S-(4-chlorophenyl) 3-oxobutanethioate | 65399-20-4

• 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-(4-chlorophenyl) 3-oxobutanethioate
• CAS: 65399-20-4
• 化学式: C₁₀H₉ClO₂S
• 分子量: 228.699
• InChiKey: SCDMVUSHBGNRKV-UHFFFAOYSA-N

物化性质

• 熔点：
  45 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  341.8±27.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  59.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-(4-chlorophenyl) 3-oxobutanethioate 在 三氯化铝 作用下， 以 苯 为溶剂， 反应 5.0h， 以23%的产率得到6-Chloro-4-methylthiochromen-2-one
  参考文献：
  名称：

  从苯硫醇和双烯酮合成 2H-1-Benzothiopyran-2-ones (Thiocoumarins) 和相关化合物

  摘要：

  苯硫醇与双烯酮在 H2SO4 存在下反应形成的产物是 (E)-β-(芳硫基)巴豆酸 (2) 和/或异构 (Z)-β-(芳硫基)巴豆酸，而不是据报道，S-苯基 3-硫代丁烷 (1)。在三乙胺的存在下，由苯硫醇和双烯酮制备化合物 1a-k 作为硫代香豆素的前体。已检查 1 与各种缩合剂的反应以制备 2H-1-benzothiopyran-2-ones（硫香豆素）。发现通过 1 与无水氯化铝反应可以方便地制备 4-甲基（硫代香豆素），产率为 16-48%。当 1 用 PPA 处理时，以 5-66% 的产率优先获得异构体 2-甲基（硫色酮），并且化合物 2 作为中间体被分离出来。

  DOI：

  10.1246/bcsj.53.2046
• 作为产物：
  描述：

  4-氯苯硫酚 在 咪唑 、 magnesium acetate 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.0h， 生成 S-(4-chlorophenyl) 3-oxobutanethioate
  参考文献：
  名称：

  Mg2+-Imidazole-Catalyzed Self-Condensation of Malonyl Thioesters: Getting Tuned for Biomimetic Polyketide Synthesis?

  摘要：

  我们报告说，在 Kobuke 和 Yoshida 最初提出的 "仿生 "条件下（Tetrahedron Lett.）

  DOI：

  10.3390/61100845

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
• Chemoselective Transesterification of β-Keto Esters under Neutral Conditions using NBS as a Catalyst
  作者：B. P. Bandgar、L. S. Uppalla、V. S. Sadavarte

  DOI：10.1055/s-2001-18082

  日期：——

  Facile and selective transesterification of β-keto esters using N-bromosuccinimide (NBS) as an efficient and neutral catalyst is described.

  简便且选择性的β-酮酯转酯化反应，采用N-溴代琥珀酰亚胺（NBS）作为高效中性的催化剂，这一方法已被描述。
• Reactions of diketen with arenethiols: preparation of arylthioisocrotonic acids and S-aryl thioacetoacetate esters
  作者：Norbert F. Yaggi、Kenneth T. Douglas

  DOI：10.1039/c39770000609

  日期：——

  The products formed by reaction of arenethiols with diketen in the presence of sulphuric acid are β-arylthioisocrotonic acids and not, as has been reported, S-aryl thioacetoacetates (which can be prepared by base catalysis).

  在硫酸存在下，芳硫醇与二酮的反应生成的产物是β-芳基硫代异丁烯酸，而不是已报道的S-芳基硫代乙酰乙酸酯（可通过碱催化制备）。
• Selective Catalytic Transesterification, Transthiolesterification, and Protection of Carbonyl Compounds over Natural Kaolinitic Clay
  作者：Datta E. Ponde、Vishnu H. Deshpande、Vivek J. Bulbule、Arumugam Sudalai、Anil S.Gajare

  DOI：10.1021/jo971404l

  日期：1998.2.1

  Transesterification and transthiolesterification of beta-keto esters with variety of alcohols and thiols and selective protection of carbonyl functions with various protecting groups catalyzed by natural kaolinitic clay are described. The clay has been found to be an efficient catalyst in transesterifying long chain alcohols, unsaturated alcohols, and phenols to give their corresponding beta-keto esters in high yields. For the first time, transthiolesterification of beta-keto esters with a variety of thiols has been achieved under catalytic conditions. Clay also catalyzes selective transesterification of beta-keto esters by primary alcohols in the presence of secondary and tertiary alcohols giving corresponding beta-keto esters. A systematic study involving the reactivity of different nucleophiles (alcohols, amines, and thiols) toward beta-keto esters is also described. Sterically hindered carbonyl groups as well as alpha,beta-unsaturated carbonyl groups underwent protection without the deconjugation of the double bond. Chemoselective protection of aldehydes in the presence of ketones has also been achieved over natural kaolinitic clay.
• A Chemoselective Route to β-Enamino Esters and Thioesters
  作者：Dongyue Xin、Kevin Burgess

  DOI：10.1021/ol5005643

  日期：2014.4.18

  Conditions were developed for syntheses of beta-enamino esters, thioesters, and amides. These reactions involve hydroxybenzotriazole derivatives in buffered media. Illustrative syntheses of some heterocyclic systems are given, including some related to protein protein interface mimics.