hex-2-yn-1-yl 4-methylbenzenesulfonate | 154659-33-3

• 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: hex-2-yn-1-yl 4-methylbenzenesulfonate
• 英文别名: 2-hexyn-1-ol p-toluenesulfonate；2-hexyn-1-yl p-toluenesulfonate；2-hexynyl tosylate；Hex-2-yn-1-yl 4-methylbenzene-1-sulfonate；hex-2-ynyl 4-methylbenzenesulfonate
• CAS: 154659-33-3
• 化学式: C₁₃H₁₆O₃S
• 分子量: 252.334
• InChiKey: HBOJUQANLMUHRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  hex-2-yn-1-yl 4-methylbenzenesulfonate 在 四氟硼酸-二乙醚络合物 、 bis(pyridine)iodonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以85%的产率得到2-iodohex-1-en-3-one
  参考文献：
  名称：

  IPy 2 BF 4促进的炔丙基酯重排直接合成α-碘烯

  摘要：

  描述了从碘鎓离子和炔丙基甲苯磺酸盐或乙酸盐直接获得α-碘酮的方法。双（吡啶）四氟硼酸碘鎓盐（IPy 2 BF 4，Barluenga的试剂）在温和条件下促进这些炔丙醇衍生物的重排。该转化以高产率产生β-未取代的，β-单取代的和β，β-二取代的α-碘烯。以优异的（Z）选择性获得β-取代的α-碘烯。

  DOI：

  10.1021/acs.joc.8b01746
• 作为产物：
  描述：

  2-己炔-1-醇 、 对甲苯磺酰氯 在 potassium carbonate 、 1-十六烷基咪唑 作用下， 以 水 为溶剂， 反应 4.0h， 以79%的产率得到hex-2-yn-1-yl 4-methylbenzenesulfonate
  参考文献：
  名称：

  在无溶剂条件下用于Schotten-Baumann型甲苯磺酸的两亲有机催化剂

  摘要：

  N-十六烷基咪唑催化剂可在含K 2 CO 3的水中有效地进行伯醇与甲苯磺酰氯的甲苯磺酸酯化反应。带有疏水性亚甲基链的催化剂的聚集体用作有机溶剂的替代物。

  DOI：

  10.1021/ol900125y

文献信息

• Nematic tolanes and acetylenes
  作者：Graham W. Skelton、Dewen Dong、Rachel P. Tuffin、Stephen M. Kelly

  DOI：10.1039/b209045g

  日期：2003.2.20

  The first liquid crystals incorporating a non-conjugated carbon–carbon triple bond in the terminal chain to exhibit a nematic phase above the melting point are reported. A variety of compounds incorporating a carbon–carbon triple bond in the terminal chain or between two phenyl rings have been synthesised as part of an investigation of the effects of the shape, conformation and rigidity of the terminal chains of liquid crystals on their mesophase behaviour. A series of related tolanes incorporating an alkenyloxy chain with an additional carbon–carbon double bond or a simple alkoxy chain as a terminal substituent also were prepared for comparison purposes.

  据报道，首次发现了在末端链中包含非共轭碳-碳三键并在熔点以上呈现向列相的液晶。为了研究液晶末端链的形状、构象和刚性对其介晶相行为的影响，合成了一系列在末端链中或两个苯环之间包含碳-碳三键的化合物。此外，还制备了一系列相关的托兰化合物，其在末端取代基为含额外碳-碳双键的烯氧链或简单的烷氧链，用于比较研究。
• Rhodium-catalyzed isomerization of unactivated alkynes to 1,3-dienes
  作者：Ryo Shintani、Wei-Liang Duan、Soyoung Park、Tamio Hayashi

  DOI：10.1039/b605368h

  日期：——

  A rhodium/binap complex has been found to effectively catalyze the isomerization of unactivated internal alkynes to the corresponding 1,3-dienes in the presence of an azomethine imine as the reaction promoter.

  研究发现，在偶氮亚胺作为反应促进剂的情况下，铑/binap 复合物可有效催化未活化的内部炔烃与相应的 1,3-二烯的异构化反应。
• 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.
• Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled “Nanozyme”
  作者：Courtney J. Hastings、Dorothea Fiedler、Robert G. Bergman、Kenneth N. Raymond

  DOI：10.1021/ja8013055

  日期：2008.8.1

  The tetrahedral assembly [Ga4L6](12-) [L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga4L6](12-) assembly, rate accelerations by factors of up to 184 compared with the background reaction rate were observed. After rearrangement, the product iminium ion is released into solution and hydrolyzed, allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a decrease in the entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics: the rate data obeyed the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a nonreactive guest was demonstrated.
• Tanabe Yoo, Yamamoto Hiromi, Yoshida Yoshihiro, Miyawaki Takashi, Utsumi +, Bull. Chem. Soc. Jap., 68 (1995) N 1, S 297-300
  作者：Tanabe Yoo, Yamamoto Hiromi, Yoshida Yoshihiro, Miyawaki Takashi, Utsumi +

  DOI：——

  日期：——