乙酰硫代乙酸S-叔丁酯 | 15925-47-0

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 乙酰硫代乙酸S-叔丁酯
• 英文名称: S-tert-butyl acetothioacetate
• 英文别名: S-tert-butyl thio acetoacetate；Butanethioic acid, 3-oxo-, S-(1,1-dimethylethyl) ester；S-tert-butyl 3-oxobutanethioate
• CAS: 15925-47-0
• 化学式: C₈H₁₄O₂S
• mdl: MFCD00013237
• 分子量: 174.264
• InChiKey: FXOMETKMHQLOHH-UHFFFAOYSA-N

物化性质

• 沸点：
  95-100 °C0.9 mm Hg(lit.)
• 密度：
  0.994 g/mL at 25 °C(lit.)
• 闪点：
  182 °F
• LogP：
  1.672 (est)
• 稳定性/保质期：
  按规定使用不会分解，避免接触氧化剂、高温、明火及碱性物质。

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  59.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  2930909090
• 储存条件：
  请将药品存放在密闭、阴凉、干燥处。

反应信息

• 作为反应物：
  描述：

  乙酰硫代乙酸S-叔丁酯 在 喹啉 、 sodium hydride 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 17.5h， 生成 ethyl 4-tert-butylsulfanylcarbonyl-5-ethenyl-2,3-dihydropyrrole-1-carboxylate
  参考文献：
  名称：

  Synthesis of the “tricyclic heart” of manzamines

  摘要：

  DOI：

  10.1016/s0040-4039(00)99482-6
• 作为产物：
  描述：

  S-叔丁基硫代乙酸酯 在 乙醚 、 异丙基溴化镁 作用下， 生成 乙酰硫代乙酸S-叔丁酯
  参考文献：
  名称：

  Evidence for low-temperature growth of fayalite and hedenbergite in MacAlpine Hills 88107, an ungrouped carbonaceous chondrite related to the CM-CO clan

  摘要：

  Abstract— The carbonaceous chondrite MacAlpine Hills (MAC) 88107 has bulk composition and mineralogy that are intermediate between those of CO and CM chondrites. This meteorite experienced minor alteration and a low degree of thermal metamorphism (petrologic type 3.1) and escaped post‐accretional brecciation. The alteration resulted in the formation of fayalite (Fa90–100). Al‐free hedenbergite (∼Fs50Wo50), phyllosilicates (saponite‐serpentine intergrowths), magnetite, and Ni‐bearing sulfides (pyrrhotite and pentlandite). Fayalite and hedenbergite typically occur as veins, which start at the opaque nodules in the chondrule peripheries, crosscut fine‐grained rims and either terminate at the boundaries with the neighboring fine‐grained rims or continue as layers between these rims. These observations suggest that fayalite and hedenbergite crystallized after accretion and compaction of the fine‐grained rims. Fayalite also overgrows isolated forsteritic (Fa1–5) and fayalitic (Fa20–40) olivine grains without any evidence for Fe‐Mg interdiffusion; it also replaces massive magnetite‐sulfide grains. The initial 53Mn/55Mn ratio of (1.58 ± 0.26) × 10−6 in the MAC 88107 fayalite corresponds to an age difference between the formation of fayalite and refractory inclusions in Allende of either ∼9 or 18 Ma, depending upon the value of the solar system initial abundance of 53Mn used in age calculations.Formation of secondary fayalite and hedenbergite requires mobilization and transport of Ca, Si, and Fe either through a high‐temperature gaseous phase (Hua and Buseck, 1995) or low‐temperature aqueous solution (Krot et al., 1998a, b). The high‐temperature nebular model for the origin of fayalite (Hua and Buseck, 1995) fails to explain (a) formation of fayalite‐hedenbergite assemblages after accretion of fine‐grained rims that lack any evidence for high‐temperature processing; (b) extreme fractionation of refractory lithophile elements of similar volatility, Ca and Al, in hedenbergite; and (c) absence of Fe‐Mg interdiffusion along fayalite‐forsterite boundaries. We conclude that fayalite and hedenbergite in MAC 88107 formed during late‐stage, low‐temperature (approximately 150–200 °C) aqueous alteration. The data for MAC 88107 extend the evidence for an early onset of aqueous activity on chondrite parent bodies and reinforce the conclusion that liquid water played an important role in the chemical and mineralogical evolution of the first chondritic planetesimals.

  DOI：

  10.1111/j.1945-5100.2000.tb01522.x
• 作为试剂：
  描述：

  乙二醇二甲醚 、 三氟甲磺酸N-吡啶鎓 在 乙酰硫代乙酸S-叔丁酯 、 sodium hydride 作用下， 以5%的产率得到S-tert-Butyl 2-fluoro-2-(2-pyridyl)thioacetate
  参考文献：
  名称：

  A General Synthesis of Quinoline-2,5,8(1H)-triones via Acylation of 2,5-Dimethoxyaniline with S-tert-Butyl Thioacetates by Application of the Knorr Cyclization

  摘要：

  描述了一种高效合成在C3和/或C4位具有烷基取代基的喹啉-2,5,8(1H)-三酮的方法。所采用的反应序列包括2,5-二甲氧基苯胺的Knorr环化，形成5,8-二甲氧基喹啉体系，随后用铈铵硝酸盐进行氧化去甲基化。起始的2,5-二甲氧基苯胺通过选择性酰化实现，根据S-叔丁基乙酰硫代乙酸酯(1)在C2和/或C4位的区域选择性烷基化制备而成。还研究了在1的C2位引入除了烷基以外的电亲体。

  DOI：

  10.1055/s-1998-2014

文献信息

• Leaving group effects in thiolester alkaline hydrolysis. Part 1. A keten-mediated (E1 cB) pathway for basic hydrolysis of S-acetoacetylcoenzyme A and analogues
  作者：Kenneth T. Douglas、Norbert F. Yaggi

  DOI：10.1039/p29800001037

  日期：——

  ylcysteamine follows a kinetic ionisation curve with an inflexion corresponding to the pK of this ester as determined by spectrophotometric and electrometric titrations. The rate constant at high pH was shown to follow a Brønsted relationship with βL.G.–1.13, where βL.G. is the slope of a plot of the logarithm of the rate constant versus the pKa of the conjugate acid of the leaving group. This, and

  在水性介质中，已经研究了一系列离去基团取代的乙酰硫基乙酸酯（CH 3 COCH 2 COSR）的碱性水解。N-乙酰基-S-乙酰乙酰半胱胺的水解遵循动力学电离曲线，其弯曲度对应于该酯的p K（通过分光光度法和静电滴定法测定）。高pH下的速率常数显示出与βL.G呈布朗斯台德关系。–1.13，其中βL.G. 是速率常数对数与p K a的对数图的斜率离去基团的共轭酸的量。这以及速率比较，活化参数和动力学溶剂同位素效应的其他证据表明，E 1 cB水解机理涉及通过烯酮过渡态使酯烯醇盐离子发生单分子塌陷。S-乙酰乙酰辅酶A也通过该机理在碱中水解。通过这种非分子过程，可以直接比较ArS和ArO离开组的驱逐速率。对于p K L.G.的离去组 如图10所示，氧阴离子离去CA。比硫醇盐阴离子快1或2个数量级；对于p K L.G. 6.0，氧气比硫的优势是103 –10 4折。在直接的结构比较中，PhS的离去速度是PhO的32倍。空间释放的在贡献ë
• Versatile synthesis of malonamic acid derivatives from a β-ketothioester
  作者：Pilar López-Alvarado、Carmen Avendaño、J Carlos Menéndez

  DOI：10.1016/s0040-4039(01)00760-2

  日期：2001.7

  An efficient synthetic route is described that allows the preparation under mild conditions of several types of malonamic acid derivatives. The S-tert-butyl acetothioacetate monoanion reacted with aryl or alkyl isocyanates to give β-amidothioesters in one step and 73–87% yield, after spontaneous deacetylation of tricarbonyl intermediates. Treatment of these thioesters with several aliphatic or aromatic

  描述了一种有效的合成路线，该路线允许在温和条件下制备几种类型的丙二酸衍生物。该小号-叔丁基acetothioacetate单价阴离子与芳基或反应异氰酸烷基酯，得到β-amidothioesters在一个步骤和73-87％的产率，三羰基中间体的脱乙酰自发后。在室温下于THF或DME中，在三氟乙酸银的存在下，用几种脂族或芳族醇和胺处理这些硫酯，分别提供了相应的丙二酸酯和丙二酰胺，收率为80-100％。
• Concise Preparation of 1,8-Diazaanthracene-2,7,9,10-Tetraones. Two Alternative Syntheses of the Natural Antifolate Diazaquinomycin A
  作者：José Marı́a Pérez、Pilar López- Alvarado、Eva Pascual-Alfonso、Carmen Avendaño、J. Carlos Menéndez

  DOI：10.1016/s0040-4020(00)00371-9

  日期：2000.6

  aromatization. Double N-oxidation of 1,8-diazaanthraquinones thus obtained is the first example of a double N-oxidation of a diaza heterocycle by UHP in trifluoroacetic acid. Treatment of the crude double N-oxides with tosyl chloride in acetonitrile–water afforded 1,8-diazaanthracene-2,7,9,10-tetraones (including diazaquinomycin A) in 25–40% overall yields. An alternative synthesis of diazaquinomycin A was

  用脲-过氧化氢配合物（UHP）处理带有一个或两个1-二甲氨基-1，4-二氢吡啶部分的化合物导致其有效的芳构化。双Ñ这样得到1,8- diazaanthraquinones氧化作用是双重的第一个例子Ñ在三氟乙酸中二氮杂环的氧化作用由UHP。用甲苯磺酰氯在乙腈-水中处理粗制的双N-氧化物，可提供1,8-二氮杂蒽-2,7,9,10-四酮（包括二氮杂喹诺霉素A），总收率为25-40％。还设计了二氮杂喹诺霉素A的另一种合成方法，其关键步骤是2-甲基-2-己二甲基hydr与3-甲基-4-丙基-2 H之间的杂狄尔斯-阿尔德反应-喹啉-2,5,8-三酮和1,8-二氮杂蒽-2,9,10-三酮衍生物的氧化官能化。
• Three-Component Synthesis of a Library of <i>m</i>-Terphenyl Derivatives with Embedded β-Aminoester Moieties
  作者：Damiano Rocchi、Juan F. González、Jorge Gómez-Carpintero、Víctor González-Ruiz、M. Antonia Martín、Vellaisamy Sridharan、J. Carlos Menéndez

  DOI：10.1021/acscombsci.8b00137

  日期：2018.12.10

  allowed the construction of a large library of highly substituted dihydro-m-terphenyl derivatives containing β-alkylamino- or β-arylamino ester moieties. This process generates three new bonds and one ring and proceeds in high atom economy, having two molecules of water as the only side product. Another domino process, in which the original MCR was telescoped with a subsequent aza Michael/retro-aza Michael

  烷基-或芳基胺之间的三组分反应，β酮酯和查耳酮在回流的含Ce（IV）铵的催化量的乙醇允许高度取代的二氢的大型文库的构建米含β -烷基氨基-三联苯衍生物-或β-芳基氨基酯部分。该过程产生三个新的键和一个环，并以高原子经济性进行，只有两个分子的水是唯一的副产物。另一个多米诺骨牌工艺，其中原始MCR用随后的aza Michael / retro-aza Michael序列进行伸缩，可以一锅制备带有N的化合物库-未取代的β-氨基酯片段。最后，为了扩展这些文库的结构多样性，我们还研究了在二氯二氰基醌存在下我们化合物中心环的芳构化。该反应序列不影响属于氨基组分的立体异构中心的完整性。
• Synthesis of Substituted Alkyl 2H-Pyran-5-carboxylates
  作者：Cornelis M. Moorhoff

  DOI：10.1055/s-1997-1400

  日期：1997.6

  The successful synthesis of substituted alkyl 2H-pyran-5-carboxylates 3 from substituted alkyl 3-oxobutanoates 1 and conjugated aldehydes 2 is described.

  成功合成了取代烷基2H-吡喃-5-羧酸酯3，这一过程是通过取代烷基3-氧代丁酸酯1和共轭醛2反应得到的。

表征谱图