4-toluenesulfonyl-sulfonyl-18O2 | 116833-54-6

• 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: 4-toluenesulfonyl-sulfonyl-18O2
• 英文别名: tosyl-(18)O2 chloride；p-Toluolsulfonylchlorid-¹⁸O；ClS(18O)2C6H4-4-Me；[ClS(18O)2]-p-toluenesulfonyl chloride；toluene-4-[¹⁸O₂]sulfonyl chloride；4-methylbenzene(18O2)sulfonyl chloride
• CAS: 116833-54-6
• 化学式: C₇H₇ClO₂S
• 分子量: 194.652
• InChiKey: YYROPELSRYBVMQ-IXQOCXOGSA-N

物化性质

• 熔点：
  66.0-67.5 °C(Solvent: Benzene ; Hexane)

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,2,2-三氟-1-(对甲苯基)乙醇 、 4-toluenesulfonyl-sulfonyl-18O2 以59%的产率得到1-(4'-tolyl)-2,2,2-trifluoroethyl tosylate-sulfonyl-18O2
  参考文献：
  名称：

  水溶液中离子对的反应动力学：甲苯磺酸根阴离子与高度不稳定的1-（4-甲基苯基）-2,2,2-三氟乙基碳正离子对的反应性。

  摘要：

  碳桥联和非桥联氧18在50 //中的4-MeC（6）H（4）CH（CF（3））OS（（18）O（2））Tos的溶剂分解和加扰速率常数的总和50（v / v）三氟乙醇/水（k（solv）+ k（iso））= 5.4 x 10（-6）s（-1），比k（solv）= 3.6 x 10（-）大50％ 6）用于磺酸酯的简单溶剂分解反应。这表明溶剂分解的离子对中间体经历显着的内部回流以形成反应物。这些数据给出了碳正离子对内部返回到底物的k（-1）= 1.7 x 10（10）s（-1）的值。该速率常数大于1-（4-甲基苯基）乙基碳正离子和五氟苯甲酸酯阴离子之间的离子对内部返回所报告的k（-1）= 7 x 10（9）s（-1）的值。中性酯（4-MeC（6）H（4）CH（CH（3））O（2）CC（6）F（5））在同一溶剂中。

  DOI：

  10.1002/poc.1642
• 作为产物：
  描述：

  4-甲苯硫酚 在 重氧水 作用下， 生成 4-toluenesulfonyl-sulfonyl-18O2
  参考文献：
  名称：

  杂芳族N-氧化物重排。异喹啉N-氧化物与甲苯磺酰氯反应中1,3-甲苯磺酰氧基迁移的再研究

  摘要：

  异喹啉N-氧化物（2）反应以18 O型富集的对甲苯磺酰氯，得到18 O形标记的4-甲苯磺酰氧基-异喹啉（4），将其评定为通过NMR氧同位素富集和质谱。在桥连氧处30–45％的18 O掺入与高水平的分子内紧密离子对（“滑动”）机理不一致。两种分子内机制的结合可能是有效的。

  DOI：

  10.1016/s0040-4039(00)79299-9

文献信息

• Scrambling of Oxygen-18 during the “Borderline” Solvolysis of 1-(3-Nitrophenyl)ethyl Tosylate
  作者：Yutaka Tsuji、Maria M. Toteva、Tina L. Amyes、John P. Richard

  DOI：10.1021/ol0484409

  日期：2004.9.1

  [reaction: see text] There is substantial isomerization (kiso=0.32 x 10(-3) s(-1)) of 3-NO2C6H4(13)CH(Me)OS(18O)2Tos during solvolysis (ksolv=1.04 x 10(-3) s(-1)) in 50/50 trifluoroethanol/water, even though the estimated lifetime of the putative 1-(3-nitrophenyl)ethyl carbocation intermediate of solvolysis (ca. 10(-13) s(-1)) is too short to allow rearrangement that exchanges the positions of 16O

  [反应：请参见文本]溶剂分解过程中3-NO2C6H4（13）CH（Me）OS（18O）2TOS发生了相当大的异构化（kiso = 0.32 x 10（-3）s（-1））（ksolv = 1.04 x 10 （-3）s（-1））在50/50三氟乙醇/水中，即使溶剂分解的估计的1-（3-硝基苯基）乙基碳正离子中间体的估计寿命（约10（-13）s（-1） ））太短，以至于无法进行重排以交换磺酸盐离去基团上16O和18O的位置。这表明异构化是通过避免形成碳阳离子-阴离子对中间体的机理进行的。
• Study of ion-pair mechanism using oxygen-18 scrambling
  作者：Mizue Fujio、Futoshi Sanematsu、Yuho Tsuno、Masami Sawada、Yoshio Takai

  DOI：10.1016/0040-4039(88)80025-x

  日期：1988.1

  within the sulfonate during acetolysis of18O13C double-labeled β-arylalkyl tosylates was determined by13C NMR tracer analysis based on18O-induced isotope shift. Ion-pair mechanism was discussed in comparison with presently accepted mechanisms.

  通过基于18 O诱导的同位素位移的13 C NMR示踪分析，确定18 O 13 C双标记的β-芳基烷基甲苯磺酸酯的乙酰化过程中磺酸盐内的18 O加扰。与目前公认的机制进行了比较，讨论了离子对机制。
• Ion Pairs in the Solvolysis of Secondary Systems. Salt Effect, 18O-Labeling, and Polarimetric Studies of 1-(4'-Tolyl)-2,2,2-trifluoroethyl Tosylate
  作者：Annette D. Allen、Mizue Fujio、Oswald S. Tee、Thomas T. Tidwell、Yutaka Tsuji、Yuho Tsuno、Ken-ichi Yatsugi

  DOI：10.1021/ja00140a012

  日期：1995.9

  The effect of added trifluoroacetate and triflate salts on the trifluoroacetolysis of 1-(4'-tolyl)-2,2,2-trifluoroethyl tosylate has been studied, including reactions of optically active and O-18-labeled substrates. With no added salt the polarimetric rate constant k(alpha) exceeds the solvolytic rate constant kw by a factor of 14.7, corresponding to a fraction 0.93 of ion pair return with racemization. On the addition of trifluoroacetate or triflate salts there is a large initial curved acceleration of k(UV), characteristic of the special salt effect, with a smaller linear increase in k(alpha). The O-18 scrambling observed in the unsolvolyzed starting material during trifluoroacetolysis corresponds to fractions of return with scrambling of 0.94 and 0.46 at [NaO2CCF3] = 0.0 and 0.201 M, respectively, as compared to fractions of return of 0.93 +/- 0.01 and 0.37 +/- 0.01 determined from k(alpha), showing that scrambling is the same or modestly more efficient than racemization in the ion pairs. The decrease in the k(alpha)/k(UV) ratio appears to level off to values between 1.07 and 1.48 for [salt] between 0.588 and 0.601 M, consistent with the presence of intimate ion pairs that are not captured by salt. The effect of the salts on k(UV) is quantitatively correlated by kinetic expressions derived for the reversible formation of ion pairs which undergo competitive return to starting material and reaction with solvent or salt leading to product. The addition of 0.1 and 0.3 M NaOTs causes common ion rate depression of k(UV) by factors of 13 and 10%, respectively, consistent with the formation and capture of dissociated ions as reactive intermediates in these reactions. The presence of 0.260 MNaOTs causes an increase in k(alpha) of 17%, consistent with a normal salt effect on racemization of an ion pair.
• BINDING, N.;HEESING, A., CHEM. BER., 1983, 116, N 5, 1822-1833
  作者：BINDING, N.、HEESING, A.

  DOI：——

  日期：——
• HEESING, A.;HERDERING, W., CHEM. BER., 1983, 116, N 3, 1081-1096
  作者：HEESING, A.、HERDERING, W.

  DOI：——

  日期：——