3-allylsulfanyl-cyclohexanone

• 分子结构分类: 有机化合物 - 有机硫化合物 - 烯丙基硫化合物
• 英文名称: 3-allylsulfanyl-cyclohexanone
• 英文别名: 3-allylsulfanylcyclohexanone；3-(allylthio)cyclohexanone；3-Prop-2-enylsulfanylcyclohexan-1-one
• 化学式: C₉H₁₄OS
• 分子量: 170.276
• InChiKey: ALCKSGIEWKWAHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-环己烯-1-酮 、 3-氯丙烯 在 sodium dodecyl sulfate 、 sodium carbonate 、 硫脲 作用下， 以 水 为溶剂， 反应 10.0h， 以80%的产率得到3-allylsulfanyl-cyclohexanone
  参考文献：
  名称：

  十二烷基硫酸钠对高效CS键形成胶束溶液（SDS）的母语发音催化作用通过一种无味的硫杂Michael加成反应通过原位的代小号-Alkylisothiouronium盐

  摘要：

  Abstractmagnified imageA pronounced catalytic effect of sodium dodecyl sulfate (SDS) was observed on thein situproduction ofS‐alkylisothiouronium saltsviathe reaction of primary, allyl and benzyl halides with thiourea in SDS droplets .Hydrolysis of the generatedS‐alkylisothiouronium salts in the palisade layer of the droplets produces the corresponding thiol moieties which are immediately added to the electron‐deficient olefins that are present in the micellar core to produce the thia‐Michael adducts. The entire route is an almost odorless process. The yields of the products are good to excellent and the method is applicable to large‐scale operation without any problem.

  DOI：

  10.1002/adsc.200800690

文献信息

• Ceric ammonium nitrate (CAN) as a green and highly efficient promoter for the 1,4-addition of thiols and benzeneselenol to α,β-unsaturated ketones
  作者：Cheng-Ming Chu、Shijay Gao、M.N.V. Sastry、Chun-Wei Kuo、Chaowei Lu、Ju-Tsung Liu、Ching-Fa Yao

  DOI：10.1016/j.tet.2006.12.018

  日期：2007.2

  efficient process for the 1,4-addition of thiols and benzeneselenols to various α,β-unsaturated ketones using a catalytic amount of CAN with excellent product yields is described. This inexpensive, nontoxic, and readily available catalytic ceric(IV) ammonium nitrate system efficiently catalyzes conjugate addition reactions between thiol derivatives and various α,β-unsaturated ketones under solvent-free conditions

  描述了一种温和而有效的方法，该方法使用催化量的CAN以优异的产品收率将硫醇和苯硒酚的1,4-加成成各种α，β-不饱和酮。这种廉价，无毒且容易获得的催化硝酸铈（IV）铵体系可在无溶剂条件下有效催化硫醇衍生物与各种α，β-不饱和酮之间的共轭加成反应。提出了一种可能的机制，即CAN在自由基链加成反应中作为促进剂以及在共轭加成过程中的催化作用。
• Iodine-catalyzed Michael addition of mercaptans to α,β-unsaturated ketones under solvent-free conditions
  作者：Cheng-Ming Chu、Shijay Gao、M.N.V. Sastry、Ching-Fa Yao

  DOI：10.1016/j.tetlet.2005.05.099

  日期：2005.7

  A simple and efficient method for the Michael reaction between various mercaptans and α,β-unsaturated ketones using a catalytic amount of iodine (5 mol %) to generate the 1,4-adduct has been reported. The significant features of the iodine catalyzed Michael addition are (a) operational simplicity, (b) inexpensive reagents, (c) high yields of products, (d) the use of relatively low or nontoxic reagents

  已经报道了一种简单有效的方法，该方法使用催化量的碘（5 mol％）来生成1,4-加合物，从而使各种硫醇与α，β-不饱和酮之间发生迈克尔反应。碘催化的迈克尔加成反应的显着特征是（a）操作简便，（b）廉价的试剂，（c）产品的高收率，（d）使用相对低或无毒的试剂和（e）无溶剂的条件。
• A facile generation of C–S bonds via one-pot, odourless and efficient thia-Michael addition reactions using alkyl, aryl or allyl halides, thiourea and electron-deficient alkenes in wet polyethylene glycol (PEG 200) under mild reaction conditions
  作者：Habib Firouzabadi、Nasser Iranpoor、Mohammad Abbasi

  DOI：10.1016/j.tet.2009.04.079

  日期：2009.7

  An efficient and odourless synthesis of thia-Michael adducts by the reaction of various organic halides (primary, secondary, tertiary, allylic, and benzylic), structurally diverse electron-deficient alkenes (ketones, esters, and acrylonitrile) and thiourea in the presence of sodium carbonate in wet polyethylene glycol (PEG 200) at 30–35 °C has been developed. This protocol is also a highly useful method

  通过在以下条件下，各种有机卤化物（伯，仲，叔，烯丙基和苄基），结构多样的电子缺陷烯烃（酮，酯和丙烯腈）和硫脲的反应，高效而无味地合成噻吩-迈克尔加合物在30–35°C的湿聚乙二醇（PEG 200）中开发了碳酸钠。该协议对于大规模操作也是非常有用的方法。
• Thia-Michael Addition Using Cheap and Odorless <i>S</i>-Alkylisothiouronium Salts as Thiol Equivalents in Water
  作者：Ze-Mei Ge、Run-Tao Li、Yan Zhao、Tie-Ming Cheng

  DOI：10.1055/s-2007-982530

  日期：2007.6

  S-Alkylisothiouronium salt has been found to be a nontoxic, odorless and simply operational alternative of thiol for the thia-Michael addition with electron-deficient olefins. The reactions were carried out under alkaline conditions in water at room temperature within 5-20 minutes to afford the expected products in good to excellent yields.

  S-烷基异硫脲盐被发现是一种无毒、无气味且操作简便的硫醇替代品，可用于与电子缺乏烯烃的硫醇-迈克尔加成反应。反应在室温下的水相碱性条件下进行，时间为5至20分钟，能够以良好到优秀的产率得到预期产品。
• Novel atom-economic reaction: comprehensive utilization of S-alkylisothiouronium salt in the synthesis of thioethers and guanidinium salts
  作者：Pengchao Gao、Penglin Leng、Qi Sun、Xin Wang、Zemei Ge、Runtao Li

  DOI：10.1039/c3ra42503g

  日期：——

  A novel atom-economic three-component one-pot reaction of a primary amine, an S-alkylisothiouronium salt and a Michael receptor is reported, which affords a guanidinium salt and thioether simultaneously. The guanidine moiety is involved in catalyzing the conjugated Michael addition of the mercaptan. The reaction proceeds under ambient conditions using a non-toxic EtOH–H2O mixture as the solvent, and the two products can be very easily purified. Complete atom economy is achieved by fully utilizing the S-alkylisothiouronium salt and converting the previously wasted mercaptan by-product into the valuable thioether.

  报道了一种新颖的原子经济性三组分一锅反应，涉及一种初级胺、一种S-烷基异硫脲盐和一个迈克尔受体，能够同时获得盐基盐和硫醚。胍基部分参与催化与巯基的共轭迈克尔加成。该反应在常温下进行，使用无毒的乙醇-水混合物作为溶剂，两个产物可以非常容易地进行纯化。通过充分利用S-烷基异硫脲盐并将之前浪费的巯基副产物转化为有价值的硫醚，实现了完全的原子经济性。