(rac)-3,3-dimethyl-2-butyl-2-p-toluenesulfonate | 25966-61-4

• 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: (rac)-3,3-dimethyl-2-butyl-2-p-toluenesulfonate
• 英文别名: 3,3-dimethylbutan-2-yl 4-methylbenzenesulfonate；3,3-Dimethylbutan-2-yl 4-toluenesulfonate；3,3-dimethylbutan-2-yl p-toluenesulfonate；3,3-dimethyl-2-butyl p-toluenesulfonate；pinacoyl p-methylbenzenesulfonate；pinacolyl tosylate；3,3-Dimethylbutan-2-yl 4-methylbenzene-1-sulfonate
• CAS: 25966-61-4
• 化学式: C₁₃H₂₀O₃S
• 分子量: 256.366
• InChiKey: YSSRIVMPJKHNTJ-UHFFFAOYSA-N

物化性质

• 沸点：
  347.5±11.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  (rac)-3,3-dimethyl-2-butyl-2-p-toluenesulfonate 在 2,6-二甲基吡啶 作用下， 以 various solvent(s) 为溶剂， 生成 3,3-二甲基-1-丁烯
  参考文献：
  名称：

  在不受限制的系统中，磺酸酯的溶剂分解中的H /α-CN与H /β-CN比率。氰基部分可对结合的碳阳离子进行共轭稳定化的其他证据

  摘要：

  已经测量了H /α-CN和H /β-CN的比率，以对相对简单的非环状脂族醇的磺酸酯进行溶剂分解。发现β-CN功能比α-CN功能具有更大的延迟速率。

  DOI：

  10.1016/s0040-4039(01)90304-1
• 作为产物：
  描述：

  3,3-二甲基-2-丁醇 、 对甲苯磺酰氯 在 N-甲基咪唑 、 三乙胺 作用下， 以 氯苯 为溶剂， 反应 1.0h， 以90%的产率得到(rac)-3,3-dimethyl-2-butyl-2-p-toluenesulfonate
  参考文献：
  名称：

  使用TsCl-N-甲基咪唑试剂作为交叉偶联伴侣的β-酮酸酯烯醇甲苯磺酸酯的常规，稳健和立体互补制备

  摘要：

  我们已经开发了使用TsCl-N-甲基咪唑（NMI）-Et3N或LiOH进行β-酮酸酯的（E）-或（Z）-立体互补烯醇甲苯磺酸酯化的通用，可靠且经济高效的方法。TsCl与NMI偶联形成高反应性的N-磺酰胺基中间体。使用Ts（Ms）Cl-NMI-Et3N将立体拥挤的仲醇顺利磺酰化。β-酮酸酯使用TsCl-NMI-Et3N进行（E）选择性甲苯磺酰化，使用TsCl-NMI-LiOH进行（Z）选择性甲苯磺酰化（共23个实例；收率60％-99％）。使用烯醇甲苯磺酸盐的立体定向Negishi和Sonogashira偶联成功进行，得到了三取代的α，β-不饱和酯。

  DOI：

  10.1021/ol800480d

文献信息

• Palladium-Catalyzed γ-C(sp³ )−H Arylation of Thiols by a Detachable Protecting/Directing Group
  作者：Likun Jin、Jianchun Wang、Guangbin Dong

  DOI：10.1002/anie.201807760

  日期：2018.9.17

  Reported herein is a palladium‐catalyzed, directed γ‐C(sp3)−H arylation of protected thiols. The key is to utilize Michael acceptors as a dual reagent to install a protecting/directing group on thiols by a thiol‐Michael click reaction, and remove it later under basic conditions. The C−H arylation proceeds with high functional‐group tolerance and the deprotected thiols can be further transformed into

  本文报道了受保护的硫醇的钯催化定向γ-C（sp 3）-H芳基化反应。关键是利用迈克尔受体作为双重试剂，通过巯基-迈克尔点击反应在巯基上安装一个保护/导向基团，然后在碱性条件下将其除去。CH芳基化反应具有较高的官能团耐受性，脱保护的硫醇可进一步转化为其他含硫化合物。这种独特的活化方式可以为未活化位置的硫醇或其他含硫化合物的位点选择性官能化打开大门。
• Kinetic Resolution of Chiral α-Olefins Using Optically Active <i>ansa-</i>Zirconocene Polymerization Catalysts
  作者：Cliff R. Baar、Christopher J. Levy、Endy Y.-J. Min、Lawrence M. Henling、Michael W. Day、John E. Bercaw

  DOI：10.1021/ja040021j

  日期：2004.7.1

  and/or 4-positions. Due to the optically pure nature of these single site catalysts, they effect kinetic resolution of racemic monomers: the polymeric product is enriched with the faster reacting enantiomer, while recovered monomer is enriched with the slower reacting enantiomer. The two components are easily separated. For most olefins surveyed, a partial kinetic resolution was achieved (s = k(faster)/k(slower)

  一系列对映纯的 C1 对称茂金属，[(SiMe2)2[eta5-C5H(CHMe2)2][eta5-C5H2((S)-CHMeCMe3)]]ZrCl2，(S)-2，[(SiMe2)2[ eta5-C5H(CHEt2)2][eta5-C5H2((S)-CHMeCMe3)]]ZrCl2、(S)-6 和 [(SiMe2)2[eta5-C5HCy2][eta5-C5H2((S)-CHMeCMe3) )]]ZrCl2、(S)-7 (Cy = 环己基)、在“上部”环戊二烯基配体上具有对映纯甲基新戊基取代基的二氯化锆，以及非对映异构纯的预催化剂，[(SiMe2)2[eta5-C5H((S) -CHMeCy)(CHMe2)][eta5-C5H3]]ZrCl2、(S)-8a 和 (S)-8b，在“低级”环戊二烯基配体上具有对映纯的 1-环己基乙基取代基，已合成用于手性α-烯烃的聚合。当用甲基铝氧烷活化时，这些茂金属对于在
• PHOTOSENSITIVE COMPOSITION, PATTERN FORMING METHOD USING THE PHOTOSENSITIVE COMPOSITION AND COMPOUND FOR USE IN THE PHOTOSENSITIVE COMPOSITION
  申请人：Wada Kenji

  公开号：US20100233617A1

  公开（公告）日：2010-09-16

  A photosensitive composition includes: (A) a resin containing a repeating unit corresponding to a compound represented by the following formula (I); the resin being capable of producing an acid group upon irradiation with an actinic ray or radiation: Z-A-X—B—R   (I) wherein Z represents a group capable of becoming an acid group resulting from leaving of a cation upon irradiation with an actinic ray or radiation; A represents an alkylene group; X represents a single bond or a heteroatom-containing divalent linking group; B represents a single bond, an oxygen atom or —N(Rx)-; Rx represents a hydrogen atom or a monovalent organic group; R represents a monovalent organic group substituted by Y; when B represents —N(Rx)-, R and Rx may combine with each other to form a ring; and Y represents a polymerizable group.

  一种感光组合物包括：（A）含有与下式（I）所表示的化合物对应的重复单元的树脂；该树脂能够在受到光敏射线或辐射照射后产生酸基团：Z-A-X—B—R   （I）其中Z代表一个能够在受到光敏射线或辐射照射后由阳离子离去而形成酸基团的基团；A代表一个烷基基团；X代表一个单键或含杂原子的二价连接基团；B代表一个单键、一个氧原子或—N（Rx）-；Rx代表一个氢原子或一个一价有机基团；R代表一个通过Y取代的一价有机基团；当B代表—N（Rx）-时，R和Rx可以结合在一起形成一个环；Y代表一个可聚合的基团。
• Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent
  作者：Elsa Deruer、Vincent Hamel、Samuel Blais、Sylvain Canesi

  DOI：10.3762/bjoc.14.101

  日期：——

  sulfonates through hypervalent iodine(III) reagent-mediated oxidation of sodium sulfinates has been developed. This transformation involves trapping reactive sulfonium species using alcohols. With additional optimization of the reaction conditions, the method appears extendable to other nucleophiles such as electron-rich aromatic systems or cyclic ethers through a ring opening pathway.

  已经开发了通过高价碘（III）试剂介导的亚磺酸钠氧化形成磺酸盐的另一种方法。该转化涉及使用醇捕获活性sulf物种。通过进一步优化反应条件，该方法似乎可以通过开环途径扩展到其他亲核试剂，例如富电子芳族体系或环状醚。
• Practical and efficient methods for sulfonylation of alcohols using Ts(Ms)Cl/Et3N and catalytic Me3H·HCl as combined base: Promising alternative to traditional pyridine
  作者：Yoshihiro Yoshida、Yoshiko Sakakura、Naoya Aso、Shin Okada、Yoo Tanabe

  DOI：10.1016/s0040-4020(99)00002-2

  日期：1999.2

  Several alcohols were smoothly and practically tosylated by two methods A and B. Method A uses the TsCl/Et3N (1.5-2.5 equiv)/cat. Me3N . HCl (0.1-1.0 equiv) reagent. Compared with the traditional qr-solvent method, the method A has merits of its much higher reaction rate, operational simplicity, economy in the use of the amine, and circumvention of the undesirable side reaction from R-OTs to R-CL Method B uses TsCl/KOH [or Ca(OH)(2)]/cat. Et3N (0.1 equiv)/cat. Me3N . HCl (0.1 equiv) as the reagent, which will be suited for practical and large scale production for primary alcohols. On both methods A and B, a clear joint action of Et3N and Me3N . HCl catalysts was observed. H-1 NMR measurements support the proposed mechanism of the catalytic cycle. Related methanesulfonylation using Et3N and cat. Me3N . HCl in toluene solvent also successfully proceeded, wherein he clear joint action was also observed. (C) 1999 Elsevier Science Ltd. All rights reserved.