S-phenyl 3-methyl(thiobutanoate) | 93500-17-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚酯
• 英文名称: S-phenyl 3-methyl(thiobutanoate)
• 英文别名: S-phenyl 3-methyl-butanethioate；5-phenyl-3-methylbutanethioate；S-phenyl 3-methylbutanethioate；S-phenyl thio-iso-valerate
• CAS: 93500-17-5
• 化学式: C₁₁H₁₄OS
• 分子量: 194.298
• InChiKey: WZCRVGBJCRPIIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  环己酮 、 S-phenyl 3-methyl(thiobutanoate) 在 lithium diisopropyl amide 作用下， 生成 (+/-)-3-Isopropyl-1-oxaspiro<3.5>nonan-2-one
  参考文献：
  名称：

  A practical and efficient method for the synthesis of .beta.-lactones

  摘要：

  This paper describes a convenient one-step preparation of beta-lactones based on the addition of thiol ester enolates to carbonyl compounds. Under the proper conditions the resulting aldolates undergo spontaneous cyclization to produce beta-lactones in good to excellent yield. The new beta-lactone synthesis provides access to 2-oxetanones with a variety of substituents and substitution patterns. In general, thiol ester enolates combine with carbonyl compounds to form the less sterically crowded beta-lactone diastereomers, and in some cases the reaction proceeds with excellent stereoselectivity. In conjunction with the stereospecific decarboxylation of beta-lactones, this chemistry also provides a very attractive approach to the synthesis of substituted alkenes.

  DOI：

  10.1021/jo00003a047
• 作为产物：
  描述：

  甲氧基甲基苯硫醚 在 aluminum oxide 、 四甲基乙二胺 、 s-butyllithium-TMEDA 、 Me₃SiCl₃ 、 仲丁基锂 、 sodium iodide 作用下， 反应 2.58h， 生成 S-phenyl 3-methyl(thiobutanoate)
  参考文献：
  名称：

  甲氧基苯基硫代三甲基甲硅烷基甲基锂是羰基化合物同源化的便捷试剂

  摘要：

  描述了一种用于羰基化合物转化为乙烯酮-O，S-乙缩醛的简便同源方法。这些中间体很容易转化为烯酮-O-甲硅烷基，S-乙缩醛，硫酯和羧酰胺。

  DOI：

  10.1016/s0040-4039(01)91070-6

文献信息

• S-Acylation of aliphatic and aromatic thiols with carboxylic acids and their esters over solid acid catalysts in the gas phase at temperatures above 200°C
  作者：Sayoko Nagashima、Hitomi Yamazaki、Kentaro Kudo、Satoshi Kamiguchi、Teiji Chihara

  DOI：10.1016/j.apcata.2013.06.011

  日期：2013.8

  Benzenethiol is reacted with acetic acid in a hydrogen stream over [(Mo6Cl8)Cl4(H2O)2]·6H2O. Catalytic activity of the clusters appears above 200 °C, yielding S-phenyl thioacetate. The selectivity is 98% at 300 °C. Niobium, tantalum, and tungsten halide clusters with the same octahedral metal framework also catalyze the reaction. Benzoic acid and aliphatic carboxylic acids afford the corresponding S-phenyl

  苯硫醇用乙酸在氢气流中在[（反应的Mo 6氯8）氯4（H 2 O）2 ]·6H 2 O.催化簇出现在200℃以上的活性，得到小号-苯基硫代乙酸酯。在300°C下的选择性为98％。具有相同八面体金属骨架的铌，钽和卤化钨簇也催化该反应。苯甲酸和脂族羧酸通过与苯硫醇反应得到相应的S-苯基碳硫盐。脂肪族硫醇也被S-酰化以产生相应的S-烷基硫代碳酸盐。当羧酸酯与苯硫醇在[（Nb 6 Cl 12）Cl 2（H 2 O）4 ]·4H 2 O上于450°C应用于反应时，该酯的空间不受阻碍的部分被并入产物中：S选择性地获得-苯基硫代乙酸酯或甲基苯基硫。通过热活化在簇状配合物上形成的布朗斯台德酸位点是催化剂的活性位点。因此，在200°C以上稳定的固体酸（例如二氧化硅-氧化铝，沸石和杂多酸）也会催化这些反应。
• A New and Efficient Esterification Reaction via Mixed Anhydrides by the Promotion of a Catalytic Amount of Lewis Acid
  作者：Mitsutomo Miyashita、Isamu Shiina、So Miyoshi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.66.1516

  日期：1993.5

  In the presence of a catalytic amount of Lewis acid, various carboxylic esters or S-phenyl carbothioates are prepared in excellent yields by the respective reactions of equimolar amounts of silyl carboxylates and alkyl silyl ethers or phenyl silyl sulfides with 4-trifluoromethylbenzoic anhydride.

  在催化量的路易斯酸存在下，通过等摩尔量的甲硅烷基羧酸酯和烷基甲硅烷基醚或苯基甲硅烷基硫化物与4-三氟甲基苯甲酸酐的相应反应，以极好的收率制备各种羧酸酯或S-苯基硫代碳酸酯。
• Preparation of 2-halogeno S-phenyl thioesters from 2-phenylsulphony -2-phenylthiooxiranes. Crystal structures of 2-phenylsulphonyloxiranes
  作者：Cheryl T. Hewkin、Richard F. W. Jackson、William Clegg

  DOI：10.1039/p19910003091

  日期：——

  the preparation of 3,3-dialkyl2-phenylsulphonyl-2-phenylthiooxiranes. The oxiranes 4 react with lithium or magnesium halides to give good yields of 2-halogeno S-phenyl thioesters 5, 6 and 7. 2-lodo S-phenyl thioesters 7 are deiodinated by further treatment with magnesium iodide. In an analogous manner, 2-bromo Smethyl thioesters 15 and a 2-bromo Se-phenyl selenoester 17b are also prepared from the

  1-苯磺酰基-1- phenylthioalkenes 8与高立体选择性为（制备ê在一个单釜法）异构体通过的反应苯基苯硫基甲基砜9与醛，随后消除。用叔丁基氢过氧化物锂对这些烯烃进行亲核环氧化，得到2-苯基磺酰基-2-苯基硫代肟酸酯4，为单一的非对映异构体，而未检测到苯硫基官能团的氧化。还可以通过用丁基锂处理苯磺酰基氧肟酮13，然后再用二苯基二硫化物来制备环氧乙烷，这使得可以制备3,3-二烷基2-苯基磺酰基-2-苯基硫代环氧乙烷。oxiranes 4与锂或卤化镁反应得到的2-卤代良好的收率小号-苯基硫酯5，6和7。通过用碘化镁进一步处理使2-卤代S-苯基硫代酯7脱碘。以类似的方式，也从相应的肟酸酯制备2-溴S甲基硫代酯15和2-溴Se-苯基硒酸酯17b。2-苯基磺酰氧杂环戊烷4b，13e和14b的X射线晶体结构，表明远离磺酰基的C-O键的一致延长，以及与磺酰基相邻的C-O键的显着缩短。
• A New and Efficient Method for the Preparation of<i>S</i>-Phenyl Carbothioates via Mixed Anhydrides Using Active Titanium(IV) Salts
  作者：Teruaki Mukaiyama、Mitsutomo Miyashita、Isamu Shiina

  DOI：10.1246/cl.1992.1747

  日期：1992.9

  In the presence of a catalytic amount of titanium(IV) salt, various S-phenyl carbothioates are prepared in excellent yields by the reaction of nearly equimolar amounts of silyl derivatives of carboxylic acids and benzenethiols with p-trifluoromethylbenzoic anhydride.

  在催化量的钛 (IV) 盐的存在下，通过几乎等摩尔量的羧酸和苯硫醇的甲硅烷基衍生物与对三氟甲基苯甲酸酐反应，可以以极好的收率制备各种 S-苯基硫代碳酸酯。
• Synthesis of Thiol Esters Using PhSZnBr as Sulfenylating Agent: A DFT-Guided Optimization of Reaction Conditions
  作者：Luca Sancineto、Caterina Tidei、Luana Bagnoli、Francesca Marini、Vito Lippolis、Massimiliano Arca、Eder João Lenardão、Claudio Santi

  DOI：10.1002/ejoc.201600366

  日期：2016.6

  The use of PhSZnBr as sulfenylating agent in a solvent-free protocol to prepare thiol esters in excellent yields from acyl chlorides is reported. The products were efficiently obtained by grinding the neat reagents for 5 min in a mortar. DFT calculations showed that the coordination of solvent molecules to the metal center of PhSZnBr results in the destabilization of the frontier MOs, thus reducing

  报道了在无溶剂方案中使用 PhSZnBr 作为亚磺酰化剂从酰氯以优异的产率制备硫羟酸酯。通过在研钵中研磨纯试剂 5 分钟，有效地获得了产品。DFT 计算表明，溶剂分子与 PhSZnBr 金属中心的配位导致前沿 MO 的不稳定，从而与无溶剂条件相比降低了对酰氯的反应性。提出了基于酰氯的羰基与 PhSZnBr 金属中心配位的可能机制。