S-2,4,6-trimethylphenyl ethanethioate | 69746-45-8

• 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-2,4,6-trimethylphenyl ethanethioate
• 英文别名: S-(2,4,6-trimethylphenyl) ethanethioate
• CAS: 69746-45-8
• 化学式: C₁₁H₁₄OS
• 分子量: 194.298
• InChiKey: LLBBDGSUIVTIGJ-UHFFFAOYSA-N

物化性质

• 熔点：
  54.5-55.5 °C
• 沸点：
  273.1±39.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  2
• 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：

  S-2,4,6-trimethylphenyl ethanethioate 在 三乙胺 、 甲烷磺酰基叠氮化物 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 水 、 乙腈 为溶剂， 反应 3.17h， 生成 S-2,4,6-trimethylphenyl 2-diazoethanethioate
  参考文献：
  名称：

  铑催化的重氮硫醇酯重整为硫基取代的乙烯酮。在合成环丁酮，环丁烯酮和β-内酰胺中的应用。

  摘要：

  将α-重氮硫醇酯（1）暴露于乙酸乙酸铑（II）的作用会导致非常容易的“ thia-Wolff重排”，产生硫代取代的乙烯酮，与各种酮基亲和剂结合提供α-硫代环丁酮，环丁烯酮和β-内酰胺类。这些环加合物的还原脱硫反应在温和的条件下以极好的收率进行，因此，该序列代表了现有的基于二氯乙烯酮的方法合成四元碳环和杂环的有用新方法。

  DOI：

  10.1021/jo000227c
• 作为产物：
  描述：

  2,4,6-三甲基苯磺酰氯 在 吡啶 、 盐酸 、 硫酸 、 汞 、 锌 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.17h， 生成 S-2,4,6-trimethylphenyl ethanethioate
  参考文献：
  名称：

  铑催化的重氮硫醇酯重整为硫基取代的乙烯酮。在合成环丁酮，环丁烯酮和β-内酰胺中的应用。

  摘要：

  将α-重氮硫醇酯（1）暴露于乙酸乙酸铑（II）的作用会导致非常容易的“ thia-Wolff重排”，产生硫代取代的乙烯酮，与各种酮基亲和剂结合提供α-硫代环丁酮，环丁烯酮和β-内酰胺类。这些环加合物的还原脱硫反应在温和的条件下以极好的收率进行，因此，该序列代表了现有的基于二氯乙烯酮的方法合成四元碳环和杂环的有用新方法。

  DOI：

  10.1021/jo000227c

文献信息

• The reactivity of sulfur nucleophiles towards arenediazonium tetrafluoroborates in aprotic solvents: Synthesis of S-aryl thioacetates
  作者：Giovanni Petrillo、Marino Novi、Giacomo Garbarino、Marcos Filiberti

  DOI：10.1016/s0040-4039(00)80451-7

  日期：1988.1
• Kuliev,A.M. et al., Journal of Organic Chemistry USSR (English Translation), 1978, vol. 14, p. 2237 - 2240
  作者：Kuliev,A.M. et al.

  DOI：——

  日期：——
• Nickel-Mediated Formation of Thio Esters from Bound Methyl, Thiols, and Carbon Monoxide: A Possible Reaction Pathway of Acetyl-Coenzyme A Synthase Activity in Nickel-Containing Carbon Monoxide Dehydrogenases
  作者：Gregory C. Tucci、R. H. Holm

  DOI：10.1021/ja00129a011

  日期：1995.6

  Current mechanistic proposals for the acetyl synthase activity of nickel-containing carbon monoxide dehydrogenases (CH3-THF + CoA . SH --> CoA . SCOCH3 + THF; THF = tetrahydrofolate, CoA . SH = coenzyme A) implicate a Ni catalytic center and the steps [Ni-CH3] --> [Ni-COCH3] --> CoA . SCOCH3. The second step presumably involves attack by the sulfur nucleophile of coenzyme A at the acyl carbon atom in the overall reaction [Ni-II-COCH3] + RS(H) --> RSCOCH(3) + Ni-II (+ H+) + 2e(-). We have previously demonstrated these steps in Ni(II) complexes with physiological-type ligation. In this work, it is shown that the reaction of acyl and thiolate ligands coordinated to Ni(II) affords thioesters in high yield, The complex [Ni(bpy)(CH3)(2)], established to be planar by an X-ray structure determination, reacts with 1 equiv of arenethiol to afford diamagnetic planar [Ni(bpy)(CH3)(SR)] (8) with R = p-C6H4CH3, 2,6-C6H3(CH3)2 (8b), mesityl (8c), 2,4,6-C(6)H(2)iPr(3), and 2,6-C6H3Cl2 (8e) (bpy = 2,2'-bipyridyl). An analogous reaction gives [Ni(bpy)(C2H5)(S-mesityl)] (12) from [Ni(bpy)(C2H5)(2)]. Planar structures of 8c,e were confirmed by X-ray analysis. Complexes 12 and 8 with different R substituents undergo thiolate ligand exchange in THF with K-eq approximate to 1. Reaction of 8e with 1 equiv of carbon monoxide yields the acyl complex [Ni(bpy)(COCH3)(S-2,6-C6H3Cl2)] (9a), whose planar coordination unit was confirmed by X-ray methods. Treatment of the complexes 8 in THF with more than 3 equiv of carbon monoxide yields [Ni(bpy)(CO)(2)] and the thioesters RSCOCH(3) in 96-100% yield in situ. A solution initially containing 8b and 12 gave under the same conditions four thioesters in equal amounts, consistent with four complexes in the equilibrated solution prior to reaction with carbon monoxide. Reaction of 9a in THF with carbon monoxide produced 2,6-dichlorophenyl thioacetate quantitatively, indicating that Ni(II)-acyl-thiolate complexes are intermediates in thioester formation. The overall reaction is [Ni(bpy)(R')(SR)] + 3CO --> RSCOR' + [Ni(bpy)(CO)2] (R' = CH3, C2H5); the two electrons in the generalized reaction are captured by the metal as Ni(0). A related and necessarily intramolecular reaction of [Ni(bpy)(SCH2CH2CH2)] was confirmed and shown to produce gamma-thiobutyrolactone in quantitative yield in situ. Evidence supporting an analogous intramolecular path for reaction systems based on 8 is summarized. This investigation provides the first examples of Ni-mediated acyclic thioester synthesis and demonstrates a possible means of enzymatic thioester formation should coenzyme A(-) and an acetyl group coordinate to the Ni(II) catalytic center.
• PETRILLO, GIOVANNI;NOVI, MARINO;GARBARINO, GIACOMO;FILIBERTI, MARCOS, TETRAHEDRON LETT., 29,(1988) N 33, C. 4185-4188
  作者：PETRILLO, GIOVANNI、NOVI, MARINO、GARBARINO, GIACOMO、FILIBERTI, MARCOS

  DOI：——

  日期：——