二硫缩醛。一些主要优点是温和的反应条件、高效率、与其他保护基团的相容性以及缺乏溶剂，特别是对于硫代缩醛化。此外，在这些实验条件下，在双键或酮位的 α 处甚至芳环中都不会发生溴化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Synthesis of High Refractive Spiroheterocyclic Derivatives Through Thioacetalization of Multi-Carbonyl Compounds
  作者：Ji-Myoung Ye、Muchchintala Maheswara、Jung-Yun Do

  DOI：10.5012/bkcs.2012.33.8.2494

  日期：2012.8.20

  Preparation of several new spirocyclic mercapto derivatives is described. Thiol protection on multi-carbonyl compounds allows of high sulfur content necessary to induce high refractive index. Condensation of 1,3-dimercapto-2-propanol and cyclohexanone followed by successive oxidation and thioacetalization affords a dispirocycle with four sulfurs. Selective S,S-protection of cyclohexane-1,4-dione is achieved with 1,3-dimercapto-2-propanol and 2,3-dimercapto-1-propanol to provide dispirocycles with four sulfurs. Olefine-oxidation of norbornene gives a useful dialdehyde intermediate which is transformed to 1,3-dithiolane for a linearly-bound-cyclic molecule. Refractive index of linearly-bound-cycles was below 1.60 and dispirocycles exhibited high refractive index of 1.57-1.69.

  本文描述了几种新型螺环硫醇衍生物的制备。在多羰基化合物上进行硫醇保护，可以使硫含量达到诱导高折射率所需的较高水平。将1,3-二巯基-2-丙醇与环己酮缩合，随后进行连续氧化和硫缩醛化，得到含有四个硫原子的双螺环化合物。通过1,3-二巯基-2-丙醇和2,3-二巯基-1-丙醇对环己烷-1,4-二酮进行选择性S,S保护，可以制得含有四个硫原子的双螺环化合物。烯烃氧化降冰片烯得到一个有用的二醛中间体，将其转化为1,3-二硫杂环戊烷，形成线性连接的环状分子。线性连接的环的折射率低于1.60，而双螺环化合物的折射率高达1.57-1.69。
• Iodine Catalyzes Efficient and Chemoselective Thioacetalization of Carbonyl Functions, Transthioacetalization of <i>O</i>,<i>O</i>- and <i>S</i>,<i>O</i>-Acetals and Acylals
  作者：Habib Firouzabadi、Nasser Iranpoor、Hassan Hazarkhani

  DOI：10.1021/jo015798z

  日期：2001.11.1
• Mesoporous silica-functionalized dual Brønsted acidic ionic liquid as an efficient catalyst for thioacetalization of carbonyl compounds in water
  作者：Majid Vafaeezadeh、Zahra Bahrami Dizicheh、Mohammad Mahmoodi Hashemi

  DOI：10.1016/j.catcom.2013.07.004

  日期：2013.11

  A novel silica-functionalized dual Bronsted acidic ionic liquid (ionic liquid with two Bronsted acidic species) has been reported as a highly efficient catalyst for thioacetalization of carbonyl compounds. The reaction was efficiently performed in water as an environmentally benign solvent with good to high yields. Thermal gravimetric analysis showed that the catalyst is stable at least up to 350 degrees C. Furthermore, the catalyst can be recycled and reused for six runs of reaction without appreciable loss of activity. The structure of the catalyst is modelized to gain more realistic structural insight about the functionalized ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.
• Chelation Assistance in the Activation of Csp3-S Bonds in Nickel-Catalyzed Cross-Coupling Reactions
  作者：Ken-Tsung Wong、Tien-Min Yuan、Maw Cherng Wang、Hsiao-Hsian Tung、Tien-Yau Luh

  DOI：10.1021/ja00099a009

  日期：1994.10

  An unprecedented chelation approach to activate C(sp)3-S bonds in nickel-catalyzed cross-coupling reactions is described. Our theme was based on the formation of a chelation complex which results in the enhancement of the reactivity of aliphatic carbon-sulfur bonds. When two dithioacetal functionalities are located in close proximity, selective olefination of one of these two dithioacetal groups can thus be achieved conveniently. Depending on the relative positions of the newly formed double bond and the remaining dithioacetal group, tandem olefination occurs to give the corresponding 1,5-bis-silyl-substituted pentadienes. Various neighboring heteroatom substituents (OR, OH, NR(2) as well as SR groups) can facilitate the olefination of a dithioacetal group. Poly(thioether) linkage afforded the corresponding degradation products via a B-sulfur elimination process. 1,3-Dimercapto- and 1,3-dithiolatopropanes furnish the cyclopropane formation under nickel-catalyzed reaction conditions. The reaction of a dihydrothiopyran with MeMgI in the presence of the nickel catalyst proceeds via a sulfur-coordinated ir-allyl complex, which can further activate the CS bond to give vinylcyclopropane.