3-methylbutan-2-yl 4-methylbenzenesulfonate | 26466-06-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-methylbutan-2-yl 4-methylbenzenesulfonate
• 英文别名: 3-Methyl-2-butyl-tosylat；3-Methylbutan-2-yl 4-methylbenzene-1-sulfonate
• CAS: 26466-06-8
• 化学式: C₁₂H₁₈O₃S
• 分子量: 242.339
• InChiKey: YFRJBSSHABTVOA-UHFFFAOYSA-N

物化性质

• 沸点：
  338.0±11.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-methylbutan-2-yl 4-methylbenzenesulfonate 在 potassium tert-butylate 作用下， 以 叔丁醇 为溶剂， 生成 3-甲基-1-丁烯
  参考文献：
  名称：

  E2C mechanism in elimination reactions. II. Substituent effects on rates of elimination from acyclic systems

  摘要：

  DOI：

  10.1021/ja00748a014
• 作为产物：
  描述：

  3-甲基-1-丁烯 在 potassium tert-butylate 作用下， 以 叔丁醇 为溶剂， 生成 3-methylbutan-2-yl 4-methylbenzenesulfonate
  参考文献：
  名称：

  E2C mechanism in elimination reactions. II. Substituent effects on rates of elimination from acyclic systems

  摘要：

  DOI：

  10.1021/ja00748a014

文献信息

• REARRANGEMENT STUDIES WITH C¹⁴: VII. THE ACETOLYSIS OF METHYL-C¹⁴-ISOPROPYLCARBINYL <i>p</i>-TOLUENESULPHONATE
  作者：A. J. Finlayson、C. C. Lee

  DOI：10.1139/v59-128

  日期：1959.5.1

  Acetolysis of methyl-C¹⁴-isopropylcarbinyl p-toluenesulphonate (I) at reflux temperature gave a mixture of 2-methyl-2-butene (II), 2-methyl-1-butene (III), and 3-methyl-1-butene (IV) with no isolatable quantity of substitution product. The relative amounts of olefins II, III, and IV were measured by gas–liquid chromatography to be 80%, 18%, and 2%, respectively, and these were substantially verified by estimations with the isotope dilution technique. When the acetolysis was carried out at 50 °C, besides olefins II, III, and IV, present in relative amounts of 83%, 16%, and 1%, respectively, as determined by gas–liquid chromatography, a small quantity of substitution product, t-amyl acetate (V), was obtained. Under the conditions of acetolysis at reflux temperature, however, V was found to decompose to olefins II and III. Degradation of the olefinic products of acetolysis gave, among other compounds, radioactive acetone. Since acetone was derived from the chief product, II, its activity could be attributed to an isotope position rearrangement resulting from a 1,2-methide shift as one of the processes that gave rise to olefin II. This rearrangement amounted to about 2.5% and 0.9%, respectively, in olefin II from acetolysis at reflux temperature and at 50 °C. Considering all these results, it may be concluded that both substitution and elimination reactions could take place during acetolysis of I. The substitution reaction proceeded with neighboring hydrogen participation to yield t-amyl acetate, which would decompose to olefins II and III at reflux temperature under the acetolysis conditions. In the E₁ reaction during acetolysis of I, processes involving no neighboring group participation to give olefins II and IV, with neighboring hydrogen participation to give olefins II and III, and with neighboring methyl participation to give isotopically rearranged olefins II and IV, all occurred, the process with neighboring hydrogen participation being predominant.

  在回流温度下，对甲基-C¹⁴-异丙基卡比尼基对甲苯磺酸酯（I）进行乙酰解反应，得到2-甲基-2-丁烯（II）、2-甲基-1-丁烯（III）和3-甲基-1-丁烯（IV）的混合物，没有可分离的取代产物。通过气液色谱测量，发现II、III和IV的烯烃相对量分别为80％、18％和2％，这些结果也通过同位素稀释技术进行了验证。当在50°C进行乙酰解反应时，除了II、III和IV的烯烃相对量为83％、16％和1％，通过气液色谱测定，还得到了少量取代产物对叔戊酸乙酯（V）。然而，在回流温度下的乙酰解反应条件下，发现V会分解为II和III的烯烃。乙酰解反应产物的降解产物中包括放射性丙酮。由于丙酮来自主要产物II，其活性可归因于1,2-甲基转移引起的同位素位置重排，导致形成烯烃II。这种重排分别约占回流温度和50°C下乙酰解反应中II的2.5％和0.9％。综合所有结果，可以得出结论，在I的乙酰解反应中，取代和消除反应都可能发生。取代反应通过邻位氢参与形成对叔戊酸乙酯，在回流温度下的乙酰解反应条件下，对叔戊酸乙酯会分解为II和III的烯烃。在I的乙酰解反应中，E₁反应包括不涉及邻位基团参与形成II和IV的烯烃，涉及邻位氢参与形成II和III的烯烃，涉及邻位甲基参与形成同位素重排的II和IV的烯烃，所有这些过程都发生了，其中涉及邻位氢参与的过程占主导地位。
• 含有哌嗪酮的喹唑啉酮类PARP-1/2抑制剂 及其制备方法、药物组合物和用途
  申请人：中国医学科学院药物研究所

  公开号：CN107098886B

  公开（公告）日：2020-07-14

  本发明公开了一类新的含有哌嗪酮的喹唑啉‑2,4(1H,3H)‑二酮类PARP‑1/2抑制剂、及其制法和药物组合物与用途。具体而言，本发明涉及通式I所示的含有哌嗪酮的喹唑啉‑2,4(1H,3H)‑二酮类衍生物及其可药用盐，及其制备方法，含有一个或多个该类化合物的组合物，和该类化合物在制备、预防和/或治疗与PARP‑1/2相关的疾病药物中的用途。
• Solvent reorganization for hydrolysis with hydrogen participation
  作者：Y. Inomoto、R. E. Robertson、G. Sarkis

  DOI：10.1139/v69-760

  日期：1969.12.15

  A study of the rates of hydrolysis of 3-Me-2-butyl bromide and methanesulfonate in water leads to values of ΔC_p^≠ of −80 and −40 cal deg⁻¹ mole⁻¹, respectively. The product was about 85–95 % t-pentanol, the remainder being olefin. The value of ΔC_p^≠ for the solvolysis of the methanesulfonate in D₂O was −44 cal deg⁻¹ mole⁻¹. The kinetic solvent isotope effect (k.s.i.e.) for the latter was unusually low (k.s.i.e. = 1.047 at 5 °C and 1.025 at 25 °C). Deuteration at C-3 led to a reduction in the rate of hydrolysis by a factor of about 2.25. This is consistent with an activation process involving "hydrogen participation" as previously reported by Winstein and Takahashi for solvolysis of the corresponding tosylate in acetic acid. In contrast to the latter work, the reaction in water appears to be uncomplicated.

  一项关于3-Me-2-butyl溴化物和甲烷磺酸盐在水中水解速率的研究表明，它们的ΔCp≠值分别为-80和-40 cal deg^-1 mole^-1。产物约为85-95%的t-戊醇，其余为烯烃。在D2O中，甲烷磺酸盐的溶剂解值ΔCp≠为-44 cal deg^-1 mole^-1。后者的动力学溶剂同位素效应（k.s.i.e.）异常地低（k.s.i.e.=1.047（5℃）和1.025（25℃））。在C-3处的氘代导致水解速率降低约2.25倍。这与Winstein和Takahashi之前在乙酸中对应对磺酸酯的溶剂解作用所报道的“氢参与”激活过程一致。与后者的研究相比，水中的反应似乎不那么复杂。
• Indole Sulfonamide Modulators of Progesterone Receptors
  申请人：Bleisch Thomas John

  公开号：US20090069400A1

  公开（公告）日：2009-03-12

  Compounds of Formula (I), wherein n is 1 or 2, and R1, R2, R3, R4, R5, R6, R7, and R8 are as defined herein, their preparation, pharmaceutical compositions, and methods of use are disclosed.

  本发明揭示了化学式（I）的化合物，其中n为1或2，R1、R2、R3、R4、R5、R6、R7和R8如本文所定义，其制备方法、药物组合物及使用方法。
• Selective, Transition Metal‐free 1,2‐Diboration of Alkyl Halides, Tosylates, and Alcohols
  作者：Mingming Huang、Jiefeng Hu、Shasha Shi、Alexandra Friedrich、Johannes Krebs、Stephen A. Westcott、Udo Radius、Todd B. Marder

  DOI：10.1002/chem.202200480

  日期：2022.4.27

  simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of readily available secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols was developed. The use of KI and DMA is critical to the methodology, which circumvents the regio- and diastereoselectivity problems. The transformation showed a broad substrate scope (75 examples)

  开发了一种无过渡金属、简单且有效的策略，通过对容易获得的仲和叔烷基卤化物（Br、Cl、I）、甲苯磺酸酯和醇进行区域和非对映选择性二硼化来获得烷基 1,2-双（硼酸酯） 。 KI 和 DMA 的使用对该方法至关重要，它可以避免区域选择性和非对映选择性问题。该转化显示了广泛的底物范围（75 个实例）以及天然产物后期修饰的实用性。