硫代苯甲酸苄酯 | 13402-51-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 硫代苯甲酸苄酯
• 英文名称: benzyl benzothioate
• 英文别名: S-benzyl benzothioate；S-benzyl thiobenzoate；S-benzyl benzenecarbothioate；Tibenzate
• CAS: 13402-51-2
• 化学式: C₁₄H₁₂OS
• mdl: MFCD00223101
• 分子量: 228.315
• InChiKey: IXTYVGVNWHFZBK-UHFFFAOYSA-N

物化性质

• 熔点：
  39.5°C
• 沸点：
  340.12°C (rough estimate)
• 密度：
  1.1696 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.071
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2930909090
• 储存条件：
  通风、低温、干燥

制备方法与用途

类别：农药
毒性分级：中毒
急性毒性：口服-小鼠 LD50: 1550 毫克/公斤；静脉-小鼠 LD50: 180 毫克/公斤
可燃性危险特性：可燃，燃烧时会产生有毒硫氧化物烟雾
储运特性：通风、低温、干燥
灭火剂：干粉、泡沫、沙土、二氧化碳、雾状水

反应信息

• 作为反应物：
  描述：

  硫代苯甲酸苄酯 在 双(三-o-甲苯磷)钯(0) 作用下， 以 对二甲苯 为溶剂， 以82%的产率得到苄基苯基硫醚
  参考文献：
  名称：

  Palladium- and Nickel-Catalyzed Decarbonylative C–S Coupling to Convert Thioesters to Thioethers

  摘要：

  This Letter describes the development of a catalytic decarbonylative C-S coupling reaction that transforms thioesters into thioethers. Both Pd- and Ni-based catalysts are developed and applied to the construction of diaryl, aryl alkyl, and heterocycle-containing thioethers.

  DOI：

  10.1021/acs.orglett.7b03305
• 作为产物：
  描述：

  苯甲酰溴 在 四丁基溴化铵 sodium hydroxide 作用下， 以 苯 为溶剂， 反应 5.0h， 生成 硫代苯甲酸苄酯
  参考文献：
  名称：

  A Novel Synthesis of ThiocarboxylicS-Esters from 1-(Acylthio)ethaniminium Halides and Alkyl Halides Using Liquid-Liquid Phase-Transfer Catalysis

  摘要：

  S-烷基、S-苄基和S-(2-烯基)硫代羧酸盐可通过硫代乙酰胺与芳基卤化物的酰化反应，并在液-液相转移条件下，将生成的1-(酰硫基)乙亚胺基卤化物与烷基卤化物反应得到，产率良好。

  DOI：

  10.1055/s-1988-27595
• 作为试剂：
  描述：

  2-苯基-1,3-二噻烷 在 正丁基锂 、 硫代苯甲酸苄酯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.03h， 以89%的产率得到1,2-Diphenyl-2-[3-[(2-phenyl-1,3-dithian-2-yl)sulfanyl]propylsulfanyl]ethanone
  参考文献：
  名称：

  Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes

  摘要：

  The autoxidative condensation of 2-aryl-2-lithio-1,3-dithianes is here reported. Treatment of 2-aryl-1,3-dithianes with n-BuLi in the absence of any electrophile leads to condensation of three molecules of 1,3-dithianes and formation of highly functionalized α-thioether ketones orthothioesters in 51-89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and α-thioether ketones in 48-97% yields. The experimental results combined with density functional theory studies support a mechanism triggered by the autoxidation of 2-aryl-2-lithio-1,3-dithianes to yield a highly reactive thioester that undergoes condensation with two other molecules of 2-aryl-2-lithio-1,3-dithiane.

  DOI：

  10.1021/acs.joc.7b02896

文献信息

• Iron-catalyzed thioesterification of methylarenes with thiols in water
  作者：Liang Wang、Jing Cao、Qun Chen、Ming-yang He

  DOI：10.1016/j.tetlet.2014.10.155

  日期：2014.12

  An iron-catalyzed coupling reaction of methylarenes with thiols leading to thioesters has been developed. The reactions were carried out in water with tert-butyl hydroperoxide (TBHP) as the oxidant and polyoxyethanyl α-tocopheryl sebacate (PTS) as the surfactant. The reaction medium is compatible with a series of functional groups and can be reused.

  已经开发了铁催化的甲基芳烃与硫醇的偶联反应，从而生成硫酯。反应在水中以氢过氧化叔丁基（TBHP）为氧化剂，以聚环氧乙烷基α-生育酚癸二酸酯（PTS）为表面活性剂进行。反应介质与一系列官能团相容，可以重复使用。
• α-Methylphenacyl thioesters as convenient thioacid precursors
  作者：Toru Hatanaka、Ryosuke Yuki、Ryota Saito、Kaname Sasaki

  DOI：10.1039/c6ob02256a

  日期：——

  α-Methylphenacyl (Mpa) thioesters are described as precursors of thioacids. Mpa thioesters are accessible via the condensation of carboxylic acids and phenacyl thiol, which is easily prepared without column chromatography. The Mpa thioesters are selectively deprotected by reduction with zinc dust in the presence of conventional thioacid protecting groups. In addition, the Mpa group exhibits orthogonal

  α-甲基苯甲酰基（Mpa）硫酯被描述为硫代酸的前体。Mpa硫酯可通过羧酸和苯甲酰硫醇的缩合反应获得，无需柱色谱即可轻松制备。在常规硫代酸保护基的存在下，通过用锌粉还原将Mpa硫酯选择性地脱保护。另外，Mpa基团与Boc基团表现出正交反应性。预期这些特征将有助于制备复杂的硫代酸，包括肽中的那些。
• Harnessing the catalytic behaviour of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP): An expeditious synthesis of thioesters
  作者：Pallavi Singh、Rama Krishna Peddinti

  DOI：10.1016/j.tetlet.2017.04.004

  日期：2017.5

  promoting the thiocarbonylation of acyl halides and thiols is disclosed. HFIP was recovered with ease and reused for further reactions without any loss of reactivity. Both aryl and alkyl thiols bearing electron-donating and electron-withdrawing groups as well as aryl- and alkyl acyl halides worked well in this reaction. Inexpensive precursors, short reaction time, obviating workup, high atom economy, and

  已经开发出一种新颖，有效，无金属，无碱和无酸的简单方法来构建有用的硫酯。公开了HFIP促进酰基卤和硫醇的硫羰基化的巨大催化潜力。可以轻松回收HFIP，并重新用于进一步反应，而不会损失任何反应性。带有给电子基团和吸电子基团的芳基和烷基硫醇以及芳基和烷基酰基卤在该反应中均表现良好。廉价的前体，短的反应时间，避免后处理，高原子经济性和克级制备是发达的硫醇S-羰基化生态友好路线的重要特征。
• Nanolayered cobalt–molybdenum sulphides (Co–Mo–S) catalyse borrowing hydrogen C–S bond formation reactions of thiols or H₂S with alcohols
  作者：Iván Sorribes、Avelino Corma

  DOI：10.1039/c8sc05782f

  日期：——

  Nanolayered cobalt–molybdenum sulphide (Co–Mo–S) materials have been established as excellent catalysts for C–S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds,

  纳米层硫化钴钼（Co-Mo-S）材料已被确定为 C-S 键构建的优异催化剂。这些催化剂可以用结构多样的硫醇和容易获得的伯醇和仲醇以良好至优异的产率制备各种硫醚。已证明在双键、腈、羧酸酯和卤素等敏感基团存在下的化学选择性。研究还表明，该反应是通过氢自转移（借氢）机制发生的，其中涉及 Co-Mo-S 介导的脱氢和氢化反应。使用这些地球上储量丰富的金属硫化物催化剂，还开发了一种基于醇与硫化氢 (H 2 S) 硫醚化以提供对称硫醚的新型催化方案。
• Ynamide-Mediated Thioester Synthesis
  作者：Xuewei Wang、Yongli Zhao、Jinhua Yang、Yanxi Li、Ying Luo、Mengyao Xu、Junfeng Zhao

  DOI：10.1021/acs.joc.1c01949

  日期：2021.12.17

  A novel ynamide-mediated thioester synthesis strategy was developed. Importantly, no detectable racemization was observed for the thioesterifications of carboxylic acids containing an α-chiral center, enabling it to be useful for the synthesis of peptide thioester, which is the key component of native chemical ligation. It is worth mentioning that amino acid side chain functional groups such as -OH

  开发了一种新的 ynamide 介导的硫酯合成策略。重要的是，对于含有 α-手性中心的羧酸的硫酯化，没有观察到可检测到的外消旋化，这使其可用于合成肽硫酯，这是天然化学连接的关键成分。值得一提的是，-OH和吲哚-NH等氨基酸侧链官能团与反应条件相容，无需对其进行保护。此外，这种方法也适用于硒代酯。